sº º º ---
tº

ź…---***#:：::：：：
#！############№Ė
§
\!
l
f
Eiții IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIN§§§§
-• …-，\，^\$$
º
º:
lººt
- Tritºriºſimilliſt:
Fº, it ()i&
w”
-
T
[]
Q
[]
D
€.
O
[]
[]
[]
0
E
!
[]
Č
C
[]
ſ.
[]
[]
[]
ſ
[]
C
{
Œ
C
Đ
D.
[]
ſ.
|
hiſtºfºrº
ae
Sſſſſſſſſſſſſſſſ IIIIIIIIIIIIIIIIIIIIII
º ſº º ºſº ſº º sººººººººº.
ſ',
Ķī£T£
lº


PO IS O N S :
TEIF. IR E FIFE CTS AND DETECTION.
EY THE SAME AUTHOR.
FIFTH EDITION, Thoroughly Revised, Greatly Enlarged and Re-written.
With additional Tables, Plates, and Illustrations. 21S.
FO O D S :
THEIR COMPOSITION AND ANALYSIS,
By A. WYNTER BLYTH, M.R.C.S., F.I.C., F.C.S.,
Barrister-at-Law, Public Analyst for the County of Devon, and Medical Officer of Health
for St Marylebone,
AND M. WYNTER BLYTH, B.A., B.Sc., F.C.S.
“Simply INDISPENSABLE in the Analyst’s laboratory.”—The Lancet.
“A new edition of Mr Wynter Blyth's Standard work, ENRICHED WITH ALL THE RECENT
DISCOVRRIES AND IMPROVEMENTS, will be accepted as a boon.”—Chemical News.
OTHE F STANDARD VVORFCS.
Crown 8vo, Handsome Cloth. With Diagrams. 7s. 6d. net.
TO XIN E S AND ANT ITO XIN E S.
By CARL OPPENHEIMER, PH.D., M.D.,
Of the Physiological Institute at Erlangen.
TRANSI/ATED FROM THE GERMAN BY
C. AINSWORTH MITCHELL, B.A., B.Sc., F.L.C., F.C.S.
With Notes, and Additions by the Author since the publication of the German Edition.
Deals with the theory of Bacterial and other Toacimes, such as Tuberculin, Ricim, Cobra Poison, etc.
THIRD EDITION, Thoroughly Revised and Enlarged. 21s.
FORENSIC MEDICINE AND TOXICOLOGY.
By J. DIXON MANN, M.D., F.R.C.P.,
Physician to the Salford Royal Infirmary ; Professor of Medical Jurisprudence and
Toxicology, Owens College, Manchester; Examiner in Forensic Medicine,
London University, and Victoria University, Manchester.
‘‘We consider this work to be one of the BEST TEXT-BOOKS ON FORENSIO MEDIOINE AND
TOXICOLOGY NOW IN PRINT, and we cordially recommend it to students who are preparing for
their examinations, and also to practitioners who may be, in the course of their professional
work, called upon at any time to assist in the investigations of a medico-legal case.”—The Lancet
With Illustrations. Handsome Cloth. 8s. 6d. net.
THE PHYSIOLOGY AND PATHOLOGY OF
THE URINE.
By J. DIXON MANN, M.D., F.R.C.P.
“Dr DIXON MANN is to be congratulated on having produced a work which cannot fail to be
of inestimable value alike to medical men and students, and which is in every respect worthy
of his high reputation.”—Brit. Med. Journ.
In Pocket size. Leather. With Frontispiece. 8s. 6d.
A HANDBOOK OF
MEDICAL JURISPRUDENCE AND TOXICOLOGY,
FOR THE USE OF STUDENTS AND PRACTITIONERS.
By WILLIAM A, BREND, M.A.CANTAB., M.B., B.Sc.LoND,
Late Scholar of Sidney Sussex College, Cambridge, of the Inner Temple, Barrister-at-Law.
“We recommend it as a trustworthy work . . . . one specially suitable for students and
practitioners of medicine . . . . the necessary facts only are stated.”—Lancet.
LONDON : CHARLES GRIFFIN & CO., LTD., ExETER ST., STRAND.
*… -
** **** 3:
# , ºf º
: Լ. **
sº, ºr .*& § .#
*
*




PO IS O N S :
THEIR EFFECTS AND DETECTION.
BY
ALEXANDER WYNTER BLYTH,
M.R.C.S., F.I.C., F.C.S., &c.,
BARRISTER-AT-LAW; PUBLIC ANALYST FOR THE COUNTY OF DEVON ; MEDICAL OFFICER OF HEALTH
AND PUBLIC ANALYST FOR THE BOROUGH OF ST. MARYLEBONE :
AND
MEREDITH WYNTER BLYTH,
B.A. (Cantab)., B.Sc. (Lond.), F.I.C., F.C.S., &c.,
PUBLIC ANALYST FOR THE BOROUGH OF BRIGHTON, AND ALSO FOR THE
BOROUGH OF EASTBOURNE.
FOURTH EDITION, THOROUGHLY REVISED, ENLARGED, AND REWRITTEN,
§ith Čables amb #Ilustrations,
L ON D O N :
CHARLES GRIFFIN AND COMPANY, LIMITED,
EXETER STREET, STRAND.
1906.
[All Rights Reserved.]
D. VAN NOSTRAND COMPANY
N H.W YORK

PREFACE TO THE FOURTH EDITION.
BY expansion in some directions, condensation in others, the
present edition contains more information, without material
enlargement of the bulk of the volume, than the edition which
immediately preceded it. -
A large portion has been rewritten, effete processes and
unreliable reactions have been omitted. Newly discovered
poisons and injurious substances which of recent years have
come into popular use, such as sulphonal and trional, have been
added. Space has been found for a condensed account of recent
ideas as to the constitution of the vegetable poisons; and we have
felt that no work on toxicology would be complete without some
mention of the most powerful of all modern poisons, i.e. epinephrin.
Special attention has naturally been given to arsenic, and to
the delicate and reliable methods which are now available for
its separation, identification, and estimation.
The authors hope that their labours have been so far success-
ful that the new edition will retain its place as a recognised
standard work on toxicology.
3 UPPER GLoUCESTER PLACE, W.,
September 1906.
268580
CONTENTS.
PART I. —INTRODUCTORY.
I. THE OLD POISON-LORE.
Section
1. Earliest Period—Myths as to Poison,
2. Egyptian Knowledge of Poison, e e e - e e
3. The Use of Poison by the Greeks and Romans—Nicander, Apollo-
dorus, Dioscorides, . º o * º g sº e *
4. Asiatic Knowledge of Poisons, ->
5. Hebrew Knowledge of Poisons, s º g º º s -
6. The part Poison has played in History—The Death of Britannicus—
A Commission of Murder—Royal Poisoners, º º º -
7. The Criminal Schools of Italy and Venice–Toffana—St. Croix—The
10.
11.
12.
13.
14.
16.
17.
18.
19.
Marchioness de Brinvilliers,
II. GROWTH AND DEVELOPMENT OF THE MODERN METHODS OF
CHEMICALLY DETECTING POISONS.
. The growth of Pathology, tº o * e ſº ar e -
. The Treatise of Barthélémy d’Anglais-—Porta's Work—Robert Boyle
—Richard Mead—Scheele and the Chemists of the Eighteenth
Century, . e e - o - º º º tº
Proust's Discovery of Arseniuretted Hydrogen—Marsh's Test,
Matthieu Joseph Bonaventura Orfila º tº - g
The Discovery of the Alkaloids e e e & e e -
Bibliography of the Chief Works on Toxicology (Nineteenth
Century), e º - º º > º º * º
PART II.
I, DEFINITION OF POISON.
Legal Definitions of Poison, . e
. The German and French Laws as to Poison,
Scientific Definition of a Poison, .
II. CLASSIFICATION OF POISONS.
General Classification of Poisons according to Symptoms,
Kobert's Classification, . - e º e e -
Classification followed in this Work, tº e
Vll
13, 14
14, 15
15, 16
16
16–19
20, 21
21, 22
22, 23
23, 24
24, 25
25–29
viii
CONTENTS,
III, STATISTICS.
Section
20.
21.
22.
intº causing Local Wariation in the Proportion of Death from
OlSOn, . tº º - e º e
English Statistics for the Ten Years ending 1903,
Relative Fatality of certain Poisons, º
Page
29
29–31
32
IV. THE CONNECTION BETWEEN TOXIC ACTION AND CHEMICAL COMPOSITION.
23.
24.
28.
29.
30.
31.
32.
33.
34.
35.
36.
Advance in Knowledge of the Relationship between Chemical and
Physiological Properties—The Influence of Hydroxyl—Bamberger's
Observations, . e - e e - º º e e
Physiological Effect of Replacing Hydrogen by Alkyls in Aromatic
Bodies—Overton's Researches—H. Meyer's Views on the Influence
of the Solubility of Narcotic Substances in the Fat of Living
Protoplasm, te º & e º g e & '•
. The Influence of CO Groups,
• Oscar Loew's Generalisations, . e º º • e -
. Michet's Experiments on the Comparative Toxicity of Poisonous
Metals on Fish, . º e
(1) Action of Poisons on the Red Blood Corpuscles; (2) on Infusoria;
(3) on Cephalopoda; (4) on Insects, . o e º - is
The Effect of Poisons on the Heart of Cold-blooded Animals—
Willliams' Apparatus—Jacobi's Apparatus, e º º e
The Effect of Poisons on the Iris—Toxic Myosis—Toxic Mydriasis, .
VI. GENERAL METHOD OF PROCEDURE IN SEARCHING FOR POISON.
Preliminary Examination—Distillation of Wolatile Matters in a
Vacuum—Drying the Sample—Treatment by Wolatile Solvents, .
Methods of Destroying Organic Matter when Searching for Arsenic—
Destruction by Heat—the Methods of G. Bertrand, Werryken,
Woehler and Siebold—Basic Method—J. Ogier's Method—
A. Williers' Method—Process of Armand Gautier—Pagel's Process
—Subsequent Treatment of Resulting Liquid by SH2 and then by
Ammonium Sulphide, e º º º o s - e
VII. THE SPECTROSCOPE AS AN AID TO THE IDENTIFICATION OF
("ERTAIN POISONS.
Use of the Micro-Spectroscope—Oscar Brasch's Observations on the
Absorption Bands produced in certain Tests,
Eacamination of Blood or of Blood-Stains.
General Procedure—Dragendorff’s Method—Solution of Blood by
Riegler's Reagent, . º º e e e e º º
Spectroscopic Appearances of Blood — Sulphaemoglobin — Carbon-
monoxide Haemoglobin — Characteristics of Carbon-monoxide
Blood—Preparation of Haematin Crystals—Guaiacum Test, . ©
Measurement of the Blood Corpuscles—Ratio of Potash to Soda in
Blood of various Animals—Biological Test for Human Blood,
32–34
34–39
39–42
42
V. LIFE TESTS : THE ACTION OF POISONS ON THE LOWER FORMS OF LIFE.
42–45
45–48
48
48–51
51–56
56–59
59, 60
60–65
65–67
CONTENTS.
PART III.-POISONOUS GASES: CARBON MONOXIDE—CHLORINE–
HYDRIC SULPHIDE.
I. CARBON MONOXIDE.
Section
37.
38.
39.
40,
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
Properties of Carbon Monoxide, . º . . .
Symptoms—Acute Poisoning—Chronic Poisoning, .
Action of the Gas on the Blood and Nervous System,
Post-mortem. Appearances, . g tº sº ge & ſº e
Mass Poisonings by Carbon Monoxide—The Leeds Cases—The Dar-
laston Cases, & tº º † ſº e g * tº
Penetration of Carbon Monoxide, . e g ſº g º tº
Detection of Carbon Monoxide—The Cuprous Chloride Reaction—
Hempel's Biological Test—The Iodine Pentoxide Method, .
II. CHLoRINE.
Preparation of Chlorine–Accidents in the Manufacture of Chlorine,
Effects and Post-mortem Appearances,
Detection of Free Chlorine, *
III. HYDRIC SULPHIDE.
General Properties, * g tº ſº gº * * &
Effects—the Hebburn-on-Tyne Cases—The Cleator Moor Cases,
Post-mortem. Appearances—Chronic Poisoning, tº g
Detection, te ę º e º
PART IV.-ACIDS AND ALKALIES.
Page
68, 69
69, 70
70, 71
71, 72
72–74
74, 75
75, 76
76, 77
77,78
78
78, 79
79, 80
80
SULPHURIC ACID—HYDROCHLoRIC ACID—NITRIC ACID—ACETIC ACID–AMMONIA
51.
52.
53.
54.
55.
56. iº & *
58. Local Action of Sulphuric Acid, .
59.
60.
61.
62.
63.
I. SULPHURIC ACID.
Commercial Forms of Sulphuric Acid—General Properties,
Sulphur Trioxide or Sulphuric Anhydride, . * º
Occurrence of Free Sulphuric Acid in Nature, .
Statistics, * tº tº * e g *
Accidental, Suicidal, and Criminal Poisoning,
Fatal Dose, . & . .
Action of Sulphuric Acid on Vegetation, on Wood, on Paper, on
Carpets, on Clothing, and on Iron—Caution in judging of Spots,
Symptoms—External Effects—Internal Effects, e º &
Treatment of Acute Poisoning by the Mineral Acids, e *
Post-mortem Appearances—Oscar Wyss' Case–Fraenkel and Reiche's
Observations on the Effects of the Acid on the Kidney, &
Pathological Preparations illustrative of Fatal Sulphuric Acid
Poisoning in the various London Museums, & tº e *
Chronic Poisoning by Sulphuric Acid, ge
—PotASH-SoDA—NEUTRAL SODIUM, PotASSIUM, AND AMMONIUM SALTS.
81, 82
82
82
82, 83
83, 84
84, 85
85, 86
86,87
87–89
89
90, 91
91, 92
92
64.
65.
66.
67.
Detection and Estimation of Free Sulphuric Acid.
Quinine Method—Solution of Free Acid by Alcohol—Hilger's Test, .
Sulphates in the Urine — Changes in the Urine produced by
Sulphuric Acid, . * wº * * ę tº * * te
Effects of the Acid on the Blood, . tº
Amount of Ordinary Sulphates in Food, .
93, 94
94-96
96, 97
CONTENTS.
II. HYDROCHLORIC ACID.
Section
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
.89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
General Properties—Uses, º e º ©
Statistics of Poisoning by Hydrochloric Acid, .
Fatal Dose, º e º - te o e e º e
Amount of Free Acid in the Gastric Juice—Researches of Lehmann,
Bernard, Schmidt and others, . º º º e &
Influence of Hydrochloric Acid on Vegetation,
Action upon Cloth and Manufactured Articles,
Poisonous Effects of Hydrochloric Acid Gas, . - º e e
Bºº of the Liquid Acid—A. Lesser's Experiments—Illustrative
ases, e e e e º º º º º e e
Post-mortem Appearances—Museum Preparations, .
Detection and Estimation of Free Hydrochloric Acid.
(1) Detection—Günzburg's Test—Benzo-Purpurin—The Process of
A. Williers and Favolle ; (2) Estimation—Method of Sjokvist—
Braun's Method, e te º e e e
Identification of Hydrochloric Acid Stains on Fabrics,
III, NITRIC ACID.
General Properties and Commercial Varieties, .
Use in the Arts, . tº © º
Statistics of Poisoning by Nitric Acid,
Fatal Dose, wº º & º -
Action of Nitric Acid on Vegetation, - - - º • •
Nitric Acid Vapour—Eulenberg's and Lassar's Researches—Illustra-
tive Cases, . e ſº G . o
Effects of Liquid Nitric Acid, .
Local Action, . e -
Symptoms, º - - - - º w
Tost-mortem Appearances—Museum Preparations, .
Detection and Estimation of Nitric Acid,
IV. ACETIC ACID.
Statistics—Symptoms—Detection, .
V. AMMONIA.
Properties, º © º º º e
Uses—Officinal and Commercial Preparations, .
Statistics, e o º © o - e
Poisoning by Ammonia Vapour,
Symptoms, . º º & º
Chronic Effects of the Gas, . º e e
Ammonia in Solution—Action on Plants, º & º e g
Action on Human Beings and Animal Life—Effects on the Blood–
Symptoms, . º dº © © º e º s *
Post-mortem Appearances—Museum Preparations, .
Separation of Ammonia, . º o º º º
Estimation, o
VI. CAUSTIC POTASH AND SODA.
Properties of Potash, tº
Page
97–99
99
99
99, 100
100, 101
101
101, 102
102, 103
103, 104
105–107
108
109
109
109
109, 110
110
110, 111
111, 112
112
112, 113
113–115
115, 116
116
116, 117
117, 118
118 -
118
118, 119
119
119
119–121
121
121, 122
122
122
Pharmaceutical Preparations, . & º e º
Carbonate of Potash, ſe e e º o tº º
Bicarbonate of Potash, . º © © º e º tº ſº
Caustic Soda—Sodium Hydrate,
122, 123
123
123
123
CONTENT8.
xi
Section
107. Sodae Carbonas—Carbonate of Soda,
108. Bicarbonate of Soda, tº O º
109. Statistics, O e tº º º
110. Effects on Animal and Vegetable Life,
111. Local Effects, . e - º
112. Symptoms, . e de º º & º º
113. Post-mortem. Appearances—Museum Preparations, .
114. Chemical Analysis, . e e e º º
115. Estimation of the Fixed Alkalies,
VII. NEUTRAL SODIUM, POTASSIUM, AND AMMONIUM SALTs.
116. General Poisonous Characters of Large Doses of Salts of the Alkalies, .
117. Effects of Sodium Salts, . - º e º º º º º
118. Effects of Potassium Salts,
119. Action on the Frog's Heart, . e
120. Action on Warm-blooded Animals, .
121. Elimination, . º g - º
122. Nitrate of Potash—General Properties,
123. Statistics of “Nitre’” Poisoning, -
124. Uses of “Nitre’ in the Arts, . e e - s e - e
125. Action of Nitrates of Sodium and Potassium—Poisonous Action of
Sodic Nitrite, . tº º º e ©
126. Post-mortem. Appearances from Potassic Nitrate,
127. Potassic Chlorate—General Properties, -
128. Uses, . . . o º o e
129. Poisonous Properties g º e º - e e - º
130. Experiments on Animals—Effects on Blood–Effects on the Kidney,
131. Effects on Man—Illustrative Cases, . e º * º - &
132. Nephritis from Chlorate Poisoning, .
133. Elimination, . º º º º
134. Essential Action of Potassic Chlorate,
Detection and Estimation of Potassic Chlorate.
135. Separation from Organic Fluids—Tests—Treatment of Urine for
Chlorate, & º º g º º & & 4. de
Toacicological Detection of Alkali Salts.
136. Separation of Potassium, Sodium, and Ammonium Salts from the
Contents of the Stomach, © e & &
Page
}23
123, 124
124
124
124, 125
125
125, 126
126, 127
127

127, 128
128
128
128
128
128
129
129
129
129
130
130
130
130
130, 131
131
131, 132
132
132
132, 133
133, 134
PART W.-MORE OR LESS WOLATILE POISONOUS SUBSTANCES CAP-
ABLE OF BEING SEPARATED BY DISTILLATION FROM NEUTRAL
OR ACID LIQUIDS.
HYDROCARBONS – CAMPHOR-ALCOHOL — AMYL NITRITE– ETHER—CHLOROFoRM
AND OTHER ANAESTHETICS—CHLORAL–CARBON DISULPHIDE—CARBOLIC ACID
—NITRO-BENZENE–PRUSSIC ACID—PHOSPHORUs.
I, HYDROOARBONS.
1. Petrolewm.
137. Petroleum : General Properties,
138. Cymogene, . e º º
139. Rhigolene, . e º º
140. Gasolene, e º e ©
135
135
135
I35
xii
CONTENTS.
Section
141.
142.
143.
144.
145.
146.
147.
148.
149.
150.
Benzoline-Petroleum Spirit—Petrol—Varieties of Naphtha and dis-
tinguishing Tests, wº & © Q tº º tº tº
Paraffin Oil, T. e
Effects of Petroleum
Cases of Poisoning, º e o e
Separation and Identification of Petroleum,
2. Coal-Tar—Naphtha-Benzene.
General Properties, e º
Case of Poisoning by the Liquid,
Eulenberg's Experiments on the Vapour, e e e
Detection and Separation of Benzene—Purification—Conversion into
Nitro-Benzene—Conversion into Aniline,
3. Terpenes—Essential Oils—Oil of Turpentine.
Terpenes–Cedrenes—Colophenes,
Page
135, 136
136
137
137
137
138
138
138
188, 189
139
151.
152.
153.
154.
155.
156.
157.
158.
159.
160,
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
172.
173.
4. Oil of Turpentine—Spirit of Turpentine—“Turps.”
French, English, and American Turpentines—Distinguishing Char-
acters and Reactions, . e e t te e e
Effects of Turpentine,
II. CAMPHOR.
General Properties, . e s
Pharmaceutical Preparations, . º
Symptoms of Poisoning by Camphor,
Post-mortem Appearances, . e º - e &
Separation of Camphor from the Contents of the Stomach,
III. ALCOHOLS,
1. Ethylic Alcohol.
Statistics of Alcohol Poisoning, ſº &
Criminal or Accidental Alcoholic Poisoning,
Fatal Dose, e º &
Symptoms, . º º
Post-mortem Appearances,
Excretion of Alcohol, . e g tº e e º & º
Toxicological Detection of Alcohol—Conversion into the Dinitro-
benzoate Esters,
2. Amylic Alcohol.
Physical Properties of the Amylic Alcohols,
Poisonous Effects of Amylic Alcohol,
Identification of Amylic Alcohol, . e º g & e e
Amyl Nitrite—Iso-amyl Ester Nitrate—Physiological Effects—
Post-mortem. Appearances, . e e & tº © e
IV. ETHER,
Ether—Ethylic Ether, Ethyl Oxide—Chemical Properties of, .
Ether as a Poison, . e e º e e º e
Fatal Dose, . e o e
Ether as an Anaesthetic, . º º g º tº o e
Separation of Ether from Organic Fluids—Tests, . e e
º
139, 140
140
141
141
141, 142
142
142
142
142–144
144
144, 145
145, 146
146, 147
147, 148
148
148
148
148, 149
149
149, 150
I50
150
150, 151
CONTENTS.
xiii
W. CHILOROFORM,
Section
174.
175.
176.
177.
178.
179.
180.
181.
182
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193,
194.
195.
I96.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
207.
208.
Physical and Chemical Properties of Chloroform—Tests for Purity, .
Method of Manufacture, e e e º s º
1. Chloroform as a Liquid.
Poisonous Effect of Liquid Chloroform—Statistics
Local Action of Chloroform, e º g
Action on Blood, Muscle, and Nervous Tissue,
General Effects of the Liquid, s
Fatal Dose of the Liquid,
Symptoms, º ©
Post-mortem Appearances,
3. º
&
2. The Vapour of Chloroform.
Statistics of Deaths from Chloroform Vapour, .
Suicidal and Criminal Poisoning by Chloroform,
Physiological Effects, . tº te e *
i. produced by the Vapour,
Chronic Chloroform Poisoning,
Post-mortem Appearances, . º s
Detection and Estimation of Chloroform,
Estimation of Chloroform, . . .
WI. CHLORAL.
Chemical Properties of Chloral—Statistics of Chloral Poisoning,
Detection of Chloral Hydrate, e e º e e *
Assay of Chloral Hydrate, . e º
Effects of Chloral Hydrate on Animals, .
Action of Chloral on the Blood,
Effects of Chloral Hydrate on Man,
Fatal Dose, . º © e -
Symptoms, . . º º e e
Treatment of Acute Chloral Poisoning, .
Chronic Poisoning by Chloral Hydrate, . e e e º
Excretion of Chloral—Separation of Uro-Chloral from the Urine,
Separation of Chloral from Organic Matters—Tests for Chloral,
VII. MINOR ANAESTHETICS AND NARCOTICs.
Substitutions of the Hydrogen by Chlorine in Methane—Methane
Dichloride, tº e & e g º g e g
Pentane—Pental, . e - e e
Aldehyde (Acetaldehyde)—Metaldehyde,
Paraldehyde, . e © º º e
Somoform, . tº º e º e º e e tº &
Sulphones—Sulphonal, Trional, Tetronal–Cases of Poisoning by
Sulphones—Separation and Identification of the Sulphones,
Page
151–153
153
156, 157
157
157, 158
158, 159
159
159, 160
160
161

161, 162
162
162, 163
163, 164
164
164
165, 166
166
166, 167
167
168
169, 170
170
170
170
170
170, 171

209.
210.
211.
212.
213.
214.
215.
Weronal (Diethyl-barbaturic Acid), e tº e º º
VIII. BISULPHIDE OF CARBON.
Properties of Carbon Bisulphide, . e º e
Poisoning by Carbon Bisulphide—Chronic Poisoning,
Post-mortem Appearances, . . . º e º º
Detection and sºon of Carbon Bisulphide,
Xanthogenic Acid, . º © e º º º
Potassic Xanthogenate and Potassic Xanthamylate,
171, 172
172
172
173, 174
174
174
174
174
xiv
CONTENTS.
Section
IX. THE TAR ACIDS—PHENOL–CIRESOL.
Page
216. Carbolic Acid (Phenol)—Properties of, . º º º . . . 174, 175
217. Commercial Varieties—Calvert's Carbolic Acid Powder—Carbolic
Acid Soaps, gº e & e e tº 176
218. Uses of Carbolic Acid, . º * 176
219. Statistics of Carbolic Acid Poisoning, 176–178
220. Fatal Dose, . º º e g º e t 178
221. Effects on Animals—Infusoria—Fish—Frogs, . º o e 178, 179
222. Effects on Warm-blooded Animals—Rabbits—Cats—Mice, etc., 179
223. Symptoms in Man—External Application—Illustrative Cases, 180–182
224. Internal Administration, e tº º º e Hº 182, 183
225. Symptoms of Carbolic Acid Poisoning, . º º 183
226. Changes in the Urine from Carbolic Acid, e e e 183–185
227. The Action of Carbolic Acid considered physiologically, 185
228. Excretion of Carbolic Acid, . e º º º º 185, 186
229. Post-mortem Appearances—Museum Preparations, . e e º 186
230. Tests for Carbolic Acid—the Pinewood Test—Ammonia and Hypo-
chlorite—Ferric Chloride—Bromine, e e e º 187
231. Quantitative Estimation of Carbolic Acid, . º - e . 187, 188
232. Cresol (Cresylic Acid, Methyl-Phenol)—Ortho-, Meta-, and Para-
Cresol—Commercial Cresol, - e º - * . 188, 189
233. Creasote and Kreozote, . º e º 189
234. Carbolic Acid in Organic Fluids, . - g º 190
235. Examination of the Urine for Phenol or Cresol, * - º . 190–191
236. Assay of Disinfectants—Carbolic Acid Powders—Bromine Method—
Colorimetric Method of Estimation, . © e - º 192
237. Analysis of Carbolic Acid Powders, 192–193
238. Analysis of Carbolic Acid Soap, 193
X. NITRO-BENZENE.
239. Properties and Commercial Varieties of Nitro-Benzene, 193
240. Effects of Poisoning by Nitro-Benzene, º 193, 194
241. Poisoning by Nitro-Benzene Vapour, 194, 195
242. Poisoning by Liquid Nitro-Benzene, 195, 196
243, Fatal Dose, º wº º te 196
244. Pathological Appearances, . º o º 197
245. Physiological Action of Nitro-Benzene, . º e o e 197
246. Detection and Separation of Nitro-Benzene from Animal Tissues, 197, 198
XI. DINITRO-1BENZOL. -
247. Dinitro-Benzol (Ortho-, Meta-, Para-)—Physical and Chemical *
Properties, e º º e - e . . º . 198, 199
248. Effects of Dinitro-Benzol, º º 199, 200
249. The Blood in Nitro-Benzol Poisoning, . 200, 201
250. Detection of Dimitro-Benzol, . ſº . 201, 202
YII. HYDROCYANIC ACID.
251. General Properties of Hydrocyanic Acid, . 202
252. Medicinal Preparations of Prussic Acid, . & O º & © 203
253. Poisoning by Prussic Acid—Use of the Acid in the Arts—Occurrence
of in the Animal and Vegetable Kingdom, . º º . 203–205
254. Laurocerasin, . e º º e º º 206
255. Statistics of Cyanide Poisoning, , . - º º 206, 207
256. Accidental and Criminal Poisoning by Prussic Acid, 207, 208
257. Fatal Dose, . º - º g º º g º * 208
258. Action of Hydric and Potassic Cyanides on Living Organisms, 208, 209
258A.Effects on Infusoria, Yeast, and Algæ, º - º 209
259. Symptoms observed in Animals, 209, 210

CONTENTS.
XV
Section
260.
261.
262.
263.
264.
265.
266.
267.
268.
269.
270.
271.
272.
273.
274.
275.
276.
277.
278.
279.
280.
281.
282.
283.
284.
285.
286.
287.
288.
289.
290.
291.
292.
293.
2.94.
295.
296.
297.
298.
299.
300.
Symptoms in Dogs,
Symptoms in Man, . e e g tº tº e te o
Poisoning by the Cyanide Glucosides—The Rotterdam Cases, .
Chronic Poisoning by Hydric Cyanide, º g º ©
Post-mortem Appearances,
Tests for Hydrocyanic Acid and Cyanide of Potassium—Schönbein’s.
Test—Kobert's Test, . tº
Separation of Hydric Cyanide
Matters, . & g tº * gº & * º g ſº
How long after Death can Hydric or Potassic Cyanides be Detected
Estimation of Hydric or Potassic Cyanides, gº * g
Case of Poisoning by Bitter Almonds,
or Potassic Cyanide from organić
Poisonous Cyanides other than Hydric and Potassic Cyanides.
Sodic and Ammonic Cyanides, tº t º * tº e ſº
Action of Potassic Ferrocyanide—Silver Cyanide—Sulphocyanides
—Methyl Cyanide—Toxic Dose of the Nitriles, . e gº
XIII. PHOSPHORUS.
Chemical and Physical Properties, .
Phosphuretted Hydrogen—Phosphine,
Medicinal Preparations of Phosphorus,
Matches and Vermin Pastes, . g
Statistics of Poisoning by Phosphorus,
Fatal Dose, . © º sº º
Effects of Phosphorus, . &
Varieties of Symptoms Produced,
Common Form, g tº
Haemorrhagic Form,
Nervous Form,
Sequelae, ſe e º tº e ge &
Period at which the First Symptoms commence,
Period of Death, . g tº tº e &
Poisoning by Phosphorus Vapour, .
Chronic Phosphorus Poisoning,
Changes in the Urinary Secretion, .
Changes in the Blood, ſe ge
Antidote—Treatment, . &
Poisonous Effects of Phosphine { } & sº
Action of Phosphine on the Blood, . º e (s
Post-mortem Appearances—Museum Preparations, .
Changes produced in the Kidneys, Heart, and Lungs, . e º
Diagnostic Differences between Acute Yellow Atrophy of the Liver
and Fatty Liver produced by Phosphorus, . tº ſº e o
The Detection of Phosphorus—Mitscherlich’s Process—The Produc-
tion of Phosphine—Tests dependent on the Combustion of Phos-
phine—Blondlot's Apparatus, . ſº * º 'e gº tº
Spectrum of Phosphine—Lipowitz's Sulphur Test—Scherer's Test, .
Chemical Examination of the Urine, e e & e
Quantitative Estimation of Phosphorus, . º e
How long can Phosphorus be recognised after Death
Page
210, 211
211, 212
212, 213
213, 214
214, 215
215–217
217-219
219, 220
220
220, 221
221
221–224
224, 225
225, 226
226
226–228
228, 229
229
229
229, 230
230, 231
231
231, 232
232
232
232
232–234
234
234, 235
235
235
235, 236
236, 237
237, 240
240, 241
241
241–243
244, 245
245, 246
246, 247
247
xvi
CONTENTS.
PART VI. —ALKALOIDS AND POISONOUS VEGETABLE PRINCIPLES
DIVISION I.--WEGETABLE ALKALOIDs.
I. GENERAL METHODS OF TESTING AND EXTRACTING ALKALOIDS.
Section
301.
302.
303.
304.
305.
306.
307.
308.
309.
3.10.
3.11.
312.
313.
3.14.
3.15.
3.16.
3.17.
3.18.
319.
320.
321.
322.
323.
324.
325.
326.
327.
328.
329.
General Tests for Alkaloids, o º e º e º e
Group Reagents—Iodine in Hydriodic Acid—Iodine and Potassic
Iodide—Mercuric Potassic Iodide—Bismuthic Potassic Iodide—
Iodised Parethoxyphenyl Succinimide — Chloride of Gold —
Platinic Chloride, © e º º º e e -> e
(1) Phosphomolybdic Acid as a Reagent for Alkaloids; (2) Silico-
Tungstic . as a Reagent for Alkaloids; (3) Scheibler's Method
for Alkaloids—Phospho-Tungstic Acid, e º &
Schulze's Reagent, e - e e º º • •
Dragendorff's Reagent—Marmè's Reagent—Potass-Zinc Iodide,
Colour Tests—Fröhde's Reagent—Mandelin's Reagent, -
General Processes for the Separation of Alkaloidal Substances
Organic Matters—Kippenberger's Process, .
Selmi’s Process, . e g o g G º © e º
Dragendorff’s Process—Kippenberger's Modification of Dragendorff’s
Process, . tº º g © t o - p º e
Scheibler's Process, º e
Grandval and Lajoux's Method, .
Identification of the Alkaloids, º e º e
Behrens’ Method of Identification of the Alkaloids, .
Sublimation of the Alkaloids, . e - º
Melting-point of the Alkaloids, , . g e e º -
Identification by Organic Analysis—Methoxyl Groups—Nitrogen,
Quantitative Estimation of the Alkaloids, * º º
from
II. LIQUID VOLATILE ALKALOIDS.
THE ALKALOIDS OF HEMLOCK–NICOTINE–PITURIE–SPARTEINE.
1. The Alkaloids of Hemlock (Conium).
Characters of the Hemlock Plant, º © te e º
Coniine—Synthesis of Coniine—Characters of Coniine—Tests,
Constitution of the Coniine Bases—Comiceines–Conhydrin—Pseudo
conhydrine—Methylconiine, º
Pharmaceutical Preparations, .
Statistics of Coniine Poisoning,
Effects on Animals, e
Effects on Man, .
Physiological Action, º -> *
Post-mortem Appearances—-Fatal Dose, . e *
Separation of Coniine from Organic Matters or Tissues,
2. Tobacco–Nicotime.
The various Species of Tobacco—Composition of the Fresh Leaves, .
Quantitative Estimation of Nicotine in Tobacco–Keller's Process—
The Polarimetric Method of Popoirci—Estimation by Cox of
Nicotine in various Tobaccos º º o º e º e
Chemical and Physical Characters of Nicotine—Tests for Nicotine, .
Effects on Animals, º e - e
Effects on Man—Illustrative Cases,
SEPARATED FOR THE MOST PART BY ALCOHOLIC SOLVENTS.
Page
248
248, 249
249–251
251
251
251
252, 253
253, 254
254–256
256, 257
257
257
257, 258
259.262
262, 263
264
264–266
266
266–268
268,269
269,270
270
270,271
271
271
271, 272
272
273
330.
331.
332.
273,274
275–277
277,278
278, 279
CONTENTS.
xvii
Section
333. Cases of Tobacco Poisoning—Tobacco Smoke—External Application
of Tobacco Leaf, º g ſº º º e g ©
334. Physiological Action,
335. Fatal Dose, e
336. Post-mortem Appearances Q o ge º
337. Separation of Nicotine from Organic Matters, .
337A. Antidote to Nicotine, © o &
3. Piturie.
338. Chemical and Physical Characters of Piturie, .
4. Sparteine.
339. Chemical and Physical Characters of Sparteine,
5. A milime.
340. Properties of Aniline, º º º e e g º º
341. Symptoms and Effects—Chronic Poisoning—Post-mortem Appear-
8,D.C6S © e º - * º - * * º -
342. Fatal Dºse, º *
343. Detection of Aniline,
III. THE opium group of ALKALoIDs.
Page
279–281
281, 282
282
282
282,283
283
283,284
284
284
284, 285
285
285
344. General Composition—List of Alkaloids and other Principles—
Analysis of Samples of Opium, . . e © e t ©
345. Action of Solvents on Opium, & e e º & & -
346. Assay of Opium—Process of Teschemacher and Smith—Dott's
Process—Douzard Method, . e e º g g -
347. Medicinal and other Preparations of Opium—(1) Officinal ; (2) Patent
and other Non-Officinal Preparations of Opium, . e º -
348. Statistics of Opium Poisoning, e - - * º
349. Poisoning of Children by Opium,
350. Doses of Opium and Morphia, . & ©
351. General Method for the Detection of Opium,
352. Morphine: Chemical and Physical Characters of,
353. Morphine Salts, . o e e e •
354. Constitution of Morphine and Codeine, . e - e e -
355. Tests for Morphine–Kobert's Test—Iodic Acid Test—Vamadic Acid
Test—Tungstic Acid Test—Titanic Acid Test and other Reactions,
356. Symptoms of Opium and Morphine Poisoning—Action on Frogs,
Dogs, Goats, Cats, and Birds, * te º e º -
Physiological Action, , , & º * - º
Physiological Effect of Morphine Derivatives, . º • . . º
The Forms of Opium and Morphine Poisoning—Illustrative Cases, .
Diagnosis of Opium Poisoning, e e
Opium-eating—Opium-smoking, e
Treatment of Opium or Morphine Poisoning,
Post-mortem Appearances, . ſº tº & º &
Separation of Morphine from Animal Tissues and Fluids,
Extraction of Morphine, . © º tº e º e e º
Narcotine : Chemical and Physical Properties—Behaviour of Nar-
cotine with Reagents—Constitution of Narcotine, w -
367. Effects of Narcotine, º e - e
368. Codeine: Chemical and Physical Properties,
369. Effects of Codeine, te e e e • e e º
370. Narceine: Physical and Chemical Properties of Narceine and its
Salts, ſº * e
357.
358.
359.
360.
361.
362.
363.
364.
365.
366.
286, 287
287
287–289
290–293
293,294
294
294, 295
295, 296
297
297, 298
298,299
300–303
303, 304
304, 305
305, 306
306–309
309, 310
310–312
312
312, 313
313, 314
314, 315
315–317
317
317, 318
318, 319
319, 320
xviii
CONTENTS.
Section
371. Effects of Narceine, te gº e º º o
372. Papaverine: Chemical Properties and Tests, e
373. Effects of Papaverine, . º e º º
374. Thebaine: Physical and Chemical Properties of,
375. Effects of Thebaine, o e o º º
376. Cryptopine, e
377. Pseudomorphine,
378. Apomorphine, º & e o e
379. Laudanine—Laudanidine—Laudanosine,
380. Tritopine,
381. Mecomine, te e o º - e º e e
382. Mecomic Acid : Chemical Properties—Tests for—Separation of,
383.
384.
385.
386.
387.
388.
389.
390.
391.
392.
393,
394.
395.
396.
397.
398.
399.
400.
401.
402.
403.
404.
405.
406.
407.
Page
320, 321
321
321, 322
322
322, 323
323
323
323, 324
324
324
324
324, 325
IV. THE STRYCHN IN E OR TETANUS-PRODUCING GROUP OF ALKALOIDS.
1. Nua, Vomica Group—Strychnine—Brucine—Igaswrime.
General Characters of Nux Womica Seeds,
Chemical Constituents of Nux Womica Seeds, . º
Strychnine: Chemical and Physical Characters of, .
Strychnine Salts, & e º -> - e & º ©
Pharmaceutical and other Preparations of Nux Womica and
Strychnine, with Suggestions for their Valuation—Separation of
the Alkaloids from Nux Womica—Tests—Wermin-killers, e
Statistics of Death from Strychnine—the Series of Murders by
Thomas Neill Cream—The Palmer Case, . º wº
Fatal Dose—Falck’s Researches—Illustrative Cases,
Action on Animals, s º e - º - º e
Effects on Man—Distinction between Tetanus from Strychnine and
“Disease Tetanus,” . e e
Diagnosis of Strychnine Poisoning,
Physiological Action,
Post-mortem Appearances,
Treatment, . e & g e º º
Separation of Strychnine from Organic Matters,
Identification of the Alkaloid, - e
The Physiological Test for Strychnine,
Hypaphorine, * e s e tº º
Quantitative Estimation of Strychnine, . º - &
Brucine—Solubility and Chemical Properties of Brucine,
Physiological Action, g º - º
Tests, . º e
- º
2. The Quebracho Group of Alkaloids.
The Alkaloids obtained from Quebracho Blancko,
Aspidospermine, . * & te e t
Quebrachine, .
3. Pereirime.
Pereirine,
325–328
326
326–328
328, 329
329–332
332–334
334–337
337, 338
338–340
340
340, 341
341, 342
342
342–345
346, 347
347, 348
348
348, 349
349, 350
350, 351
351, 352
353
353
358
353
408.
409.
410.
411.
412,
4. Gelsemime.
Gelsemine and Gelseminine,
Fatal Dose, . ſº
Effects on Animals,
Effects on Man, . * * º & e & º
Extraction from Organic Matters or the Tissues of the Body, .
353, 354
354
354, 355
355
355
\
-
CONTENTS.
xix
5. Coca Alkaloids—Cocaine.
Section Page
413. The Alkaloids in the Leaves of Erythroacylon coca—Cocaine, 356
414. Cocaine Hydrochloride, . º g e * • • 357
415. Pharmaceutical Preparations, . 357
416. Separation of Cocaine and Tests, 357, 358
417. Symptoms, e g tº 358, 359
418. Post-mortem. Appearances, 359
419. Fatal Dose, © & 359
6. Corydaline.
420. Alkaloids extracted from the Root of Corydalis cava—Corydaline, 359, 360
V. THE ACONITE GROUP OF ALKALOIDS.
421. Description of the Acomitum napellus, 360
422. Pharmaceutical Preparations of Aconite, . e e g ſº . 360, 361
423. Dunstan's Researches—The Groups of Aconitine Alkaloids—The
Aconitine Group—The Pseudaconitines and the Atisine Group—
The Melting-points and Specific Rotations of the Alkaloids and
the Melting-point of the Gold Salts, g g * tº . 361, 363
424. Aconitine: Extraction and Properties, . . . 363
425. Tests for Aconitine, te ſº e 364
426. Benzoyl-Aconine, .. º e 364, 365
427. The Lethal Dose of Aconitines, e º ſº tº g . 365, 366
428. Effects of Aconitine on Animal Life: Insects, Fish, Reptiles, Frogs—
_ Action of Aconitine on the Heart—Effects of Indaconitine—Birds
—Mammals, & g * $º * e g sº g . 366–370
429. Statistics of Aconite Poisoning, 370
430. Effects on Man, ſº e * 370
431. Poisoning by the Root, . © & 370, 371
432. Poisoning by the Alkaloid Aconitine, 372–374
433. The Lamson Case, . tº g e tº g 37.4
434. Poisoning by Medicinal Preparations of Aconite, 375
435. Physiological Action, º wº e 375
436. Post-mortem Appearances, . e e ſº g e tº . 375, 376
437. Separation of Aconitine from the Contents of the Stomach or the
Organs, . 376, 377
VI. THE MY DRIATIC GROUP OF ALKALOIDS—ATROPINE–HYOSCYAMINE–
SOLAN INE–CYTISINE.
1. Atropime
438. Alkaloids in Plants belonging to the Solanaceae, . t tº 377, 378
439. Atropine–Alkaloidal Content of the Belladonna Plant, . tº . 378, 379
440. The Datura stramoniwm—Distinction between Seeds of the Datura
and those of Capsicum, ſº e º e & e 379, 380
441. Pharmaceutical Preparations of Belladonna, • • 380
442. Properties of Atropine—Constitutional Formula, . e tº . 380, 381
443. Tests for Atropine–Distinction between Hyoscyamine and Atropine
—Strychnine and Atropine–Action of Atropine on the Iris, . 381–384
444. Statistics of Atropine Poisoning, . e º e o 384, 385
445. Accidental and Criminal Poisoning by Atropine, 385, 386
446. Fatal Dose, . e e e * & e 386
447. Action on Animals, 386, 387
448. Action on Man, º tº º 387–389
449. Physiological Action of Atropine, 389, 390
450. Diagnosis, . º & e 390
451. Post-mortem Appearances, 390
452. Treatment, . * g g ę * º 390, 391
453. Separation of Atropine from Organic Tissues, . 391
XX CONTENTS.
2. Hyoscyamine.
Section
454. Distribution and Properties of Hyoscyamine, . tº
455. Pharmaceutical and other Preparations of Henbane,
456. Dose and Effects, . o © iº e ge º
457. Separation of Hyoscyamine from Organic Matters, .
3. Scopolamine.
458. Scopolamine, . wº
459. Pseudo-hyoscyamine
460. Atropamine, . ſº
460A.Belladonnine,
9
4. Solamine.
461. Distribution of Solanine,
462. Properties of Solanine,
463, Solanidine, . ſº tº ſº
464. Poisoning from Solanine, º º * {} *
465. Separation of Solanine from the Tissues of the Body,
5. Cytisine.
466. The Cytisus labwrnwm—Cytisine,
467. Reactions of Cytisine, tº
468. Effects on Animals,
469. Effects on Man,
VII. THE ALKALOIDS OF THE WERATRUMS,
470. The Active Principles in Veratrum sabadilla, V. album, and
V. viride—Chemical Properties of the Alkaloids, ſº g
471. Weratridine—Weratric Acid–Cevadine, . gº
472. Jervine, . *
473. Pseudo-jervine,
474. Protoveratridine,
475. Rubi-jervine, .
476. Weratralbine, .
477. Weratroidine, . e
478. Commercial Weratrine, g
479. Pharmaceutical Preparations, .
480. Fatal Dose, . g § g & te
481. Effects on Animals—Physiological Action,
482. Effects on Man, e e tº º
483. Symptoms, . tº wº
484. Post-mortem Appearances,
485. Separation from Organic Matters,
VIII. PHYSOSTIGMINE.
486. The Ordeal Bean of Calabar,
487. Physostigmine or Eserine,
488. Tests, . e te e e
489. Pharmaceutical Preparations, . *
490. Effects on Animals—Effects on Man,
491. Physiological Action, tº tº
492. Post-mortem Appearances,
493. Separation of Physostigmine, .
494. Fatal Dose of Physostigmine, .
Page
391-393
393, 394
395
395
395, 396
396
396
396
396, 397
397
397, 398
398
398
398, 399
399, 400
400
400, 401
401–403
403, 404
404
404
404, 405
405
405
405, 406
406
406, 407
407
407
407, 408
408
408
408, 409
409
409, 410
410, 411
411
411, 412
412
412
412, 413
413
r
CONTENTS.
xxi
IX. PILOCARPINE,
Section Page
495. The Alkaloids of the Jaborandi, 414
496. Pilocarpine, . * { } º 414
497. Tests, . {º g & tº & g & tº 414, 415
498. Effects of Pilocarpine–Isopilocarpine—Pilocarpidine, 415, 416
X. TAXINE.
499. Poisonous Properties of Taxine—Chemical Properties of Taxine, 416
500. Poisoning by Yew, . & • . g ſº e 416
501. Effects on Animals—Physiological Action, 416, 417
502. Effects on Man, e tº te tº 417
503. Post-mortem Appearances, 417
XI. CURARE ALKALOIDS.
504. The Warieties of Curare—Isolation of the Curare Alkaloids, 418, 419
505. Physiological Effects, . e tº {º * e º 419, 420
506. Separation of Curarine, 420
XII. COLOHICINE.
507. Content of Alkaloid in Colchicum Seeds, . e 421
508. Colchicine—Extraction—Chemical Composition, 421, 422
509. Tests, . ſº ſº & g o º e ſº tº 422
510. Pharmaceutical Preparations—Quack and Patent Medicines, 422, 423
511. Fatal Dose, . e wº {º e tº © 423
512. Effects of Colchicine on Animals, 423
513. Effects of Colchicine on Man, . † © e g ſº g 424, 425
514. Symptoms produced by Colchicine—Post-mortem. Appearances, 425
515. Separation of Colchicine from Organic Matters, tº g 425, 426
ExIII, MUSCARINE AND THE ACTIVE PRINCIPLES OF CERTAIN FUNGI.
516. The Amanita muscaria — Botanical Characters—Effects on the
Inhabitants of Kamschatka, ſº ge º g tº & 426, 427
517. Poisoning by the Amanita, and Post-mortem Characteristics, 427
518. Muscarine: Chemical and Physiological Properties, 427, 428
519. Antagonistic Action of Atropine and Muscarine, 428, 429
520. Detection of Muscarine, . e e * 429
521. The Agaricus phalloides, 429, 430
522. Post-mortem. Appearances, . & º ſº 430
523. The Agaricus pantherinus—The Agaricus ruber, 430, 431
524. The Boletus satanas, ë & tº 431
525. The Common Morelle, 431
DIVISION II.—GLUCOSIDES.
I. DIGITALIS GROUP.
526. Description of the Foxglove, 431, 432
527. Chemical Composition, 432
528. Digitalein, (s e 432
529. Digitonin–Digitogenin, . 432
530. Digitalin, e tº 432, 433
531. Digitaletin, 433
532. Digitoxin, , . tº e & ſº tº g 433
532A.Separation of Digitoxin from Organic Matters, 433, 434
533. Digitaleretin—Paradigitaletin, ſº g 434
534. Inert Derivatives—Digitin, Digitalacrin, 434
xxii CONTENTS.
Section
535. Reactions of the Digitalins, . $ º &
536. Pharmaceutical Preparations of Digitalin, &
537. Fatal Dose, {º tº tº tº e ſº
538. Statistics, g º te º
539. Effects on Man—Illustrative Cases,
540. Physiological Action of the Digitalins,
541. Local Action, . ę ſº e *
542. Action on the Heart, . e © & gº tº tº ſº *
543. Aº of the Digitalins on the Muco-intestinal Tract and other
rgans * ſº e © © * e e g g g
544. The Action of Digitalin on the Common Blow-Fly, .
545. Action of the Digitalins on the Frog's Heart, . §
546. Post-mortemi Appearances, . e • *
547. Separation of the Digitalins from Animal Tissues,
II. OTHER POISONoUs GLUGOSIDES ACTING ON THE HEART:
1. Crystallisable Glucosides.
548. Antiarin, tº &
549. Effects of Antiarin, . &
550. Separation of Antiarin, . ë ſe e tº ſº º * º
551. The Active Principles of the Hellebores—Helleborin–Helleborein—
Helleboretin, . ſº e tº ſº * tº e tº g
552. Cases of Poisoning by Hellebore Root,
553. Euonymin, . e e * e
554. Thevetin,
2. Substances partly Crystallisable, but which are not Glucosides.
555. Strophantin,
3. Non-Crystallisable Glucosides almost Insoluble in Water.
556. Scillain, .
557. Adonidin, ſe
558. Oleandrin, . e ſº e
559. Neriin or Oleander Digitalin, .
560. Poisoning by the Nerium oleander, .
561. The Madagascar Ordeal Poison,
4. Substances which behave like the Digitalins.
562. Apocynin,
III. saponin-saponin substances.
563. Varieties of Saponin,
564. Properties of Saponin,
565. Effects of Saponin, .
566. Action on Man,
567. Separation of Saponin,
568. Identification of Saponin,
Bage
434
434, 435
435, 436
436
436–439
439, 440
440
440–442
442
442
442, 443
443, 444
444, 445
445
445
445, 446
446
446, 447
447
447
447
448
448
448
448, 449
449
449
449
450
450, 451
451, 452
452
452, 453
453
DIVISION III.--WARIOUs WEGETABLE POISONOUS PRINCIPLES NOT READILY
ADMITTING OF CLASSIFICATION IN THE PREVIOUS DIVISION.
I, SANTONIN.
Physical and Chemical Properties of Santonin,
569.
570. Poisoning by Santonin, . g ſº
453
453
CONTENTS. xxiii
Section *- Page
571. Fatal Dose, . tº e e gº * & e dº º º 454
572. Effects on Animals, . 454
573. Effects on Man, s gº 454, 455
574. Post-mortem. Appearances, . e i. g tº e gº * 455
575. Separation of Santonin from the Contents of the Stomach, . tº 455
II. MEZEREoN.
576. The Daphne mezereon, . gº e e * o tº ſº e 456
III. ERGOT OF RYE.
577. Description of Ergotised Grain, . § tº e g § e 456
578. Chemical Constituents of Ergot—Scleromucin—Sclerotic Acid—
~ —Secalin-Toxin–Cornutin—Inert Principles of Ergot, º . 457–460
579. Detection of Ergot in Flour, ſº g tº * } * g 460
580. Pharmaceutical Preparations of Ergot, . « » e * & § 460
581. Dose, . . . . . . . . . . . . 460, 461
582. Ergotism, g * 461
583. Convulsive Form of Ergotism, & * & g * * 461, 462
584. The Gangrenous Form of Ergotism—The Wattisham Cases, . . 462, 463
585. Symptoms of Acute Poisoning by Ergot, . g * § * ſº 463
586. Physiological Action as shown by Experiments on Animals, . . 463-465
587. Separation of the Active Principles of Ergot from Animal Tissues, . 465
II. PICROToxin, THE ACTIVE PRINCIPLE OF THE COCCULUS INDICUS
(INDIAN BERRY, LEVANT NUT).
588. Active Principles of the Memispermum cocculus, . g © . 465, 466
589. Picrotoxin—Picrotoxinin—Picrotin, º e * e e . 466, 467
590. Fatal Dose, . e g º º º & † tº & tº 467
591. Effects on Animals, g e º e tº & e g . 467, 468
592. Effects on Man, . gº * tº ge e Hº e tº g 468
593. Physiological Action, . º g * & • • tº º 468
594. Separation from Organic Matters, . * º e e p . 468, 469
594A. III. TUTIN–CORIAMYRTIN.
IV. THE POISON OF ILLICIUM RELIGIOSUM-A JAPANESE PLANT.
595. The Chemistry and Pharmacology of the Illicium religiosum, . * 470
V. PICRIC ACID AND PICRATES.
596. Picric Acid, . {e ſº e ſº © * & * º º 470
597. Effects of Picric Acid, . ſº iº º tº tº º e . 470, 471
598. Tests for Picric Acid, . e tº & to • • te * 471
VI. CICU'TOXIN.
599. The Botanical Characters of Cicuta virosa, . ſº tº te . 471, 472
600. Effects on Animals, º tº e g ſº * & g ſe 472
601. Effects on Man, . dº tº * g wº º te tº tº 472
602. Separation of Cicutoxin from the Body, . † * te tº & 473
VII. ACTHUSA CYNAPIUM (Fool's PARSLEY).
603. Poisoning by Fool's Parsley, . . . . . . . . 473
xxiv. CONTENTS,
VIII. CENANTHE CROCATA.
Section Page
604. The Water Hemlock: Poisonous Properties of, * w º . 473, 474
605. Illustrative Cases, . º e e e º 474
606. Post-mortem Appearances, . º e ſº 474, 475
IX, OIL OF SAWIN.
607. Effects of the Oil of Savin, . ſe tº c * o º tº 475
608. Post-mortem Appearances, . e s © o e º e 476
609. Separation of the Poison and Identification, . e º - & 476
Y. CROTON OIL.
610. Chemical Composition of Croton Oil, . wº & e • s 476
611. Dose and Effects, . o & tº - - . º . . . 477
612. Post-mortem Appearances, . e º º e - - t 477
613. Chemical Analysis, . e - e e º e e -> c 477
XI. THE TOXALBUMINS OF CASTOR-OIL SEEDS AND OF ABRUS.
614. The Toxalbumins of Castor-Oil Seeds, . o ſº o & e 478
615. Toxalbumin of Abrus, . e sº e e e e - . 478, 479
XII, ICTROGEN,
616. Ictrogen–Poisoning by Lupin Seeds, . - e e & e 479
XIII. COTTON SEEDS.
617. Poisoning by Cotton Seeds, . te º e e - - . 479, 480
XIV. LATHYRUS SATIVU.S.
618. Effects of Warious Species of Lathyrus, . º e • . * 480
XV. ARUM-BRYONY–LOCUST TREE-MALE FERN,
619. Arum maculatum, . tº º te e º & e - 481
620. The Black Bryony, e º tº * O g tº tº & 481
621. The Locust Tree, . ſº & & e e ſº e & o 481
622. Mále Fern, . e e º e e º & & - . 481, 482
PART VII.-POISONS DERIVED FROM LIVING OR DEAD ANIMAL
SUBSTANCES.
DIVISION I.-Poisons SECRETED BY LIVING ANIMALS.
I. POISONOUS AMPEIIBIA,
623. The Salamander, . e º g e º * e e . 483, 484
624. Poisoning by the Samandarins, ſº e tº º e e * 484
625. The Water Salamander, . º e e e s e º e 484
626. Poisons of the Toad, º G te - o º º e . 484, 485
627. The Heloderma, . . º e e o o º s . 485, 486
CONTENTS.
xxv
II. THE POISON OF THE SCORPION.
Section
628. Effects of Scorpion Poison,
III. POISONOUS FISH.
629. Muraena helena—the Fugu-Poison of Japan—Tetrodonin–Tetro-
donic Acid, . o º G. g g ſº º e * ©
630. Other Poisonous Fish—The Toad Fish,
IV. POISONOUS SPIDERS AND INSECTS.
630A.Varieties of Spiders known to be Poisonous,
631. The Katipo, ". e º e e -
632. Ants, . e e & & g -
633. Wasps,
634. Cantharides,
635. Cantharidin, . º & © e -
636. Pharmaceutical Preparations of Cantharides,
637. Fatal Dose, . e e - º e
638. Effects on Animals—Effects on Man,
639. Illustrative Cases, e g
640. Post-mortem Appearances, . g -> & &
641. Tests for Cantharidin, and its Detection in the Tissues,
W. POISONOUS SNAKES.
642.
643.
644.
Classification of Poisonous Snakes, .
The Poison of the Cobra,
Fatal Dose, . e e
645. Effects on Animals,
646. Effects on Man, º o
647. Cobra Anti-Toxin, . º e º e
647A.Other Colubrine Snakes—The Viperidae, .
647B. Duboča Russellº, . e º & &
647c.The Poison of the Common Viper,
VI. MAMMALIAN POISON.
6471). Epinephrin, , . e º º e
647E, Physiological Action of Epinephrin,
DIVISION II.-PTOMAINEs—ANIMAL Toxin Es.
648. Definition of Ptomaine,
Isolation of Animal Toacimes.
649.
650.
651.
652.
653.
654.
655.
656.
657.
658.
659.
660.
Gautier's Process,
Brieger's Process, . &
Benzoyl Chloride Method,
The Amines, . e ū.
Methylamine, .
Dimethylamine,
Trimethylamine,
Ethylamine,
Diethylamine,
Triethylamine,
Propylamine, .
Iso-amylamine,
Page
486, 487
487, 488
488, 489
489–491
491
491
491
491, 492
492
493
493
493–495
494, 495
495
495–497
498
498–500
500
500, 501
501, 502
502, 503
503
504
504
505, 506
506
506, 507
507
507–509
509, 510
510–512
513
513
513
513
513
513
513, 514
514
xxvi CONTENTS,
Diamºnes.
Section
661. Rate of Formation of Diamines,
662. Ethylidenediamine,
663. Neuridine, *
664. Cadaverine,
665. Putrescine, . te
666.
667.
668.
669.
670.
671.
672.
673.
674.
675.
676.
677.
678.
679.
680.
681.
682.
683.
684.
685.
686.
687.
688.
689.
690.
691.
692.
693.
694.
695.
696,
697.
698.
699.
700.
701.
702.
703.
704.
705.
706.
Metaphenylenediamine, .
Paraphenylenediamine,
Hexamethylenediamine, .
Diethylenediamine,
Mydaleine,
Guanidine, .
Methylguanidine,
Saprine, . º tº
The Choline Group, § g e
Neurine—Trimethyloxyammonium,
Betaine, . * sº ſº
Peptotoxine, . tº * ge g º
Pyridine Alkaloid from the Cuttle Fish, .
Poisons connected with Tetanus, ſº
Tetanotoxine, . &
Mydatoxine, . *
The Poison of Mussels,
Tyrotoxine, . º *
Toxines of Hog Cholera, .
Other Animal Toxines,
DIVISION III. —FooD PoisonING.
The Development of Toxic Principles in Food–Various Mass Poison-
ings—Statistics, .
German Sausage Poisoning,
PART VIII. —THE OXALIC ACID GROUP OF POISONS,
Distribution of Oxalic Acid, . †
Chemical Properties of Oxalic Acid,
Oxalate of Lime, g G
Use in the Arts,
Hydropotassic Öxalate Binoxalate of Potash,
Statistics of Oxalic Acid Poisoning,
Fatal Dose,
£ffects ofäxalic Acid and oxalates on Animals,
Kobert and Küssner's Researches,
Effects of Vaporised Oxalic Acid,
Effects of Oxalic Acid and Hydropotassic oxalate on M ań.
Physiological Action,
Pathological Changes,
Specimens of Oxalic Acid Poisoning in Museums,
Pathological Changes produced by Hydropotassic Oxalate,
Separation of Oxalic Acid from Organic Substances,
Oxalate of Lime in the Urine,
Estimation of Oxalic Acid,
Certaim, Oaxalic Bases–oralmethyline—oxalºropyline.
Schulz and Mayer's Researches on the Oxalic Group of Poisons,
525
525, 526
526
526, 527
527, 528
528
528, 529
529–531
532
533
533, 534
534, 535
535
535
535
535
535, 536
536
537
537 -539
539, 540
540
541
541
541–544
544
544–545
545
CONTENTS.
xxvii
PART IX. —INORGANIC POISONS.
I. PRECIPITATED FROM A HYDROCHLORIC ACID SOLUTION BY HYDRIC SULPHIDE
—PRECIPITATE YELLOW or ORANGE.
ARSENIC–ANTIMONY–CADMIUM.
1. Arsenic.
Section
707.
708.
709.
710.
711.
712.
713.
714.
715.
716.
717.
718.
719.
720.
721.
722.
723.
724.
725.
726,
727.
728.
729.
730.
731.
Metallic Arsenic, . tº e g º & º &
Arsenious Anhydride—Arsenious Acid—White Arsenic, .
Arsine-Arseniuretted Hydrogen, º t
Arsine in the Arts, . * e g * & º
Effects on Animals and Man of Breathing Arsine, .
The Sulphides of Arsenic, fe g te º
Orpiment, or Arsenic Trisulphide, . e s e * e e
Haloid Arsenical Compounds—The Chloride of Arsenic—the Iodide
of Arsenic, . e g º * e e º -> te
Arsenic in the Arts, tº º g te & e º s
Pharmaceutical, Non-Officinal, and other Preparations of Arsenic,
Statistics, º º e & e e e e e º
The Law relative to Sale of Arsenic,
Dose, . c is e e e
Effects of Arsenious Acid on Plants,
Effects on Animal Life, . tº º
Effects of Arsenious Acid on Man, .
Manner of Introduction of Arsenic, e º * º
Cases of Poisoning by the External Application of Arsenic,
Arsenic in Wall-Papers, . {} s & º g
Forms of Arsenical Poisoning,
The Subacute Form, e
The Nervous Form,
Absence of Symptoms,
Slow Poisoning, .
The Maybrick Case,
731A.Poisoning by Arsenical Beer, g
732.
733.
734.
735.
736.
737.
738.
739.
740.
741.
742.
743.
744.
745.
746.
Post-mortem. Appearances in Animals, º e -
Post-mortem. Appearances in Man—Museum Preparations,
Changes in Gullet, Stomach, Liver, and Kidneys,
Physiological Action of Arsenic, . e s
Elimination of Arsenic, . g e
Antidote and Treatment,
Detection of Arsenic,
Arsenic in Glycerin,
Arsenic in Organic Matters, º
Imbibition of Arsenic after Death, .
Analysis of Wall-Paper for Arsenic,
Estimation of Arsenic, . sº e
Electrolytic Methods,
Page
546
546–548
548, 549
549
549–551
551
551
551
552
552–556
556, 557
557
557, 558
558
558–560
560, 561
561, 562
562, 563
564
564, 565
565–567
567, 568
568
568, 569
569–571
571, 572
572, 573
573, 574
574–576
576, 577
577
577
577–585
585
585–587
587–590
590, 591
591, 592
592–594
594, 595
747.
748.
749.
750.
Gautier's Method, to e º e e e - e e
Precipitation as Tersulphide—(a) Solution of the Precipitate in
Ammonia and Estimation by Iodine ; (b) Oxidation of the
Sulphide and Precipitation as Ammonio-Magnesian Arseniate ;
(c) Conversion of the Trisulphide into the Arseno-Molybdate of
Ammonia; (d) Conversion of the Sulphide into Metallic Arsenic,
2. Antimony.
Metallic Antimony,
Antimonious Sulphide, . e e *
Tartarated Antimony or Tartar Emetic, .
Metantimonic Acid, º e g
595–600
600
600, 601
601
601
xxviii CONTENTS.
Section
751. Pharmaceutical, Veterinary, and Quack Preparations of Antimony
—Antimonial Preparations used in Pyrotechny, .
Alloys containing Antimony, . e º
Antimonial Pigments, º
Dose, . tº t º º º © tº © º ſº
Effects of Tartar Emetic and of Antimony Oxide on Animals, .
Effects of Tartar Emetic on Man, - e
Chronic Antimonial Poisoning,
The Chapman Case, e
Post-mortem Appearances,
Elimination of Antimony, s -
Antidotes for Tartar Emetic, . e -
Effects of Chloride or Butter of Antimony, . - º e e
Detection of Antimony in Organic Matters—Identification of Anti-
mony Sulphide : (a) Dry Method, (b) Wet Processes—Hyposulphite
Method—Tartaric Acid Method—Sodium Peroxide Method,
763A.Stibine, . e & g & º º º e º
764. Quantitative Estimation,
752.
753.
754.
755.
756.
757.
758,
759.
760.
761.
762.
763.
3. Cadmiwan.
Properties of the Metal Cadmium,
Cadmium Oxide, . g e
Cadmium Sulphide,
Medicinal Preparations, .
Cadmium in the Arts,
Fatal Dose of Cadmium, º tº
Separation and Detection of Cadmium,
765.
766.
767.
768.
769.
770.
771.
Page
602–604
604
605
605
605, 606
606, 607
607, 608
608, 609
609, 610
610
610
610, 611
61.1—614
614
614, 615
615
615
615
615
615
615, 616
616
II. PRECIPITATED BY HYDRIG SULPHIDE IN HYDROCHLoRIC ACID Solution
—PRECIPITATE BLACK.
LEAD-COPPER—BISMUTH–SILVER—MERCURY.
1. Lead.
Metallic Lead—Oxide of Lead—Red Lead,
Sulphide of Lead, . e e º e
Sulphate of Lead, tº
Acetate of Lead, . * e º
Chloride of Lead–Carbonate of Lead, e º - º e
Preparations of Lead used in Medicine—Quack Nostrums containing
Lead—Lead Pigments—Salts used in the Arts—Alloys of Lead, .
Statistics of Lead-Poisoning, & e e e © © e
Lead as a Poison, . e o & º º º
Effects of Lead Compounds on Animals, . e º
Effects of Lead Compounds on Man—Acute Poisoning,
Chronic Poisoning by Lead, . º e e e
Lead Encephalopathy, . e e & º e - t e
Lead-Poisoning in White-lead Factories—Distribution of Lead in the
Brain, ſº º º e e e º e e º
785. Influence of Lead on the Excretion of Uric Acid,
786. Effects of Lead-Poisoning on the Offspring, . -
786A. Lead in Drinking Water—Testing for Lead in Water,
786B. The Plumstead Murder Case, º º e
787. Post-mortem. Appearances,
788. Physiological Action of Lead, .
789. Elimination of Lead, e e º e o º º e
790. Fatal Dose—(a) Sugar of Lead; (b) Basic Acetate; (c) Carbonate,
791. Antidote and Treatment, ſº o º e - ©
792. Localisation of Lead, º e .
793. Detection and Estimation of Lead, .
772.
773.
774.
775.
776.
777.
778.
779.
780.
781.
782.
783.
784.
616, 617
617
617
6.17
617, 618
618, 619
620
620–622
622, 623
623–625
625, 626
626
627, 628
628, 629
629
629–631
631
632
632, 633
633
633, 634
634
634
635
CONTENTS.
xxix
Section
793A.Tetra - methyl-diamino - phenyl - methane as a Test for Lead
795.
796.
797.
798.
799.
800.
801.
802.
803.
804.
805.
806.
807.
808.
809.
810.
811.
812.
813.
814.
815.
816.
817.
818.
819.
820.
821.
822.
823.
824.
825.
826.
827,
828.
829.
830.
831.
832.
833.
834.
835.
836.
Peroxide, . e
793B.Electrolytic Method of separating fead as Dioxide,
794. º & G - e. º
Estimation of Lead,
2. Copper.
Metallic Copper, e º
Cupric Oxide, º e º º
Cupric Sulphide, . & º tº º º * tº
Solubility of Copper in Water and Various Fluids, . - -
Copper in the Wegetable and Animal Kingdom and in Foods, .
The Coppering of Vegetables, . º º º
Preparations of Copper used in Medicine and the Arts,
Dose—Medicinal Dose of Copper, . º &
Effects of Soluble Copper Salts on Animals,
Toxic Dose of Copper Salts, . . -
Cases of Acute Poisoning, e º -> - - º ->
Effects of Subacetate, Subchloride, and Carbonate of Copper, .
Post-mortem Appearances, . e º º º • •
Chronic Poisoning by Copper, . º - - - - e e
Detection and Estimation of Copper—Electrolysis of Copper Salts—
Special Tests for Copper, . º º º - e º e
Volumetric Processes for the Estimation of Copper, .
3. Bismuth.
Properties of Metallic Bismuth,
The Peroxide of Bismuth,
The Sulphide of Bismuth, & º - e o º
Preparations of Bismuth used in Medicine and the Arts, .
Medicinal Doses of Bismuth, . o
Toxic Effects of Bismuth, - • - te º
Extraction and Detection of Bismuth in Animal Matters, e
Estimation of Bismuth–Estimation of Bismuth by Potassic Dichro-
mate—Electrolytic Estimation, . - - - -
4. Silver.
Properties of Metallic Silver, .
Chloride of Silver, . e
Sulphide of Silver, . º º - tº º º
Preparations of Silver used in Medicine and the Arts,
Medicinal Dose of Silver Compounds,
Effects of Nitrate of Silver on Animals, . * * * º º
Toxic Effects of Silver Nitrate on Man—(1) Acute Poisoning;
(2) Chronic Poisoning, - - • - - *
Post-mortem. Appearances, º
Detection and Estimation of Silver,
5. Mercury.
Properties of the Metal—Mercurous Chloride, .
Mercury Sulphide, . G ſº e - e
Medicinal Preparations of Mercury,
Mercury in the Arts, . O - e e º º e te
The more common Patent and Quack Medicines containing Mercury,
Mercury in Veterinary Medicine, - º
Medicinal and Fatal Dose, . e
Poisoning by Mercury—Statistics, . º e tº © tº e
Effects of Mercurial Vapour and of the Non-Corrosive Compounds of
Mercury, . e e e e º -> º & e e
Page
635, 636
636
636, 637
637
637
637, 638
638–640
640, 641
641–643
643, 644
644
644–646
646, 647
647, 648
648
648
648–650
650, 651
651, 652
652
652
652
652, 653
653
653, 654
654, 655
655–657
657
657
657, 658
658, 659
659
659, 660
660
660, 661
661, 662
662
662
663–667
667,668
668
669
669
669, 670
670, 671
XXX CONTENTS.
Section
837. Effects on Man, . w tº tº
838. Absorption of Mercury by the Skin, o
839. Symptoms of Poisoning by Mercury Vapour,
840. Mercurial Tremor, . ſº e º sº
841. Mercuric Methide, . g tº
842.
843.
844.
845.
846.
847.
848.
849.
850.
851.
852.
853.
Effects of the Corrosive Salts of Mercury, ſo ſº º ſº
Poisoning by the External Application of Corrosive Sublimate,
The Nitrates of Mercury, * ſº e e * tº &
Case of Poisoning by Mercury Nitrate,
Mercuric Cyanide, . g * e
White Precipitate, . ſº e e g
Treatment of Acute and Chronic Poisoning,
Post-mortem Appearances—Museum Specimens,
Pathological Appearances after Nitrate of Mercury,
Elimination of Mercury, . tº * g * º
Tests for Mercury, . te e e e e te gº Çı
The Detection of Mercury in Organic Substances and Fluids, .
853A. Separation of Mercury by Hydroxylamine, . º
853B. Detection of Mercury in the Urine, † tº
854.
855.
856.
857.
858.
859.
860.
861.
Estimation of Mercury, . e
Volumetric Processes for the Estimation of Mercury,
ZINC-NICKEL–COBAL.T.
1. Zºmc.
The Properties of Metallic Zinc,
The Carbonate of Zinc, &
The Oxide of Zinc, . e º s tº e
The Sulphide of Zinc–The Sulphate of Zinc, .
Chloride of Zinc, . tº
Zinc in the Arts-chromate of Ziné–Contamination of Liquids by
Page
671, 672
672
672, 673
673, 674
674, 675
675, 676
676
676
676,677
677
677
677
677, 678
677,678
679,680
680,681
681–683
683
683–685
685
685, 686
III. PRECIPITATED BY HYDRIC SULPHIDE FROM A NEUTRAL Solution.
686, 687
687
687
687
687, 688
862.
863.
864.
865.
866.
867.
868.
869.
870.
871.
872.
873.
874.
875.
876.
877.
Zinc, . ſº § tº tº º e * º
Effects of Zinc, as shown by Experiments on Animals,
Effects of Zinc Compounds on Man—(a) Zinc Oxide,
(b) Sulphate of Zinc, te e ſº & tº
(c) Zinc Chloride, * §
Post-mortem Appearances, . ſº § tº
Detection of Zinc in Organic Liquids or Solids,
Identification of Zinc Sulphide, e e
2. Nickel–Cobalt.
Poisonous Dose of Nickel Salts, * & e e ſº
Symptoms in Frogs, Pigeons, Guinea-Pigs, Rats, Rabbits,
Effects on the Circulation—Nervous System, * s
Action on Striped Muscle,
Separation of Nickel or Cobalt from the organic Matters or Tissues,
Estimation of Cobalt and Nickel,
IV. PRECIPITATED BY AMMONIUM SULPHIDE.
IRON –CHROMIUM–THALLIUM-ALUMINIUM —URANIUM.
1. Iron,
Poisonous Properties of Iron, . g & tº
Ferric Chloride—Pharmaceutical Preparations,
Effects of Ferric Chloride on Animals, º
688, 689
689
689, 690
690
690, 691
691, 692
692, 693
693
693, 694
694, 695
695
695
695, 696
696
696
696, 697
697
CONTENTS.
xxxi
Section
878. Effects on Man, . e o
879. Elimination of Iron Chloride, .
880. Post-mortem. Appearances, . &
881.
882,
883.
884.
885.
886.
887.
888.
889.
890.
891.
892.
893.
894.
895.
Ferrous Sulphate, Copperas, or Green Vitriol, º . *
Search for Iron Salts in the Contents of the Stomach, etc.
2. Chromium.
Poisonous Salts of Chromium—Neutral Chromate of Potash,
Potassic Bichromate, & & º º e
Neutral Lead Chromate, .
Use in the Arts, . º © tº º º e e o
Effects of some of the Chromium Compounds on Animal Life, .
Effects of some of the Chromium Salts on Man— Bichromate Disease,
*: Poisoning by Potassic Bichromate—Statistics—Illustrative
ases, . º º & º º - g g g º º
Poisoning by Chromate of Lead,
Post-mortem Appearances, . • • * & e º º
Detection of the Chromates, and Separation of the Salts of Chromium
from the Contents of the Stomach, . -> º º º e
3. Thallium.
Thallium–General Properties,
Effects of Thallium, &
Separation of Thailium from organic Fluids or solids,
Page
697, 698
698
698, 699
699, 700
700, 701
701
701
701, 702
702
702
702, 703
703, 704
704, 705
705
706
707
707
707
896.
897.
898.
899,
900.
901,
902.
903.
904,
905.
906.
907.
908.
909,
910.
911.
4. Alwmºnium.
Aluminium and its Salts,
Action of Alum Salts,
Post-mortem Appearances,
Detection of Alumina,
5. Uranium.
Poisonous Properties of Uranium Salts,
Detection and Estimation of Uranium, ..
W. ALKALINE EARTHS.
Bari wºm.
Poisonous Salts of Barium, . tº º º tº tº
Chloride of Barium, ->
Baric Carbonate,
Sulphate of Barium, * º - te © -
Effects of the Soluble Salts of Barium on Animals, .
Effects of the Salts of Barium on Man—Fatal Dose,
Symptoms, . e e e º - *
Distribution of Barium in the Body,
Post-mortem Appearances, . e e º e e º º
The Separation of Barium Salts from Organic Solids or Fluids, and
their Identification, º e © t e
707, 708
708, 709
709
, 710
710
710
710, 711
711
711
711
711, 712
713
713, 714
714, 715
715
715, 716
xxxii CONTENTS.
APPENDIX.
TREATMENT BY ANTIDOTES OR OTHERwise of CASEs of PoisonING,
Section - Page
912. Instruments—Emetics—Antidotes, . e tº o 0. e o
913. Alphabetical List of the Chief Poisons, with Antidotes and Treatment, 719, 733
DOMESTIC READY REMEDIES For PoisonING.
914. The Multiple Antidote and Simple Remedies . º º - . 733, 734
INDEx, © - e e º te e * º º . 735–772
LIST OF ILLUSTRATIONS.
Williams’ Apparatus for Investigating the Action of Poisons on the Frog's Heart, 45
Jacobi's Apparatus, • 47
Mercury Pump, . e - & tº c g tº o tº te º 50
Ether Recovery Apparatus, . º ū e e º o e º º 51
Micro-Spectroscope, º o © Q e º o 0. Q e e 57
Diagram showing Absorption Bands produced from Colour Reactions, . ſº 58
Spectroscopic Appearances of Blood, . e e o º o e º 61
Haematin Crystals, - tº e e e © º - tº e e 64
Deaths per Million Living from Alcohol, 1875–1903, . - g g . 143
Tube for Treatment of Liquids by Ethereal Solvents, . e tº e . 163
Diagram of Visual Field in Nitro-Benzol Poisoning, º º te g , 200
Blondlot's Apparatus for Production of Phosphine, tº º º & . 244
Subliming Cell, . • º o e e º º º e t . 260
Crystals of Methyl-Brucine Iodide, tº e g & * t º , 352
Diagram Indicating Action of Atropine on the Heart, . 390
Curves showing Changes in the Pulse, and Arterial Tension produced by an
* Infusion of Digitalis, . º ſº e e © º e ſº 441
Bocklisch's Flask for Distillation in a Vacuum, . e º º e . 508
Berzelius' Tube for Reduction of Arsenic, e o e º º º . 578
Thorpe's Electrolytic Apparatus for Determination of Arsenic, º g . 592
Gabriel Bertrand’s Apparatus for same, . º e e o º e . 595
Bent Tube for Assay of Mercury, . ſº o º • º º tº . 685
PO IS O N S :
THEIR EFFECTS AND DETECTION.
PART I. —INTRODUCTORY.
I.—The Old Poison-LOre.
§ 1. It is significant that the root “tox” of the modern word towicology
can be traced back to a very ancient word meaning “bow ’’ or “arrow,”
or, in its broadest sense, some “tool" used for slaying: hence it is no
far-fetched supposition that the first poison-knowledge was that of the
septic poisons. Perchance the savage found that weapons soiled with
the blood of former victims made wounds fatal; from this observation
the next step naturally would be that of experiment—the arrow or
spear would be steeped in all manner of offensive pastes, and smeared
with the vegetable juices of those plants which were deemed noxious;
and as the effects were mysterious, they would be ascribed to the
supernatural powers, and covered with a veil of superstition.
The history of the poison-lehre, like all history, begins in the region
of the myths: there was a dark saga prevailing in Greece, that in the
far north existed a land ruled by sorcerers—all children of the sun–
and named Aeëtes, Perses, Hecate, Medea, and Circe. Later on, the
enchanted land was localised at Colchis, and Aeëtes and Perses were
said to be brothers. Hecate was the daughter of Perses; she was
married to Aeëtes, and their daughters were Medea and Circe. Hecate
was the discoverer of poisonous herbs, and learned in remedies both evil
and good. Her knowledge passed to Medea, who narcotised the dragon,
the guardian of the golden fleece, and incited Jason to great undertakings.
In the expedition of the Argonauts, the poets loved to describe
Hecate's garden, with its lofty walls. Thrice-folding doors of ebony
barred the entrance, which was guarded by terrible forms: only the
initiated few, only they who bore the leavened rod of expiation, and the
concealed conciliatory offering of the Medea, could enter into the
Sanctuary. Towering above all was the temple of the dread Hecate,
whose priestesses offered to the gods ghastly sacrifices.
I
2 POISONS : THEIR EFFECTS AND DETECTION. [$ 2, 3.
§ 2. The oldest Egyptian king, Menes, and Attalus Phylometer, the
last king of Pergamus, were both famous for their knowledge of plants.
Attalus Phylometer was acquainted with hyoscyamus, aconite, conium,
veratrum, and others; he experimented on the preparation of poisons,
and occupied himself in compounding medicines. Mithradetes Eupator
stood yet higher : the receipt for the famous theriaca, prepared in later
years at an enormous price, and composed of fifty-four different ingredi-
ents, is ascribed to him. The wonderful skill shown by the Egyptians
in embalming and technical works is sufficient to render it fairly certain
that their chemical knowledge was considerable ; and the frequent opera-
tions of one caste upon the dead must have laid the foundations of a
pathological and anatomical culture, of which only traces remain. .
The Egyptians knew prussic acid as extracted in a dilute state from
certain plants, among the chief of which was certainly the peach ; on a
papyrus preserved at the Louvre, M. Duteil read, “Pronounce not the
name of I. A. O. under the penalty of the peach l’ in which dark threat,
without doubt, lurks the meaning that those who revealed the religious
mysteries of the priests were put to death by waters distilled from the
peach. That the priests actually distilled the peach-leaves has been
doubted by those who consider the art of distillation a modern inven-
tion; but this process was well known to adepts of the third and fourth
centuries, and there is no inherent improbability in the supposition that
the Egyptians practised it.*
§ 3. From the Egyptians the knowledge of the deadly drink appears
to have passed to the Romans. At the trial of Antipater,t Verus brought
a potion derived from Egypt, which had been intended to destroy Herod;
this was essayed on a criminal, he died at once. In the reign of Tiberius,
a Roman knight, accused of high treason, swallowed a poison, and fell
dead at the feet of the Senators: in both cases the rapidity of action
appears to point to prussic acid.
The use of poison by the Greeks, as a means of capital punishment,
without doubt favoured suicide by the same means; the easy, painless
death of the state prisoner would be often preferred to the sword by one
tired of life. The ancients looked indeed upon suicide, in certain in-
stances, as something noble, and it was occasionally formally sanctioned.
Thus, Walerius Maximus tells us that he saw a woman of quality, in the
island of Ceos, who, having lived happily for ninety years, obtained
leave to take a poisonous draught, lest, by living longer, she should
happen to have a change in her good fortune; and, curiously enough,
* Zosemus of Alexandria gives a drawing of a still which he states is copied from
the ancient temple of Memphis in Egypt. Analyst, xxx. 295, 1905, and Hoeffer,
Histoire de Chemie, vol. i. p. 262.
+ Jos., Ant., b. xvii. c. 5,
\!
§ 3.] THE OLD POISON-LORE. 3
this sanctioning of self-destruction seems to have been copied in Europe.
Mead relates that the people of Marseilles of old had a poison, kept by
the public authorities, in which cicuta was an ingredient ; a dose was
allowed to any one who could show why he should desire death. What-
ever use or abuse might be made of a few violent poisons, Greek and
Roman knowledge of poisons, their effects and methods of detection,
was stationary, primitive, and incomplete.
Nicander of Colophon (204–138 B.C.) wrote two treatises, the most
ancient works on this subject extant, the one describing the effects of
snake venom; the other, the properties of opium, henbane, certain
fungi, colchicum, aconite, and conium. He divided poisons into those
which kill quickly, and those which act slowly. As antidotes, those
medicines are recommended which excite vomiting—e.g., lukewarm oil,
warm water, mallow, linseed tea, etc.
Apollodorus lived at the commencement of the third century B.C. :
he wrote a work on poisonous animals, and one on deleterious medicines;
these works of Apollodorus were the sources from which Pliny, Heraclitus,
and several of the later writers derived most of their knowledge of poisons.
Dioscorides (40–90 A.D.) well detailed the effects of cantharides, sul-
phate of copper, mercury, lead, and arsenic. By arsenic he would
appear sometimes to mean the sulphides, sometimes the white oxide.
Dioscorides divided poisons, according to their origin, into three classes,
V17. ...—
1. Animal Poisons.—Under this head were classed cantharides and
allied beetles, toads, salamanders, poisonous snakes, a particular variety
of honey, and the blood of the ox, probably the latter in a putrid state.
He also speaks of the “sea-hare.” The sea-hare was considered by the
ancients very poisonous, and Domitian is said to have murdered Titus
with it. It is supposed by naturalists to have been one of the genus
Aplysia, among the gasteropods. Both Pliny and Dioscorides depict the
animal as something very formidable: it was not to be looked at, far
less touched. The aplysiae exhale a very nauseous and foetid odour
when they are approached : the best known of the species resembles,
when in a state of repose, a mass of unformed flesh ; when in motion, it
is like a common slug; its colour is reddish-brown; it has four horns
on its head; and the eyes, which are very small, are situated between
the two hinder ones. This aplysia has an ink reservoir, like the sepia
and ejects it in order to escape from its enemies; it inhabits the muddy
bottom of the water, and lives on small crabs, mollusca, etc.
2. Poisons from Plants.-Dioscorides enumerates opium, black
and white hyoscyamus (especially recognising the activity of the seeds),
mandragora, which was probably a mixture of various solanaceae, conium
(used to poison the condemned by the people of Athens and the dwellers
Y
bº.
4. POISONS : THEIR EFFECTS AND DETECTION. [Š 4.
of ancient Massilia), elaterin, and the juices of species of euphorbia and
apocynea. He also makes a special mention of aconite, the name of
which is derived from Akon, a small city in Heraclea. The Greeks were
well aware of the deadly nature of aconite, and gave to it a mythical
origin, from the foam of the dog Cerberus. Colchicum was also known
to Dioscorides; its first use was ascribed to Medea. Veratrum album
and nigrum were famous medicines of the Romans, and a constituent of
their “rat and mice powders”; they were also used as insecticides.
According to Pliny, the Gauls dipped their arrows in a preparation of
veratrum.* Daphne mezereon, called by the Romans also smilax and
taxus, appears to have been used by Cativolcus, the king of the Eburones,
for the purpose of suicide; or possibly by “taxus.” the yew-tree is
meant.t
The poisonous properties of certain fungi were also known. Nicander
calls the venomous mushrooms the “evil fermentation of the earth,” and
prescribes the identical antidotes which we would perhaps give at the
present time—viz., vinegar and alkaline carbonates.
3. Mineral Poisons.—Arsenic has been already alluded to. The
ancients used it as a caustic and depilatory. Copper was known as
sulphate and oxide; mercury only as cinnabar: lead oxides were used,
and milk and olive-oil prescribed as an antidote for their poisonous
properties. The poison-lehre for many ages was considered as something
forbidden. Galen, in his treatise “On Antidotes,” remarks that the
only authors who dared to treat of poisons were Orpheus, Theologus
Morus, Mendesius the younger, Heliodorus of Athens, Aratus, and a
few others; but none of these treatises have come down to us. From
the close similarity of the amount of information in the treatises of
Nicander, Dioscorides, Pliny, Galen, and Paulus AEgineta, it is probable
that all were derived from a common source.
§ 4. If we turn our attention to early Asiatic history, a very cursory
glance at the sacred writings of the East will prove how soon the art of
poisoning, especially in India, was used for the purpose of suicide, revenge,
or robbery. .
The ancient practice of the Hindoo widow—self-immolation on the
burning pile of her husband—is ascribed to the necessity which the
Brahmins were under of putting a stop to the crime of domestic poison-
ing. Every little conjugal quarrel was liable to be settled by this form
of secret assassination, but such a law, as might be expected, checked
the practice.
Poison was not used to remove human beings alone, for there has
been from time immemorial in India much cattle-poisoning. In the
Institutes of Menu, it is ordained that when cattle die the herdsman
* Pliny, xxv. 5. + De Bello Gallico, vi. 31.
§ 5.] THE OLD POISON-LORE. 5
shall carry to his master their ears, their hides, their tails, the skin
below their navels, their tendons, and the liquor oozing from their
foreheads. Without doubt these regulations were directed against
cattle-poisoners.
The poisons known to the Asiatics were arsenic, aconite, opium, and
various solanaceous plants. There has been a myth floating through
the ages that a poison exists which will slay a long time after its intro-
duction. All modern authors have treated the matter as an exaggerated
legend, but, for my own part, I see no reason why it should not, in
reality, be founded on fact. There is little doubt that the Asiatic
poisoners were well acquainted with the infectious qualities of certain
fevers and malignant diseases. Now, these very malignant diseases
answer precisely to the description of a poison which has no immediate
effects. Plant smallpox in the body of a man, and for a whole fortnight
he walks about, well and hearty. Clothe a person with a garment
soaked in typhus, and the same thing occurs—for many days there will
be no sign of failure. Again, the gipsies, speaking a tongue which is
essentially a deformed prakrit, and therefore Indian in origin, have long
possessed a knowledge of the properties of the curious “mucor
phycomyces.” This was considered an alga by Agaron, but Berkeley
referred it to the fungi. The gipsies are said to have administered the
spores of this fungi in warm water. In this way they rapidly attach
themselves to the mucous membrane of the throat, all the symptoms of
a phthisis follow, and death takes place in from two to three weeks.
Mr. Berkeley informed me that he has seen specimens growing on broth
which had been rejected from the stomach, and that it develops in
enormous quantities on oil-casks and walls impregnated with grease.
The filaments are long, from 12 to 18 inches, and it is capable of very
rapid development.
There is also a modern poison, which, in certain doses, dooms the
unfortunate individual to a terrible malady, simulating, to a considerable
extent, natural disease—that is phosphorus. This poison was, however,
unknown until some time in the eleventh century, when Alchid Becher,
blindly experimenting on the distillation of urine and carbon, obtained
his “escarboucle,” and passed away without knowing the importance of
his discovery, which, like so many others, had to be rediscovered at a
later period. -
§ 5. The Hebrews were acquainted with certain poisons, the exact
nature of which is not quite clear. The words “rosch " and “chema”
seem to be used occasionally as a generic term for poison, and sometimes
to mean a specific thing ; “rosch,” especially, is used to signify some
poisonous parasitic plant. They knew yellow arsenic under the name of
“8am,” aconite under the name of “boschka,” and possibly “son” means
6 POISONS : THEIR EFFECTS AND DETECTION. [$ 6.
ergot.” In the later period of their history, when they were dispersed
through various nations, they would naturally acquire the knowledge of
those nations, without losing their own.
§ 6. The part that poison has played in history is considerable.
The pharmaceutical knowledge of the ancients is more graphically and
terribly shown in the deaths of Socrates, Demosthenes, Hannibal, and
Cleopatra, than in the pages of the older writers on poisons.
In the reign of Artaxerxes II. (Memnon), (B.C. 405–359), Phrysa
poisoned the queen Statira by cutting food with a knife poisoned on one
side only. Although this has been treated as an idle tale, yet two
poisons, aconite and arsenic, were at least well known; either of these
could have been in the way mentioned introduced in sufficient quantity
into food to destroy life.
In the early part of the Christian era professional poisoners arose,
and for a long time exercised their trade with impunity.i Poisoning
was so much in use as a political engine that Agrippina (A.D. 26)
refused to eat of some apples offered to her at table by her father-in-
law, Tiberius.
It was at this time that the infamous Locusta flourished. She is said
to have supplied, with suitable directions, the poison by which Agrippina
got rid of Claudius; and the same woman was the principal agent in the
preparation of the poison that was administered to Britannicus, by order
of his brother Nero. The details of this interesting case have been
recorded with some minutemess.
It was the custom of the Romans to drink hot water, a draught
nauseous enough to us, but, from fashion or habit, considered by them a
luxury; and, as no two men's tastes are alike, great skill was shown by
the slaves in bringing the water to exactly that degree of heat which
their respective masters found agreeable. }
The children of the Imperial house, with others of the great Roman
families, sat at the banquets at a smaller side table, while their parents
reclined at the larger. A slave brings hot water to Britannicus; it is too
hot ; Britannicus refuses it. The slave adds cold water; and it is this
cold water that is supposed to have been poisoned ; in any case,
Britannicus had no sooner drunk of it than he lost voice and respiration.
Agrippina, his mother, was struck with terror, as well as Octavia, his
sister. Nero, the author of the crime, looks coldly on, saying that such
fits often happened to him in infancy without evil result ; and after a
few moments’ silence the banquet goes on as before. If this were not
* R. J. Wunderbar, Biblisch-talmudische Medicin. Leipzig, 1850–60.
† Tacitus, lib. xii., xiii. Mentioned also by Juvenal and Suetonius.
# The death of Arius (A.D. 325) is ascribed by Gibbon either to a miracle or to
poison—“his bowels suddenly burst out in a privy.”
§ 6.] THE OLD POISON-LORE. 7
sudden death from heart or brain disease, the poison must have been
either a cyanide or prussic acid.
In those times no autopsy was possible : although the Alexandrian
school, some 300 years before Christ, had dissected both the living and
the dead, the work of Herophilus and Erasistratus had not been pursued,
and the great Roman and Greek writers knew only the rudiments of
human anatomy, while as to pathological changes and their true inter-
pretation, their knowledge may be said to have been absolutely nil. It
was not, indeed, until the fifteenth century that the Popes, silencing
ancient scruples, authorised dissections; and it was not until the
sixteenth century that Vesalius, the first worthy of being considered a
great anatomist, arose. In default of pathological knowledge, the
ancients attached great importance to mere outward marks and discolora-
tions. They noted with special attention spots and lividity, and supposed
that poisons singled out the heart for some quite peculiar action, altering
its substance in such a manner that it resisted the action of the funeral
pyre, and remained unconsumed. It may, then, fairly be presumed that
many people must have died from poison without suspicion, and still
more from the sudden effects of latent disease, ascribed wrongfully to
poison. For example, the death of Alexander was generally at that time
ascribed to poison; but Littré has fairly proved that the great emperor,
debilitated by his drinking habits, caught a malarious fever in the
marshes around Babylon, and died after eleven days' illness. If, added
to sudden death, the body, from any cause, entered into rapid putrefac-
tion, such signs were considered by the people absolutely conclusive of
poisoning; this belief, indeed, prevailed up to the middle of the
seventeenth century, and lingers still among the uneducated at the
present day. Thus, when Britannicus died, an extraordinary lividity
spread over the face of the corpse, which they attempted to conceal by
painting the face. When Pope Alexander VI. died, probably enough
from poison, his body (according to Guicciardini) became a frightful
spectacle—it was livid, bloated, and deformed ; the gorged tongue
entirely filled the mouth ; from the nose flowed putrid pus, and the
stench was horrible in the extreme.
All these effects of decomposition, we know, are apt to arise in coarse,
obese bodies, and accompany both natural and unnatural deaths; indeed,
if we look strictly at the matter, putting on one side the preservative
effects of certain metallic poisons, it may be laid down that generally the
Corpses of those dying from poison are less apt to decompose rapidly than
those dying from disease—this for the simple reason that a majority of
diseases cause changes in the fluids and tissues, which render putrefactive
changes more active, while, as a rule, those who take poison are suddenly
killed, with their fluids and tissues fairly healthy.
8 POISONS : THEIR EFFECTS AND DETECTION. [$ 6
When the Duke of Burgundy desired to raise a report that John,
Dauphin of France, was poisoned (1457), he described the imaginary
event as follows:—
“One evening our most redoubtable lord and nephew fell so grievously
sick that he died forthwith. His lips, tongue, and face were swollen;
his eyes started out of his head. It was a horrible sight to see—for so
look people that are poisoned.”
The favourite powder of the professional poisoner, arsenic, was known
to crowned heads in the fourteenth century, and there has come down
to us a curious document, drawn out by Charles le Mauvais, King of
Navarre. It is a commission of murder, given to a certain Woudreton,
to poison Charles VI., the Duke of Valois, brother of the king, and his
uncles, the Dukes of Berry, Burgundy, and Bourbon —
“Go thou to Paris; thou canst do great service if thou wilt; do what
I tell thee; I will reward thee well. Thou shalt do thus: There is a
thing which is called sublimed arsenic ; if a man eat a bit the size of a
pea he will never survive. Thou wilt find it in Pampeluna, Bordeaux,
Bayonne, and in all the good towns through which thou wilt pass, at
the apothecaries' shops. Take it and powder it ; and when thou shalt
be in the house of the king, of the Count de Valois, his brother, the
Dukes of Berry, Burgundy, and Bourbon, draw near, and betake thyself
to the kitchen, to the larder, to the cellar, or any other place where thy
point can be best gained, and put the powder in the soups, meats, or
wines, provided that thou canst do it secretly. Otherwise, do it not.”
Woudreton was detected, and executed in 1384.”
A chapter might be written entitled “royal poisoners.”f King
Charles IX. even figures as an experimentalist. # An unfortunate cook
has stolen two silver spoons, and, since there was a question whether
“Bezoar” was an antidote or not, the king administers to the cook a
lethal dose of corrosive sublimate, and follows it up with the antidote ;
but the man dies in seven hours, although Paré also gives him oil.
Truly a grim business
The subtle method of removing troublesome subjects has been more
often practised on the Continent than in England, yet the English throne
in olden time is not quite free from this stain.S The use of poison is
* Trésor de Chartes. Charles de Navarre. P. Mortonval, vol. ii. p. 384.
+ Napoleon Bonaparte poisoned at Jaffa (1799) those of his soldiers who had
plague and were too ill to be moved.—Memoirs of Napoleon Bonaparte, by F. de
Bourrienne.
# CEuvres de Paré, 2nd ed., liv. xx. Des Vemines, chap. xliv, p. 507.
§ For example, King John is believed to have poisoned Maud Fitzwalter by “a
poisoned egg.”
“In the reign of King John, the White Tower received one of the first and
fairest of a long line of female victims in that Maud Fitzwalter who was known to
§ 7.] THE OLD POISON-LORÉ. 9
wholly opposed to the Anglo-Saxon method of thought. To what anger
the people were wrought on detecting poisoners is seen in the fact that,
in 1542, a young woman was boiled alive in Smithfield for poisoning
three households.”
§ 7. Two great criminal schools arose from the fifteenth to the
seventeenth centuries in Venice and Italy. The Venetian poisoners are
of earlier date than the Italian, and flourished chiefly in the fifteenth
century. Here we have the strange spectacle, not of the depravity of
individuals, but of the government of the State formally recognising
secret assassination by poison, and proposals to remove this or that
prince, duke, or emperor, as a routine part of their deliberations. Still
more curious and unique, the dark communings of “the council of tem. "
were recorded in writing, and the number of those who voted for and
who voted against the proposed crime, the reason for the assassination,
and the sum to be paid, still exist in shameless black and white. Those
who desire to study this branch of secret history may be referred to a
small work by Carl Hoff, which gives a brief account of what is known
of the proceedings of the council. One example will here suffice. On
the 15th of December 1513 a Franciscan brother, John of Ragubo,
offered a selection of poisons, and declared himself ready to remove any
objectionable person out of the way. For the first successful case he
required a pension of 1500 ducats yearly, which was to be increased on
the execution of future services. The presidents, Girolando Duoda and
Pietro Guiarina, placed the matter before the “ten " on the 4th of
January 1514, and on a division (10 against 5) it was resolved to accept
the singers of her time as Maud the Fair. The father of this beautiful girl was
Robert, Lord Fitzwalter, of Castle Baynard, on the Thames, one of John's greatest
barons. Yet the king, during a fit of violence with the queen, fell madly in love
with this young girl. As neither the lady herself nor her powerful sire would listen
to his disgraceful suit, the king is said to have seized her by force at Dunmow, and
brought her to the Tower. Fitzwalter raised an outcry, on which the king sent
troops into Castle Baynard and his other houses ; and when the baron protested
against these wrongs, his master banished him from the realm. Fitzwalter fled to
France with his wife and his other children, leaving his daughter Maud in the
Tower, where she suffered a daily insult in the king's unlawful suit. On her proud
and scornful answer to his passion being heard, John carried her up to the roof, and
locked her in the round turret, standing on the north-east angle of the keep.
Maud's cage was the highest, chilliest den in the Tower; but neither cold, nor
Solitude, nor hunger could break her strength. In the rage of his disappointed
love, the king sent one of his minions to her room with a poisoned egg, of which the
brave girl ate and died.”—Her Majesty's Tower, by Hepworth Dixon. Lond., 1869;
i. p. 46.
* “This yeare, the 17th of March, was boyled in Smithfield one Margaret Davie,
a mayden, which had pouysoned 3 householdes that she dwelled in. One being her
mistress, which dyed of the same, and one Darington and his wyfe, which she also
dwelled with in Coleman Street, which dyed of the same, and also one Tinleys,
which dyed also of the same.”—Wriotherley's Chronicle, A.D. 1542.
IO POISONS : THEIR EFFECTS AND DETECTION. [$ 7.
so patriotic an offer, and to experiment first on the Emperor Maximilian.
The bond laid before the “ten” contained a regular tariff—for the great
Sultan 500 ducats, for the King of Spain 150 ducats, but the journey
and other expenses were in each case to be defrayed; the Duke of Milan
was rated at 60, the Marquis of Mantua at 50, the Pope could be removed
at 100 ducats. The curious offer thus concludes:—“The farther the
journey, the more eminent the man, the more it is necessary to reward
the toil and hardships undertaken, and the heavier must be the pay-
ment.” The council appear to have quietly arranged thus to take away
the lives of many public men, but their efforts were only in a few cases
successful. When the deed was done, it was registered by a single
marginal note, “factum.”
What drugs the Venetian poisoners used is uncertain. The Italians
became notorious in the sixteenth and seventeenth centuries for their
knowledge of poisons, partly from the deeds of Toffana and others, and
partly from the works of J. Baptista Porta, who wrote a very comprehen-
sive treatise, under the title of Natural Magic,” and managed to slide
into the text, in the sections on cooking (De Re Coquinaria, lib. xiv.), a
mass of knowledge as to the preparation of poisons. There are prescrip-
tions that little accord with the title, unless indeed the trades of cook
and poisoner were the same. He gives a method of drugging wine with
belladonna root, for the purpose of making the loaded guest loathe drink;
he also gives a list of solanaceous plants, and makes special mention of
nux vomica, aconite, veratrum, and mezereon. Again, in the section (De
Ancupio, lib. xv.) he gives a recipe for a very strong poison which he calls
“venenum lupinum ”; it is to be made of the powdered leaves of Aconi-
tum lycoctonum, Taacus baccata, powdered glass, caustic lime, Sulphide
of arsenic, and bitter almonds, the whole to be mixed with honey, and
made into pills the size of a hazel-nut.
In the section De Medicis Experimentis he gives a process to poison
a sleeping person : the recipe is curious, and would certainly not have
the intended effect. A mixture of hemlock juice, bruised datura,
stramonium, belladonna, and opium is placed in a leaden box with a
perfectly fitting cover, and fermented for several days; it is then opened
under the nose of the sleeper. Possibly Porta had experimented on
small animals, and had found that such matters, when fermented, exhaled
enough carbonic acid gas to kill them, and imagined, therefore, that the
same thing would happen if applied to the human subject. However
this may be, the account which Porta gives of the effects of the solana-
ceous plants, and the general tone of the work, amply prove that he
was no theorist, but had studied practically the actions of poisons.
* J. Bapt. Porta, born 1537, died 1615. Neapolitani Magiae Naturalis. Neapoli,
1589.
§ 7.] THE OLD POISON-LORE. I I
The iniquitous Toffana (or Tophana) made solutions of arsenious acid
of varying strength, and sold these solutions in phials under the name of
“Acquetta di Napoli” for many years. She is supposed to have poisoned
more than 600 persons, among whom were two Popes—viz., Pius III.
and Clement XIV. The composition of the Naples water was long a
profound secret, but it is said to have been known by the reigning Pope
and by the Emperor Charles VI. The latter told the secret to Dr
Garelli, his physician, who, again, imparted the knowledge to the famous
Friedrich Hoffman in a letter still extant. Toffana was brought to justice
in 1709, but, availing herself of the immunity afforded by convents,
escaped punishment, and continued to sell her wares for twenty years
afterwards. When Kepfer * was in Italy he found her in a prison at
Naples, and many people visited her, as a sort of lion (1730). With
the Acqua Toffana, the “Acquetta di Perugia’’ played at the same
time its part. It is said to have been prepared by killing a hog, dis-
jointing the same, strewing the pieces with white arsenic, which was
well rubbed in, and then collecting the juice which dropped from
the meat; this juice was considered far more poisonous than an
ordinary solution of arsenic. The researches of Selmi on compounds
containing arsenic, produced when animal bodies decompose in arsenical
fluids, lend reason and support to this view ; and probably the juice
would not only be very poisonous, but act in a different manner,
and exhibit symptoms different from those of ordinary arsenical
poisoning. Toffana had disciples; she taught the art to Hieronyma
Spara, who formed an association of young married women during
the popedom of Alexander VII. ; these were detected on their own
confession.f
Contemporaneously with Toffana, another Italian, Exili or Egide or
Gilles, attached to the service of Queen Christiana of Sweden, devoted
himself to similar crimes. He made the acquaintance of M. de St.
Croix or Godin, a captain of horse in the Tracy regiment, when both
were imprisoned in the Bastille. It is popularly supposed that he it
was who instructed St. Croix in the use of poisons, and St. Croix, in his
turn, imparted the secret to his partner Madame (or Marchioness) de
Brinvilliers, a little woman with very soft blue eyes, and said to be of
marvellous beauty. Frantz Funck Brentano i denies this account, saying
that the true version is that St. Croix and Madame de Brinvilliers got
their knowledge from Christopher Glaser, a Swiss chemist, author of
a treatise on chemistry, and discoverer of potassium sulphate. The
* Kepfer's Travels. Lond., 1758.
f Le Bret's Magazin zu Gebrauche der Staat w. Kirchen-Geschichte, Theil 4.
Frankfort and Leipzig, 1774.
# Princes and Poisoners: Studies of the Cowrt of Lowis XIV.
I 2 POISONS : THEIR EFFECTS AND DETECTION. [$ 7.
lovers, at all events, wrote of their poisons as “Glaser's recipes,” the
chief ingredient of which was without doubt arsenic.
Madame de Brinvilliers poisoned her father, her brothers, and other
members of her family; she is also said to have experimented on the
patients at the Hôtel Dieu, in order to test the strength of the powders
prepared for her by St. Croix. These powders were afterwards called
“Les poudres de succession,” from a joking remark made by Madame
in her cups. St. Croix robbed the executioner by dying a natural death,
and Madame de Brinvilliers, after a sensational trial, at the end of which
the first president wept bitterly and all the judges shed tears, was
sentenced to torture * and death. The tale that St. Croix was suffocated
through the breaking of a glass mask while he was preparing some
poisonous substances, and that Madame de Brinvilliers was courted and
arrested by a police officer disguised as an abbé, according to Funck
Brentano, has no foundation in fact.f
The numerous attempts of the Italian and Venetian poisoners on the
lives of monarchs and eminent persons cast for a long time a cloud over
regal domestic peace. Bullets and daggers were not feared, but in their
place the dish of meat, the savoury pasty, and the red wine were re-
garded as possible carriers of death. No better example of this dread
can be found than, at so late a period as the reign of Henry VIII., f the
extraordinary precaution thought necessary for preserving the infant
Prince of Wales.
* The Marchioness was imprisoned in the Conciergerie and tortured. Victor
Hugo, describing the rack in that prison, says, “The Marchioness de Brinvilliers
was stretched upon it stark naked, fastened down, so to speak, quartered by four
chains attached to the four limbs, and there suffered the frightful extraordinary
torture by water,” which caused her to ask, “How are you going to contrive to put
that great barrel of water in this little body ?”—Things seen by Victor Hugo, vol. i.
The water torture was this:—a huge funnel-like vessel was fitted on to the neck,
the edge of the funnel coming up to the eyes; on now pouring water into the
funnel so that the fluid rises above the nose and mouth, the poor wretch is bound to
swallow the fluid or die of suffocation ; if indeed the sufferer resolve to be choked,
in the first few moments of unconsciousness the fluid is swallowed automatically,
and air again admitted to the lungs; it is therefore obvious that in this way pro-
digious quantities of fluid might be taken.
+ For the court of poisoners (chambre ardente) and the histories of St. Croix, De
Brinvilliers, the priest Le Sage, the women La Voisin, and La Vigoureux, the reader
may be referred to Voltaire's Siècle de Louis XIV., Madame de Sévigné's Lettres,
Martinière’s Hist, de la Règne de Lowis XIV., Strutzel, De Venenis, etc.
† Henry VIII., at one time of his life, was (or pretended to be) apprehensive of
being poisoned; it was, indeed, a common belief of his court that Anne Boleyn
attempted to dose him. “The king, in an interview with the young Prince Henry,
burst into tears, saying that he and his sister (meaning the Princess Mary) might
thank God for having escaped from the hands of that accursed and venomous harlot,
who had intended to poison them.”—A Chronicle of England during the Reign of the
Tudors, by W. J. Hamilton. Introduction, p. xxi.
§ 8.] MoDERN METHODS OF CHEMICALLY DETECTING POISONS. 13
“No person, of whatsoever rank, except the regular attendants in the
nursery, should approach the cradle, except with an order from the king's
hand. The food supplied to the child was to be largely ‘assayed,’ and
his clothes were to be washed by his own servants, and no other hand
might touch them. The material was to be submitted to all tests. The
chamberlain and vice-chamberlain must be present, morning and evening,
when the prince was washed and dressed, and nothing of any kind
bought for the use of the nursery might be introduced until it was
washed and perfumed. No person, not even the domestics of the palace,
might have access to the prince's rooms except those who were specially
appointed to them, nor might any member of the household approach
London, for fear of their catching and conveying infection.” ”
However brief and imperfect the foregoing historical sketch of the
part that poison has played may be, it is useful in showing the absolute
necessity of a toxicological science—a science embracing many branches
of knowledge. If it is impossible now for Toffanas, Locustas, and other
specimens of a depraved humanity to carry on their crimes without
detection; if poison is the very last form of death feared by eminent
political persons; it is not so much owing to a different state of society,
as to the more exact scientific knowledge which is applied during life to
the discrimination of symptoms, distinguishing between those resulting
from disease and those due to injurious substances, and after death to a
highly developed pathology, which has learned, by multiplied observa-
tions, all the normal and abnormal signs in tissues and organs; and,
finally, to an ever-advancing chemistry, which is able in many instances
to separate and detect the hurtful and noxious thing, although hid for
months deep in the ground.
II.-Growth and Development of the Modern Methods of
Chemically Detecting Poisons.
$ 8. The history of the detection of poisons has gone through several
phases. The first phase has already been incidentally touched upon—
i.e., detection by antecedent and surrounding circumstances, aided some-
times by experiments on animals. If the death was sudden, if the post-
mortem decomposition was rapid, poison was indicated: sometimes a
portion of the food last eaten, or the suspected thing, would be given
to an animal ; if the animal also died, such accumulation of proof would
render the matter beyond doubt. The modern toxicologists are more
sceptical, for even the last test is not of itself satisfactory. It is now
* Froude's History qf England, vol. iii. p. 262.
I4. POISONS : THEIR EFFECTS AND DETECTION. [$ 9.
known that meat may become filled with bacilli and produce rapid death,
and yet no poison, as such, has been added.
In the next phase, the doctors were permitted to dissect, and to
familiarise themselves with pathological appearances. This was a great
step gained: the apoplexies, heart diseases, perforations of the stomach,
and fatal internal haemorrhages could no longer be ascribed to poison.
If popular clamour made a false accusation, there was more chance of
a correct judgment. It was not until the end of the eighteenth and
the beginning of the last century, however, that chemistry was far
enough advanced to test for the more common mineral poisons; the
modern phase was then entered on, and toxicology took a new departure.
§ 9. From the treatise of Barthélémy d'Anglais * in the thirteenth
century (in which he noticed the poisonous properties of quicksilver
vapour), up to the end of the fifteenth century, there are numerous
treatises upon poison, most of which are mere learned compilations, and
scarcely repay perusal. In the sixteenth century, there are a few works,
such, for example, as Porta, which partook of the general advancement of
science, and left behind the stereotyped doctrine of the old classical
schools.i
In the seventeenth century the Honourable Robert Boyle made some
shrewd observations, bearing on toxicology, in his work on The Useful.
ness of Natural Philosophy, etc. : Oxford, 1654, Nicolas L'Emery also
wrote a Cours de Chimie—quite an epitome of the chemical science of
the time. .
In the eighteenth century still further advances were made. Richard
Mead published his ingenious Mechanical Theory of Poisons. Great
chemists arose—Stahl, Marggraf, Brandt, Bergmann, Scheele, Berthollet,
Priestley, and lastly, Lavoisier—and chemistry, as a science, was born.
Of the chemists quoted, Scheele, in relation to toxicology, stands chief.
It was Scheele who discovered prussic acid,S without, however, noting
its poisonous properties; the same chemist separated oxalic acid from
sorrel, and made the important discovery that arsenic united with
hydrogen, forming a foetid gas, and, moreover, that this gas could be
* De Rerum Proprietaribw8.
† In the sixteenth century it was not considered proper to write upon poisons.
Jerome Cardan declared a poisoner worse than a brigand, “and that is why I have
refused not only to teach or experiment on such things, but even to know them.”—
J. Carden : De Subtilitate. Basel, 1558.
f Cours de Chimie, contenant la manière de faire les opérations qui sont en usage
dans la Médicine. Paris, 1675.
§ Opuscula Chemica, vol. ii. pp. 148–174.
|| De Terra Rhubarbi et Acido Acetosellae. Nova Acta Acad. Veg. Swed. Amni,
1784. Opuscula Chemica, vol. ii. pp. 187–195.
Bergmann first described oxalic acid as obtained by the oxidation of saccharine
bodies; but Scheele recognised its identity with the acid contained in sorrel.
§ IO, II.] MODERN METHODS OF CHEMICALLY DETECTING POISONS. I 5
decomposed by heat.” From this observation, a delicate test for arsenic
was afterwards elaborated, which for the first time rendered the most
tasteless and easily administered poison in the whole world at once the
easiest of detection. The further history of what is now called “Marsh's
Test' is as follows:—
§ 10. Proust f observed that a very foetid hydrogen gas was disengaged
when arsenical tin was dissolved in hydrochloric acid, and that arsenic
was deposited from the inflamed gas on cold surfaces which the flame
touched. Trommsdorff next announced, in 1803, that when arsenical
zinc was introduced into an ordinary flask with water and sulphuric
acid, an arsenical hydrogen was disengaged ; and if the tube was
sufficiently long, arsenic was deposited on its walls.; Stromeyer, Gay-
Lussac, Thenard, Gehlen, and Davy later studied this gas, and Serullas
in 1821 proposed this reaction as a toxicological test. Lastly, in 1836,
Marsh published his Memoir.S He constructed a special apparatus
of great simplicity, developed hydrogen by means of zinc and sulphuric
acid, inflamed the issuing gas, and obtained any arsenic present as a
metal, which could be afterwards converted into arsenious acid, etc.
This brief history of the so-called “Marsh's Test" amply shows
that Marsh was not the discoverer of the test. Like many other useful
processes, it seems to have been evolved by a combination of many
minds. It may, however, be truly said that Marsh was the first who
perfected the test and brought it prominently forward.
§ 11. Matthieu Joseph Bonaventura Orfila must be considered the
father of modern toxicology. His great work, Traité de Toacicologie,
was first published in 1814, and went through many editions. Orfila's
chief merit was the discovery that poisons were absorbed and accumu-
lated in certain tissues—a discovery which bore immediate fruit, and
greatly extended the means of seeking poisons. Before the time of
Orfila, a chemist not finding anything in the stomach would not have
troubled to examine the liver, the kidney, the brain, or the blood. The
immense number of experiments which Orfila undertook is simply
marvellous. Some are of little value, and teach nothing accurately
as to the action of poisons—as, for example, many of those in which he
tied the gullet in order to prevent vomiting, for such are experiments
under entirely unnatural conditions; but there are still a large number
which form the very basis of our pathological knowledge.
Orfila's method of experiment was usually to take weighed or
* Mémoires de Scheele, t. i., 1775.
t Proust, Annales de Chimie, t. xxviii., 1798.
# Nicholson's Journal, vol. vi.
§ “Description of a New Process of Separating Small Quantities of Arsenic from
Substances with which it is mixed.” Ed. New. Phil. Jowrmal, 1836.
I6 POISONS: THEIR EFFECTS AND DETECTION. [$ 12, 13.
measured quantities of poison, to administer them to animals, and then
after death—first carefully noting the changes in the tissues and organs
— to attempt to recover by chemical means the poison administered.
In this way he detected and recovered nearly all the organic and
inorganic poisons then known ; and most of his processes are, with
modifications and improvements, in use at the present time.*
§ 12. The discovery of the alkaloids at the commencement of the
nineteenth century certainly gave the poisoner new weapons; yet the
same processes (slightly modified) which separated the alkaloids from
plants also served to separate them from the human body. In 1803
Derosne discovered narcotine and morphine, but he neither recognised
the difference between these two substances, nor their basic properties.
Sertürner from 1805 devoted himself to the study of opium, and made
a series of discoveries. Robiquet, in 1807, recognised the basic characters
of narcotine. In 1818 Pelletier and Caventou separated strychnine;
in 1819, brucine; and in the same year delphinine was discovered
simultaneously by Brande, Lassaigne, and Feneuille. Coniine was
recognised by Giesecke in 1827, and in the following year, 1828,
nicotine was separated by Reimann and Posselt. In 1832 Robiquet
discovered codeine; and in 1833 atropine, aconitine, and hyoscyamine
were distinguished by Geiger and Hesse. Since them, every year has
been marked by the separation of some new alkaloid, from either
animal or vegetable substances. So many workers in different countries
now began to study and improve toxicology, that it would exceed the
limits and be foreign to the scope of this treatise to give even a brief
résumé of their labours. It may, notwithstanding, be useful to append
a short bibliography of the chief works on toxicology of the last
century.
s 13. BIBLIOGRAPHY OF THE CHIEF WORKS ON TOXICOLOGY
(NINETEENTH CENTURY).
ANGLADA, Jos.—“Traité de Toxicologie Générale,” etc. Montpellier et Paris, 1835.
AUTENRIETH.—“Kurze Anleitung zur Auffindung der Gifte.” Freiburg, 1892.
BANDLIN, O. —“Die Gifte.” Basel, 1869–1873.
BAUMERT, G.—“Lehrbuch der gerichtl, Chemie.” Braunschweig, 1889–92.
BAyARD, HENRI.—“Manuel Pratique de Médecine Légale.” Paris, 1843.
* Orfila’s chief works are as follows:–
Traité des Poisons, 2 vols., 8vo, Paris, 1814.
Leçons de Chimie, appliquées à la Mèd. Pratique. 16mo. Brussels, 1836.
Mémoire swr la Nicotime et la Comicine. Paris, 1851.
Leçons de la Méd. Légale, 8vo. Paris, 1821.
Traité des Earhwmations Juridiques, et Considérations sur les Changements
Physiques que les Cadavres eprouwent en se pourrissant, 2 tom. Paris, 1831.
§ 13.] BIBLIOGRAPHY. - 17
BELLINI, RANIERI. -“Manuel de Tossicologia.” Pisa, 1878.
BERLIN, N. J.-"Nachricht, die gewöhnlichen Gifte chemisch zu entdecken.”
Stockholm, 1845.
BERNARD, C.—“Leçons sur les Effets des Substances Toxiques et Médicamenteuses.”
Paris, 1857.
BERTRAND, C. A. R. A.—“Manuel Médico-Légale des Poisons introduits dans
l’Estomac, et les Moyens Thérapeutiques qui leur conviennent: suivi d'un
Plan d’Organisation Médico-Judiciare, et d’un Tableau de la Classification
Générale des Empoisonnemens.” Paris, 1818.
Binz, C.—“Intoxicationen” in Gerhardt’s “Handbuch der Kinderkrankheiten.”
iii. Heft. Tubingen, 1878.
BLyTH, A. WYNTER.—“A Manual of Practical Chemistry: The Analysis of Foods
and the Detection of Poisons.” London, 1879.
BookER, FRIEDER. WILHELM.—“Die Vergiftungen in forensischer u. klinischer
Beziehung.” Iserlohn, 1857.
BöHM, R., NAUNYN, B., and von BoECK, H.-" Handbuch der Intoxicationen.”
(Bd. 15 of the German edition of Ziemssen's Cyclopædia.)
BRANDT, PHöBus, and RATZEBURG.—“Deutschlands Giftgewächse.” Berlin,
1834–38 (2 vols., with 56 coloured plates).
BRIAND, J., and CHAUDE, ERN.—“Manuel Complet de Médecine Légale.” (The
latest edition, 1879.) The chemical portion is by J. Bouis.
BUCHNER, E. –“Lehrbuch der gerichtlichen Medicin für Aerzte u. Juristen.” 3rd
ed. München, 1872.
CASPER, J. L.—“Handbuch der gerichtlichen Medicin.” 7th ed. Berlin, 1881.
CHEvALLIER, A.—“Traité de Toxicologie et de Chimie Judiciaire.” Paris, 1868.
CHIAJE, STEF.—“Enchiridis di Tossicologia teorico-pratica.” 3rd ed. Napoli,
1858,
CHRISTIsoN, RoBERT.-“A Treatise on Poisons.” Edinburgh, 1830. (A third
edition appeared in 1836.)
CoRNEVIN, C.—“Des Plantes Wénéneuse.” Paris, 1887.
DEVERGIE, ALPHoNSE.—“Médecine Légale, Théorique, et Pratique.” 3rd ed.
Paris, 1852.
DRAGENDoRFF, JEAN GEORGES.—“Die gerichtlich-chemische Ermittelung von
Giften in Nahrungsmitteln, Luftgemischen, Speiseresten, Körpertheilen,”
etc. St. Petersburg, 1868. 3rd ed. Göttingen, 1888.
— “Untersuchungen aus dem Pharmaceutischen Institute in Dorpat. Beiträge
zur gerichtlichen Chemie einzelner organischer Gifte.” Erstes Heft. St.
Petersburg, 1871.
— “Jahresbericht tiber die Fortschritte der Pharmacognosie, Pharmacie, und
Toxicologie.” Herausgegeben von Dr. Dragendorff. 1876.
DUFLOs, A.—“Handbuch der angewandten gerichtlich-chemischen Analyse der
chemischen Gifte, ihre Erkennung in reinem Zustande u. in Gemengen
betreffend.” Breslau u. Leipzig, 1873. .
EULENBERG, Dr. HERMANN.—“Handbuch der Gewerbe-Hygiene.” Berlin, 1876.
FALOK, C. PH.—“Die Klinischwichtigen Intoxicationen.” (Handbuch der spec,
Pathologie u. Therapie red. von R. Virchow, Bd. 2.) Erlangen, 1854.
FALCK, FERD. AUG.—“Lehrbuch der praktischen Toxicologie.” Stuttgart, 1880.
FLANDIN, C.—“Traité des Poisons, ou Toxicologie appliquée à la Médecine Légale,
à la Physiologie, et à la Thérapeutique.” Paris, 1847, 1853.
FRöHNER, EUG.-“Lehrbuch der Toxicologie für Thierärzte.” Stuttgart, 1890.
GALTIER, C. P.-‘‘Traité de Toxicologie Medico-Légale et de la Falsification des
Aliments,” etc. Paris, 1845.
—— “Traité de Toxicologie Médicale, Chimique et Légale,” etc. Paris, 1855. A
later edition of the same work.
2
I8 POISONS : THEIR EFFECTS AND DETECTION. [š I3.
GREENE, WILL. H.-‘‘A Practical Handbook of Medical Chemistry, applied to
Clinical Research and the Detection of Poisons.” Philadelphia, 1880.
GUERIN, G.-“Traité Pratique d’Analyse Chimique et de Recherches Toxicologiques.”
Paris, 1893.
GUY, W. A., and FERRIER, DAVID.—“Principles of Forensic Medicine.” London,
1874.
HARNACK, ERICH.-“Lehrbuch der Arzneimittellehre,” etc. Hamburg, 1883.
HAssELT, VAN, A. W. M.–" Handbuch der Giftlehre für Chemiker, Aerzte,
Apotheker, u. Richtspersonen.” (A German translation of the original
Dutch edition, edited by J. B. Henkel. Braunschweig, 1862. Supplemental
vol. by N. Husemann, Berlin, 1867.)
HELWIG, A.-“Das Mikroskop in der Toxicologie.” 64 photographs, roy. 8vo.
Mainz, 1865.
HEMMING, W. D.—“Aids to Forensic Medicine and Toxicology.” London, 1877.
HERMANN, L. —“Lehrbuch der experimentellen Toxicologie.” 8vo. Berlin,
1874. -
HoFFMANN, E. R.—“Lehrbuch der gerichtlichen Medicin.” 5th ed. Wien,
1890–91.
HUSEMANN and A. HILGER.—“Die Pflanzenstoffe in chemischer, pharmakolog-
ischer, u. toxicologischer Hinsicht.” 2nd ed. Berlin, 1882.
HUSEMANN, TH., and HUSEMANN, A.—“Handbuch der Toxicologie.” Berlin,
1862. (Suppl. Berlin, 1867.) -
KOBERT, RUD.—“Lehrbuch der Intoxicationen.” Stuttgart, 1893.
KOEHLER, R.—“Handbuch der speciellen Therapie, einschliesslich der Behandlung
der Vergiftungen.” 3rd ed. 2 vols., roy. 8vo. Tübingen, 1869.
LESSER, ADOLF.— “Atlas der gerichtlichen Medicin.” Berlin, 1883.
LoDw, OsCAR.—“Ein natürliches System der Giftwirkungen.” München, 1893.
LUDWIG, E.-‘‘Medicinische Chemie in Anwendung auf gerichtliche Untersuch-
ungen.” -
MAHON, A.—“Médecine Légale et Police Médicale.” Paris, 1807.
MARx, K. F. H.-‘‘Die Lehre von den Giften.” Göttingen, 1827–29.
MASCHKA, J.-‘‘Handbuch der gerichtlichen Medicin.” Tübingen, 1881–82. This
work is under the editorship of Dr. Maschka, and contains separate articles
on medico-legal and toxicological questions by various eminent toxicologists,
somewhat after the manner of Ziemssen’s Clyclopaedia.
MENDE, LUD. JUL. CASP.—“Ausführliches Handbuch der gerichtlichen Medicin.”
1819–32.
MoHR, FRIED.—“Chemische Toxicologie.” Braunschweig, 1874.
MonTGARNY, H. DE. —“Essai de Toxicologie, et specialement avec la Jurisprudence
Médicale.” Paris, 1878.
MonTMAHON, E. S. DE.-‘‘Manuel Médico-Légale des Poisons,” etc. Paris, 1824.
MUTEL, D. PH.—“Des Poisons, considerés sous le rapport de la Médecine Pratique,”
etc. Montpellier et Paris, 1835. -
NACQUET, A.—“Legal Chemistry : A Guide to the detection of Poisons, Examina-
tion of Stains, etc., as applied to Chemical Jurisprudence.” New York,
1876.
A translation from the French.
NICOLAI, JoH, ANT, HEINR.—“Handbuch der gerichtlichen Medicin.” Berlin, 1841.
The chemical portion is by F. R. Simon.
OGSTON, F.—“Lectures on Medical Jurisprudence.” London, 1878.
ORFILA, MATTHIEU Jos. BonAvRNTURA.—“Traité des Poisons, ou Toxicologie
Générale.” Paris, 1st, ed., 1814; 5th ed., 1852. -
ORFILA et LESUEUR.—“Traité de Médecine Légale.” Paris, 1821; 4th ed., Paris,
48.
§ 13.] BIBLIOGRAPHY. I9
OTTO, F. G.—“Anleitung zur Ausmittelung der Gifte.” Braunschweig, 1856; 5th
ed., 1875. 6th ed. by Robert Otto, Braunschweig, 1884.
PRAAG, VAN, LEONIDEs, and OPwy RDA, R. J.-‘‘Leerboek voor practische giftleer.”
In Zwee Theilen. Utrecht, 1871. º
RABUTEAU, A.—“Elémens de Toxicologie et de Médecine Légale, appliquées à
l'Empoisonnement.” Paris, 1873. 2nd ed. by Ed. Bourgoing. Paris, 1888.
REESE, JoHN J.-‘‘Manual of Toxicology, including the Consideration of the Nature,
Properties, Effects, and Means of Detection of Poisons, more especially in
their Medico-legal relations.” Philadelphia, 1874.
REMER, W. H. G.-“Lehrbuch der polizeilich-gerichtlichen Chemie.” Bd. 1 u, 2.
3. Auflage, Helmstadt, 1824.
SCHNEIDER, F. C.—“Die gerichtliche Chemie für Gerichtsärzte u. Juristen.”
Wien, 1852.
SCHNIEIDER, P. J.-‘‘Ueber die Gifte in medicinisch-gerichtlicher u. gerichtlich-
polizeilicher Rücksicht.” 2nd ed., 1821.
SELMI, F.—“Studi di Tossicologio Chimica.” Bologna, 1871.
SoBERNHEIM, Jos. FR., and SIMON, J. F.—“Handbuch der praktischen Toxicologie,”
etc. Berlin, 1838.
SoNNENSCHEIN, L.-‘‘Handbuch der gerichtlichen Medicin.” Berlin, 1860. A
new edition by Dr. A. Classen. Berlin, 1881.
TARDIEu, A.—“Etude Médico-Légale et Clinique sur l'Empoisonnement, avec la
Collaboration de M. T. Roussin pour la partie de l’expertise relative à la
Recherche Chimique des Poisons.” Paris, 1867.
TAYLOR, ALFRED SWAINE. –“ On Poisons in relation to Medical Jurisprudence and
Medicine.” 3rd ed. 1875. Manual, 1879.
— “Principles and Practice of Medical Jurisprudence.” 3 vols. London,
1873,
VIBERT, CH.-‘‘Précis de Toxicologie.” Paris, 1900.
WEBBER, ANT.-“Lehrbuch der praktischen Toxicologie.” Erlangen, 1869.
WooD, HoRATIO C.—“Therapeutics, Materia Medica, and Toxicology.” Phila-
delphia, 1874.
WooDMANN, W. BATHURST, and TIDY, CH.-“A Handy-Book of Forensic Medicine
and Toxicology.” London, 1877.
WoRMLEY, THEODORE G.—“Micro-Chemistry of Poisons, including their Physio-
logical, Pathological, and Legal Relations.” New York, 1857.
WURTz, A.—“Traité Élémentaire de Chimie Médicale, comprenant quelques notions
de Toxicologie,” etc. 2nd ed. Paris, 1875.
P A R T I I.
I.—-Definition of Poison.
§ 14. The term “Poison” may be considered first in its legal, as
distinct from its scientific, aspect.
The legal definition of “poison” is to be gathered from the various
statute-books of civilised nations.
The English law enacts that : “Whoever shall administer, or cause to
be administered to, or taken by any person, any poison or other destruc-
tive thing, with intent to commit murder, shall be guilty of felony.”
Further, by the Criminal Consolidation Act, 1861 : “Whosoever
shall, by any other means other than those specified in any of the
preceding sections of this Act, attempt to commit murder, shall be
guilty of felony.”
It is therefore evident that, by implication, the English law defines
a poison to be a destructive thing administered to, or taken by, a person,
and it must necessarily include, not only poisons which act on account
of their inherent chemical and other properties after absorption into the
blood, but mechanical irritants, and also specifically-tainted fluids.
Should, for example, a person give to another milk, or other fluid,
knowing, at the same time, that such fluid is contaminated by the
specific poison of scarlet fever, typhoid, or any serious malady capable
of being thus conveyed, we believe that such an offence could be brought
under the first of the sections quoted. In fine, the words “destructive
thing ” are widely applicable, and may be extended to any substance,
gaseous, liquid, or solid, living or dead, which, if capable at all of being
taken within the body, may injure or destroy life. According to this
view, the legal idea of “poison” would include such matters as boiling
water, molten lead, specifically-infected fluids, the flesh of animals dying
of diseases which may be communicable to man, powdered glass, diamond
dust, etc. Evidence must, however, be given of guilty intent.
The words, “administered to or taken by,” imply obviously that the
framers of the older statute considered the mouth as the only portal of
entrance for criminal poisoning, but the present law effectually guards
29
§ 15.] DEFINITION OF POISON. 2 I
against any attempt to commit murder, no matter by what means.
There is thus ample provision for all the strange ways by which poison
has been introduced into the system, whether it be by the ear, nose,
brain, rectum, vagina, or any other conceivable way, so that, to borrow
the words of Mr. Graves (Notes on Criminal Law Consolidation), “the
malicious may rest satisfied that every attempt to murder which their
perverted ingenuity may devise, or their fiendish malignity suggest,
will fall within some clause of this Act, and may be visited with penal
servitude for life.”
Since poison is often exhibited, not for the purpose of taking life,
but from various motives, and to accomplish various ends—as, for
example, to narcotise the robber's victim (this especially in the East),
to quiet children, to create love in the opposite sex (love philters), to
detect the secret sipper by suitably preparing the wine, to expel the
inconvenient fruit of illicit affection, to cure inebriety by polluting the
drunkard's drink with antimony, and, finally, to satisfy an aimless spirit
of mere wantonness and wickedness, the English law enacts “that whoso-
ever shall unlawfully or maliciously administer to, or cause to be taken
by, any other person, any poison or other destructive or noxious thing, so
as thereby to endanger the life of such person, or so as thereby to inflict
upon such person any grievous bodily harm, shall be guilty of felony.”
There is also a special provision, framed, evidently, with reference to
volatile and stupefying poisons, such as chloroform, tetrachloride of
carbon, etc.:—
“Whoever shall unlawfully apply, or administer to, or cause to be
taken by any person, any chloroform, laudanum, or other stupefying or
overpowering drug, matter, or thing, with intent, in any such case,
thereby to enable himself or any other person to commit, or with intent,
etc., to assist any other person in committing, any indictable offence,
shall be guilty of felony.”
§ 15. The German statute, as with successive amendments it now
stands, enacts as follows: *—
“Whoever wilfully administers (beibringt) to a person, for the
* “Wer vorsätzlich einem Andern, um dessen Gesundheit zu beschäedigen, Gift
oder andere Stoffe beibringt, welche die Gesundheit zu zerstören geeignet sind, wird
mit Zuchthaus von zwei bis zu zehn Jahren bestraft.
“Ist durch die Handlung eine schwere Körperverletzung verursacht worden, so
ist auf Zuchthaus nicht unter fünf Jahren, und wenn durch die Handlung der Tod
verursacht worden, auf Zuchthaus nicht unter zehn Jahren oder auf lebenslängliches
Zuchthaus zu erkennen.
“Ist die vorsätzliche rechtswidrige Handlung des Gift—etc.,-Beibringens auf
das ‘Tödten’ gerichtet, soll also durch dieselbe gewollter Weise der Tod eines Anderen
herbeigeführt werden, so kommt in betracht: Wer vorsätzlich einen Menschen todtet,
wird, wenn er die Tödtung mit Ueberlegung ausgeführt hat, wegen Mordes mit dem
Tode bestraft.”
22 POISONS : THEIR EFFECTS AND DETECTION. [$ 16.
purpose of injuring health, poison, or any other substance having the
property of injuring health, will be punished by from two to ten years'
imprisonment.
“If by such act a serious bodily injury is caused, the imprisonment
is not to be less than five years; if death is the result, the imprisonment
is to be not under ten years or for life.
“If the death is wilfully caused by poison, it comes under the
general law : “Whoever wilfully kills a man, and if the killing is pre-
meditated, is on account of murder punishable with death.’”
The French law runs thus (Art. 301, Penal Code):—“Every attempt
on the life of a person, by the effect of substances which may cause
death, more or less suddenly, in whatever manner these substances may
have been employed or administered, and whatever may have been the
results, is called poisoning.”.”
There is also a penalty provided against any one who “shall have
occasioned the illness or incapacity for personal work of another, by the
voluntary administration, in any manner whatever, of substances which,
without being of a mature to cause death, are injurious to health.” i
§ 16. Scientific Definition of a Poison.—A true scientific definition
of a poison must exclude all those substances which act mechanically
—the physical influences of heat, light, and electricity ; and parasitic
diseases, whether caused by the growth of fungus, or the invasion of an
organism by animal parasites, as, for example, “trichinosis,” which are
not, so far as we know, associated with any poisonous product excreted
by the parasite;—on the other hand, it is now recognised that
pathogenic micro-organisms develop poisons, and the symptoms of all
true infections are but the effects of “toxines.” The definition of
poison, in a scientific sense, should be broad enough to comprehend not
only the human race, but the dual world of life, both animal and
vegetable.
Husemann and Kobert are almost the only writers on poisons who
have attempted, with more or less success, to define poison by a
generalisation, keeping in view the exclusion of the matters enumerated.
Husemann says:—“We define poisons as such inorganic, or organic
substances as are in part capable of artificial preparation, in part existing,
ready-formed, in the animal or vegetable kingdom, which, without being
* “Est qualifié empoisonmement—tout attentat à la vie d’une personne par l’effet
de substances qui peuvent donner la mort plus on moins promptement, de quelque
manière que ces substances aient été employées ou administrées, et quelles qu’en
aient été les suites.”—Art. 301, Penal Code.
+ “Celui qui aura occasionné à autrui une maladie ou incapacité de travail
personnel en lui administrant volontairement, de quelque maniére que ce soit, des
substances qui, sans étre de nature à donner la mort, sont nuisibles à la Santé.”—
Art, 317, Penal Code.
§ 17.] CLASSIFICATION OF POISONS. 23
able to reproduce themselves, through the chemical nature of their
molecules under certain conditions, change in the healthy organism the
form and general relationship of the organic parts, and, through anni-
hilation of organs, or destruction of their functions, injure health, or,
under certain conditions, destroy life.” Kobert says:–“ Poisons are
organic or inorganic unorganised substances originating in the organism
itself, or introduced into the organism, either artificially prepared, or
ready formed in nature, which through their chemical properties,
under certain conditions, so influence the organs of living beings,
that the health of these beings is seriously influenced temporarily or
permanently.”
In the first edition of this work an attempt was made to define a
poison : the definition slightly abbreviated is thus:—A substance may
be called a poison if it is capable of being taken into any living
organism, and causes, by its own inherent chemical nature, impairment or
destruction of function. We prefer this definition to Kobert's, and
believe that it fairly agrees with what we know of poisons.
II.-Classification of Poisons.
§ 17. At some future time, with a more intimate knowledge of the
way in which each poison acts upon the various forms of animal and
vegetable life, it may be possible to give a truly scientific and philoso-
phical classification of poisons—one based neither upon symptoms, upon
local effects, nor upon chemical structure, but upon a collation and com-
parison of all the properties of a poison, whether chemical, physical, or
physiological. No perfect systematic arrangement is at present attain-
able : we are either compelled to omit all classification, or else to arrange
poisons with a view to practical utility merely.
From the latter point of view, an arrangement simply according to
the most prominent symptoms is a good one, and, without doubt, an
assistance to the medical man summoned in haste to a case of real or
Suspected poisoning, Indeed, under such circumstances, a scheme some-
What similar to the following probably occurs to every one versed in
toxicology:-
A. Poisons CAUSING DEATH IMMEDIATELY, or IN A FEw MINUTEs.
There are but few poisons which destroy life in a few minutes.
Omitting the strong mineral acids, carbon monoxide, carbon dioxide,
With the irrespirable gases—Prussic acid, the cyanides, ovalic acid, and
occasionally strychnine, are the chief poisons coming under this head.
24 |POISONS : THEIR EFFECTS AND DETECTION. [S 18.
B. IRRITANT POISONs (symptoms mainly º vomiting, and purging).
Arsenic, antimony, phosphorus, caktharitieś, savin, ergot, digitalis,
colchicum, zinc, mercury, lead, copper, silver, iron, baryta, chrome, yew,
laburnum, and putrīd animal substances.
C. IRRITANT AND NARCOTIC Poisons (symptoms those of an irritant
nature, with the addition of more or less pronounced cerebral
indications).
To this class more especially belong oacalic acid and the oa'alates,
with several poisons belonging to the purely narcotic class, but which
produce occasionally irritant effects. +
D. Poisons MORE ESPECIALLY AFFECTING THE NERVOUs SYSTEM.
1. NARCOTICS (chief symptom insensibility, which may be preceded
by more or less cerebral excitement): Opium, Chloral, Chloroform.
2. DELIRLANTS (delirium for the most part a prominent symptom):
Belladonna, hyoscyamus, Stramonium, with others of the Solanaceae,
to which may be added—poisonous fungi, Indian hemp, Lolium temulen-
tum, CEnanthe crocata, and camphor.
3. CONVULSIVES.—Almost every poison has been known to produce
convulsive effects, but the only true convulsive poisons are the alkaloids
of the Strychnos class.
4. COMPLEX NERVOUS PHENOMENA : Aconite, digitalis, hemlock,
calabar bean, tobacco, Lobelia inflata, and curara.
§ 18. KOBERT's CLASSIFICATION. – Kobert has classified poisons
according to the following scheme:—
I. POISONS WHICH CAUSE COARSE ANATOMICAL CHANGES OF THE
ORGANS.
A. Those which specially irritate the part to which they are applied.
1. Acids. -
2. Cawstic alkalies.
3. Caustic salts, especially those of the heavy metals.
4. Locally irritating organic substances which neither can be classified as
corrosive acids nor alkalies, nor as corrosive salts; such are:—canthari-
dime, phrynine, and others in the animal kingdom, croton oil and savin
in the vegetable kingdom. Locally irritating colours, such as the aniline
dyes.
5. Gases and vapours which cause local irritation when breathed, such as
ammonia, chlorime, iodine, bromine, and Swlphur dioxide.
B. Those which have but little effect locally, but change anatomically other
parts of the body; such as lead, phosphorus, and others.
§ 19.] CLASSIFICATION OF POISONS. 25
II. BLOOD POISONS.
1. Blood poisons interfering with the circulation in a purely physical manner,
such as peroacide of hydrogen, ricine, abrine.
2. Poisons which have the property of dissolving the red blood corpuscle,
such as the saponins.
3. Poisors which, with or without primary solution of the red blood cor-
puscles, produce in the blood methaemoglobin ; such as potassic chlorate,
hydrazine, nitrobenzene, aniline, picric acid, carbon disulphide.
4. Poisons having a peculiar action on the colouring matter of the blood, or on
its decomposition products, such as hydric sulphide, hydric cyanide, and
the cyanides and carbon monoacide.
III. POISONS WHICH KILL WITHOUT THE PRODUCTION OF COARSE
ANATOMICAL CHANGE.
1. Poisons affecting the cerebro-spinal system ; such as chloroform, ether,
mitrows oa;ide, alcohol, chloral, cocaine, atropime, morphine, nicotime,
contine, acomitime, Strychnine, curarine, and others.
2. Heart Poisons; such as, digitalis, helleborin, muscarine.
IV. POISONOUS PRODUCTS OF TISSUE CHANGE.
1. Poisonous albumin.
2. Poisons developed in food.
3. Auto-poisoning, e.g., uraemia, glycosuria, oxaluria.
4. The more important products of tissue change ; such as, fatty acids, oxy-
acids, amido-fatty acids, amines, diamines, and ptomatimes.
§ 19. In this work the arrangement is one which, as far as
possible, follows the order in which a chemical expert would search for
an unknown poison—hence an arrangement partly chemical and partly
symptomatic. First the chief gases which figure in the mortality
statistics are treated, and then follow in order other poisons.
A chemist, given a liquid to examine, would naturally test first its
reaction, and, if strongly alkaline or strongly acid, would at once direct
his attention to the mineral acids or to the alkalies. In other cases, he
would proceed to separate volatile matters from those that were fixed,
lest substances such as prussic acid, chloroform, alcohol, and phosphorus
be dissipated or destroyed by his subsequent operations.
Distillation over, the alkaloids, glucosides, and their allies would
next be naturally sought, since they can be extracted by alcoholic and
ethereal solvents in such a manner as in no way to interfere with an
after-search for metals.
The metals are last in the list, because by suitable treatment, after
all organic substances are destroyed, either by actual fire or powerful
chemical agencies, even the volatile metals may be recovered. The
metals are arranged very nearly in the same order as that in which they
would be separated from a solution—viz., according to their behaviour
to hydric and ammonium sulphides.
26 Poisons: THEIR EFFECTS AND DETECTION, [Š 19.
There are a few poisons, of course, such as the oxalates of the
alkalies, which might be overlooked, unless sought for specially ; but it
is hoped that this is no valid objection to the arrangement suggested,
which, in greater detail, is as follows:—
A.—POISONOUS GASES.
Carbon monoxide.
Chlorine.
Hydric sulphide.
B.—ACIDS AND ALKALIES.
Sulphuric acid.
. Hydrochloric acid.
Nitric acid.
Potash.
. Soda.
Ammonia.
Neutral sodium, potassium, and ammonium salts.
i
In nearly all cases of death from any of the above, the analyst, from
the symptoms observed during life, from the surrounding circumstances,
and from the pathological appearances and evident chemical reactions
of the fluids submitted, is put at once on the right track, and has no
difficulty in obtaining decided results.
C.—POISONOUS SUBSTANCES CAPABLE OF BEING SEPAR-
ATED BY DISTILLATION FROM EITHER NEUTRAL OR
ACID LIQUIDS.
1. Hydrocarbons.
Camphor.
Alcohols.
Amyl-nitrite.
Chloroform and other anaesthetics.
. Carbon disulphide.
Carbolic acid.
Nitro-benzene.
. Prussic acid.
. Phosphorus.
:
:
l
The volatile alkaloids, which may also be readily distilled by strongly
alkalising the fluid, because they admit of a rather different mode of
treatment, are not included in this class.
§ 19.]
CLASSIFICATION OF POISONS. 27
D.—ALKALOIDS AND POISONOUS VEGETABLE PRINCIPLES
SEPARATED FOR THE MOST PART BY ALCOHOLIC
SOLVENTS.
DIVISION I.-VEGETABLE ALKALOIDS.
. Liquid volatile alkaloids, alkaloids of hemlock, nicotine,
piturie, sparteine, aniline.
The opium group of alkaloids.
The strychnine or tetanic group of alkaloids—strychnine,
brucine, igasurine.
4. The aconite group of alkaloids.
5
. The mydriatic group of alkaloids—atropine, hyoscyamine,
Solanin, cytisine.
. The alkaloids of the veratrines.
. Physostigmine.
Pilocarpine.
. Taxine.
. Curarine.
. Colchicin.
. Muscarin and the active principles of certain fungi.
There would, perhaps, have been an advantage in arranging several
of the individual members somewhat differently—e.g., a group might
be made of poisons which, like pilocarpine and muscarine, are antago-
mistic to atropine ; and another group suggests itself, the physiological
action of which is the opposite of the Strychnos class; solamin (although
classed as a mydriatic, and put near to atropine) has much of the
nature of a glucoside, and the same may be said of colchicin; so that,
if the classification were made solely on chemical grounds, solanin
would have followed colohicin, and thus have marked the transition
from the alkaloids to the glucosides.
1.
2.
3.
DIVISION II.—GLUCOSIDES.
The digitalis group.
Other poisonous glucosides acting on the heart.
Saponin.
The glucosides, when fairly pure, are easily recognised; they are
destitute of nitrogen, neutral in reaction, and split up into sugar and
other compounds when submitted to the action of saponifying agents,
such as boiling with dilute mineral acids.
28 POISONS : THEIR EFFECTS AND DETECTION. [š 19.
DIVISION III.—WARIOUS VEGETABLE POISONOUS PRINCIPLES NOT
READILY ADMITTING OF CLASSIFICATION IN THE PREVIOUS
DIVISIONS.
1. Santonin. 2. Mezerein.
It is probable that this class will in a few years be extended, for
several other organic amitrogenous poisons exist, which, when better
known, will most likely prove to be anhydrides.
Ergot, picrotoxin, Tutin, the poison of Illicium religiosum, picric acid,
cicutoxin, AEthusa cynapium, CEnanthe crocata, croton oil, savin oil, the
toxalbumins of castor oil and Abrus, Ictrogen, Lathyrus sativus, arum,
and others. -- . -
The above division groups together various miscellaneous toxic
principles, none of which can at present be satisfactorily classified.
E. —POISONS DERIVED FROM LIVING OR DEAD
ANIMAL SUBSTANCES.
DIVISION I.-Poisons SECRETED BY THE LIVING.
. Poisonous amphibia.
. Poison of the scorpion.
Poisonous fish.
. Poisonous insects—spiders, wasps, bees, beetles, etc.
. Snake poison.
. Mammalian poison. Epinephrin.
:
DIVISION II.—Poisons ForMED IN DEAD ANIMAL MATTERS.
1. Ptomaines.
2. Poisoning by putrid or changed foods—sausage poisoning.
F.—THE OXALIC ACID GROUP.
G.—INORGANIC POISONS.
DIVISION I.-PRECIPITATED FROM A HYDROCHLORIC ACID Solution
By HYDRIC SULPHIDE—PRECIPITATE, YELLOW OR ORANGE.
Arsenic, antimony, cadmium.
DIVISION II.-PRECIPITATED BY HYDRIC SULPHIDE IN HYDRO-
CHLORIC ACID SOLUTION.—BLACK.
Lead, copper, bismuth, silver, mercury.
§ 20, 21.] STATISTICS. 29
DIVISION III.—PRECIPITATED FROM A NEUTRAL SOLUTION BY
HYDRIC SULPHIDE.
Zinc, nickel, cobalt.
DIVISION IV. PRECIPITATED BY AMMONIUM SULPHIDE.
Iron, chromium, thallium, aluminium.
DIVISION V.—ALKALINE EARTHS.
Barium.
III.-Statistics.
§ 20. The number of deaths from poison (whether accidental,
suicidal, or homicidal), as compared with other forms of violent, as
well as matural deaths, possesses no small interest ; and this is more
especially true when the statistics are studied in a comparative manner,
and town is compared with town, country with country.
The greater the development of commercial industries (especially
those necessitating the use or manufacture of powerful chemical
agencies), the more likely are accidents from poisons to occur. It may
also be stated, further, that the higher the mental development of a
nation, the more likely are its homicides to be caused by subtle poison
—its suicides by the euthanasia of chloral, morphine, or hemlock.
Other influences causing local diversity in the kind and frequency
of poisoning are those of race, of religion, of age and sex, and the
mental stress concomitant with sudden political and social changes.
§ 21. During the ten years ending December 1903 there have died
from poisons and poisonous vapours 11,035 persons. The following list
deals only with those poisons which are definite and fairly common, and
accounts for 8544, or over 77 per cent. of the whole. The balance is
made up of deaths from the following among others: coal gas, sul-
phuretted hydrogen, sewer gas, carbon dioxide, carbon monoxide,
arseniuretted hydrogen, various so-called “fumes from kilns,” “from
coke,” etc.; there are also a few deaths recorded under each of the
following heads: tobacco, yew leaves or berries, poisonous berries,
ergot, castor-oil seeds, oil of cloves, parsnip wine, cantharides, bryony,
opodeldoc, sheep dip, weed killer, fungus, water hemlock, colchicum.
wine, quinine, Gregory's powder, antifebrin, buttercup, sulpholine, and
vague things such as overdose of medicine, limiment, ptomaines,
poisonous fish, and, generally, bad or changed food.
3O POISONS : THEIR EFFECTS AND DETECTION. [$ 21.
DEATHS FROM POISON IN ENGLAND AND WALES DURING THE TEN
YEARS ENDING DECEMBER 1903.
§: Suicide. | Murder. Total.
M. F. M. F. | M. | F. M. F.
METALs.
Arsenic, e e tº $ . 58 || 107 || 32 | 1.4 ... 90 | 121
Antimony, . e s tº {º 2 3 2 2 1 4 6
Copper, t * te tº o 2 | ... 2 1 e e is 4 1
Lead, . g g ſº {} . 754 | 165 6 1 760 | 166
Silver Nitrate, . e º ſº 1 tº tº º l 1 2 1
Zinc Chloride or Sulphate, . º 7 2 2 9 9 || 11
Mercury, Salts of, g e . 14 || 17 || 48 || 18 62 || 35
Chromic Acid or Preparations of 8 6 I I 7
Chromium, g * g e g : * * *
Iron Perchloride, e 1 ... . . . . . . . . . . . . . ... I
ALKALINE EARTHS.
Barium Chloride, . ë tº e l tº º ſº * - ſº e is tº I e º 'º tº $ tº 1 | ...
Lime, . g tº tº * e tº $ tº I {e tº a a s e i s is a e º gº tº gº º I
THE ALKALIES AND THEIR SALTS,
Caustic Potash, . g e * 6 4 ... . . . . . . . . . . . . 6 4
Potassium Chlorate, g tº s e º e s e I e º e i e s \ } m e º * * * * * * : * * *
5 y Nitrate, & g g tº € $ 1 ... a s tº e g º a * * sº tº º I
5 2 Bromide, tº 2 . . tº ºn tº a ſº e a s s dº e Q 2 ...
2 3 Bichromate, . 7 4 22 4 | ... . ..., | 29 || - 8
Caustic Soda, ſº e 6 7 ... . . . . . . . . . ... 6 7
Ammonia, . º tº . 60 | 63 || 39 54 || 1 | ... 100 | 117
ACIDs.
(a) Mineral.
Acid, Sulphuric, . g tº . 34 9 || 30 22 || 2 | ..., | 66 || 31
,, Nitric, . g g t . 13 8 || 46 || 23 ... . ... 59 || 31
,, Hydrochloric, . º . 91 || 33 204 || 165 ..., | ... 295 || 198
,, Hydrofluoric, © g e 1 tº $ tº tº $ tº I & e a g e s s 1 | ...
(b) Organic.
Acid, Carbolic, . o © , 184 || 153 || 796 || 826 2 || 3 || 982 982
,, Acetic, * , g e * 1 5 2 6 | ... . ... 3 || || 1
,, Oxalic, § e & . 27 | 28 || 65 49 || 2 | ..., | 94 || 77
ELEMENTS.
Phosphorus, . e º tº . 29 || 38 || 21 | 60 | . . . . . . . 50 | 98
Iodine . º g º e tº 2 | ... I 1 | . . . . . . . 3 I
Carry forward, , 1310 || 655 |1320 1257 || 7 || 4 ||2637 |1916


§ 2 I.] STATISTICS. 3 I
DEATHS FROM POISON IN ENGLAND AND WALES DURING THE TEN
YEARS ENDING DECEMBER 1903—continued.
§: Suicide. Murder. Total.
M. F. | M. | F. M. F. | M. F.
Brought forward, . 1310 || 655 (1320 (1257 || 7 || 4 |2637 1916
WoLATILE LIQUIDs.
Paraffin (Petroleum), . ſº . 19 4 19 4
Benzoline, . e tº ſº º 4 ... e tº & 1 | . . . . ... 4 1
Nitrobenzol, e ſº e º 1 ... . ... . . . . . . ... 1 | ...
Ether, . e tº & # . 38 33 ... . . . . . . . . . ... 38 33
Chloroform, . º te gº . 520 292 9 8 . . . . . 1 || 529 301
Chloroform and Ether, . e * 6 6 & a i e is s : * * * : * * * 6 6
Alcohol, Chloroform, and Ether, . 6 4 * * * 6 4
Turpentine, . g g e ſº 1 4 3 1. 4 5
Sweet Nitre, tº $ tº 1 tº tº e * c & 1
Methyl Alcohol, ſº e i e º s 1 gº tº g 1
Nitrous Oxide, . e * . . . 9 6 9 6
Alcohol, c ſº g te . 56 || 26 3 2 59 || 28
Fusel Oil, . e tº § tº º & sº º 1 & & © 1
Spirit of Camphor, tº g tº tº º is e is a e º e
Brandy, {º {º & º tº g g is 3 § ºr & tº º ſº 3
Paraldehyde, tº g e * 1 4 * * * 1 4
Coal Naphtha, . e ſº * I e º ſº 1 1 e tº tº 2
Anaesthetic (kind not stated), . 117 | 59 * tº tº 117 | 59
OPIATES OR NARCOTICS.
Opium, Laudanum g &
Morphine, ! 536 346 || 432 189 ... || 2 | 968 537
Soothing Syrup, . tº e º 6 3 ... . ... . . . . . ... 6 3
Chlorodyne, . º º ſº . 66 || 36 36 3 102 || 39
Chloral, #3 * * * . 66 | 16 | 12 2 78 18
Sulphonal, 2 5 l 2 6
Cocaine, § & 5 6 1 ... 6 6
5 3 and Ether, 3 tº g tº * - e. 3 gº º tº
3 2 Atropine, 1 tº º & I tº a º
§º and Opium, * 1 ... . ... 1 ... . ... l I
elladonna. . tº & e } ſ
Atropine, ſº te e \ 33 || 33 | 12 || 17 | ... . ... 45 50
Henbane, . tº e e e tº dº º 1 | ... . . . . . . . . ... I
Narcotic (kind not stated), . . 16 || 13 3 5 : ... . ..., | 19 18
CYANIDEs.
Prussic Acid and Oil of Almonds, . 30 3 272 22 1 || 302 26
Potassic Cyanide, . g g . 17 2 | 166 21 ... | 1 | 183 || 24
Ammonium Sulpho-Cyanide, * | * * * | g o e 2 | . . . . . . . . . . 2 ...
STRYCHNINE AND some oth ER
ORGANIC Poisons.
Strychnine and Nux Womica, . 43 || 24 || 79 || 92 || 4 || 2 | 126 || 118
Aconite, & º º te . 22 3 | 1.4 6 | ... . ... 36 9
Digitalis, . ſº & e tº 3 ... . ... . . . . ... . ... 3
Total, , 2938 [1586 |2364 (1634 11 || 11 |5313 3231
Tºtal poisonous substances, includ- 3880 |2078 (2923 |2128 || 14 | 12 6317 421s
ing gases and various other poisons,


11,035
32 POISONS: THEIR EFFECTS AND DETECTION. [$ 22, 23.
§ 22. Although so large a number of substances destroy life by accident
or design, yet there are in the list only about 26 which kill about 2 persons
or above each year. It must at the same time be confessed that several
of the 26 are not simple substances, so that the statement underrates
the actual facts. The 26 substances arranged in the inverse order of
their fatality are as follows:—
Number of deaths
in ten years.
Antimony, . e e e º e º e o º 10
Potash, . tº e e * º e o e o 10
Soda, e • tº g º • º g º º 13
Acetic acid, e º e e e o º º - 14
Nitrous oxide, & e & - o º tº & 15
Cocaine, either alone or with other substances, . - & 16
Zinc salts (chloride and sulphate), . o e º . 20
Paraffin, . º º e e e 23
Aconite, . º e º p te o & o 45
Chromic acid and preparations of bichromate of potash, . 53
Ether, & e º t - º e g º • 71
Alcohol, . º e g º © tº e g º 87
Belladonna preparations, including atropine, . º o 95
Chloral, . • º & º º e s e º 96
Mercuric salts, . º e 0. - º . e º 97
Phosphorus, - 4. e b - º e - s 148
Oxalic acid, 4. º t º - e g tº - 171
Arsenic, . tº º & e º - g e - 211
Ammonia, . e - e º - - º º - 217
Strychnine, o º g g º - * e º 244
Prussic acid and cyanides, . e • - e º * 535
Mineral acids, . - & e º º g s - 680
Chloroform, º {- tº & e º g tº e 852
Lead, e - º e g e - t e . 926
Opiates, including laudanum, soothing syrup, morphine, . 1655
Carbolic acid, . - º * & © & tº º 1964
IV.-The Connection between Toxic Action and Chemical
Composition.
§ 23. Considerable advance has been made of late years in the study
of the connection which exists between the chemical structure of the
molecule of organic substances and physiological effect. The results
obtained, though important, are as yet too fragmentary to justify any
great generalisation; the problem is a complicated one, and as Lauder
Brunton justly observes:—
“The physiological action of a drug does not depend entirely on its
chemical composition, nor yet on its chemical structure, so far as that
can be indicated even by graphic formula, but upon conditions of solu-
bility, instability, and molecular relations, which we may hope to discover
in the future, but with which we are as yet imperfectly acquainted.””
* Introduction to Modern Therapeutics, Lond., 1892. 136.
§ 23.]
TOXIC ACTION AND CHEMICAL COMPOSITION. 33
The occurrence of hydroxyl, whether the substance belong to the
simpler chain carbon series or to the aromatic carbon compounds, appears
to usually endow the substance with more or less active and frequently
poisonous properties, as, for example, in the alcohols, and as in hydro-
xylamine. It is also found that among the aromatic bodies the toxic
action is likely to increase with the number of hydroxyls: thus phenol
has one hydroxyl, resorcin two, and phloroglucin three ; and the toxic
power is strictly in the same order; for, of the three, phenol is least and
phloroglucin most poisonous. -
Replacing hydrogen by a halogen, especially by chlorine, in the fatty
acids mostly produces substances of narcotic properties, as, for instance,
monochloracetic acid. In the sulphur compounds, the entrance of
chlorine modifies the physiological action and intensifies toxicity: thus
ethyl sulphide (C2H5)2S is a weak poison, monochlorethyl sulphide
C.H.C, H,ClS a strong poison, and dichlorethyl sulphide C, HsCl,S
a very strong poison : the vapour kills rabbits within a short time, and
a trace of the oil applied to the ear produces intense inflammation of
both the eyes and the ear.”
The weight of the molecule has an influence in the alcohols and acids
of the fatty series; for instance, ethyl, propyl, butyl, and amyl alcohols
show as they increase in carbon a regular increase in toxic power; the
narcotic actions of sodium propionate, butyrate, and valerianate also
increase with the rising carbon. Nitrogen in the triad condition in
the amines is far less poisonous than in the pentad condition.
Bamberger f distinguishes two classes of hydrogenised bases derived
from a and 8 naphthylamine, by the terms “acylic ’’ and “aromatic.”
The acylic contains the four added hydrogens in the amidogen nucleus,
the aromatic in the other nucleus, thus—
CH CNH, CH CH
C C
H O CH CH /YN CNH,
CH CH CH CH
w NZGN/
Cú9öH C#9öH
a Naphthylamine. B Naphthylamine.
Cºogh, CH, CH
NC
CH / Sº CNH, CH, & N CNH,
CH CH CH CH
NZ ~~~ *** Ny/NZ
Cú9či, Că.9öf.
Acylic tetrahydro- Aromatic tetrahydro-
a Naphthylamine.
* W. Meyer, Ber. d. chem. Ges., xx. 1725.
A Naphthylamine.
+ Ber., xxii. 777–778.
3
34 POISONS : THEIR EFFECTS AND DETECTION. [$ 24.
The acylic Stetrahydro-naphthylamine, the B tetrahydroethylnaphthy-
lamine, and the B tetrahydromethylnaphthylamine all cause dilatation of
the pupil and produce symptoms of excitation of the cervical sympa-
thetic nerve ; the other members of the group are inactive.
$ 24. The result of replacing hydrogen by alkyls in aromatic bodies
has been studied by Schmiedeberg and others; replacing the hydrogen of
the amidogen by ethyl or methyl, usually results in a body having a
more or less pronounced narcotic action. The rule is that methyl is
stronger than ethyl, but it does not always hold good; ortho-amido-
phenol is not in itself poisonous, but when two hydrogens of the
amidogen group are replaced by two methyls thus—
HO HO
ſ NH, N(CH3)2
N/
the resulting body has a weak narcotic action.
It would naturally be inferred that the replacement of the H in the
hydroxyl by a third methyl would increase this narcotic action, but this
is not so : on the other hand, if there are three ethyl groups in the same
situation a decidedly narcotic body is produced.
The influence of position of an alkyl in the aromatic bodies is well
shown in Ortho-, para-, and meta-derivatives. Thus the senior author
proved some years ago that with regard to germicidal properties, ortho-
cresol was more powerful than meta-; meta-cresol more powerful than
para-; so again ortho-aceto-toluid is poisonous, causing acute nephritis;
meta-aceto-toluid has but feeble toxic actions but is useful as an
antipyretic ; and para-aceto-toluid is inactive.
In the trioxybenzenes, in which there are three hydroxyls, the toxic
action is greater when the hydroxyls are consecutive, as in pyrogallol,
than when they are symmetrical, as in phloroglucin.
OH OH
º OH
OH H
U O NZ OH
Pyrogallol. Phloroglucin.
The introduction of methyl into the complicated molecule of an
alkaloid often gives curious results: thus methyl strychnine and methyl
brucine instead of producing tetanus have an action on voluntary muscle
like curare.
Benzoyl-ecgonine has no local anaesthetic action, but the introduction'
of methyl into the molecule endows it with a power of deadening the
$ 24.] TOXIC ACTION AND CHEMICAL COMPOSITION. 35
sensation of the skin locally; on the other hand, cocethyl produces no
effect of this kind.
Drs. Crum Brown and Fraser * have suggested that there is some
relation between toxicity and the saturated and non-saturated condition
of the molecule.
Hinsberg and Treupel have studied the physiological effect of sub-
stituting various alkyls for the hydrogen of the hydroxyl group in para-
aceto-amido-phenol.
Para-aceto-amido-phenol when given to dogs in doses of 0.5 grim. for
every kilogr. of body weight causes slight narcotic symptoms, with slight
paralysis; there is cyanosis and in the blood much methaemoglobin.
In men doses of half a gramme (7-7 grains) act as an antipyretic,
relieve neuralgia, and have weak narcotic effects.
The following is the result of substituting certain alkyls for H in
the HO group.
(1) Methyl.—The narcotic action is strengthened and the antipyretic
action unaffected. The methaemoglobin in the blood is somewhat less.
(2) Ethyl.—Action very similar, but much less methaemoglobin is
produced.
(3) Propyl-Antipyretic action a little weaker. Methaemoglobin
in the blood smaller than in para-aceto-amido-phenol, but more than
when the methyl or ethyl compound is administered.
(4) Amyl.—Antipyretic action decreased.
The smallest amount of toxicity is in the ethyl substitution ; while
the maximum antipyretic and antineuralgic action belongs to the methyl
substitution.
Next substitution was tried in the Imid group. It was found that
substituting ethyl for H in the imid group annihilated the narcotic and
antipyretic properties. No methaemoglobin could be recognised in the
blood.
Lastly, simultaneous substitution of the H of the HO group by ethyl
and the substitution of an alkyl for the H in the NH group gave the
following results:— s -
Methyl.—In dogs the narcotic action was strengthened, the methae.
moglobin in the blood diminished. In men the narcotic action was also
more marked as well as the anti-neural action. The stomach and kid-
neys were also stimulated.
Ethyl.—In dogs the marcotic action was much strengthened, while
the methaemoglobin was diminished. In men the antipyretic and anti-
neural actions were unaffected.
Propyl.-In dogs the narcotic action was feebler than with methyl
or ethyl, and in men there was diminished antipyretic action.
* Jowrm. Amat. and Phys., vol. ii. 224.
36 POISONS: THEIR EFFECTS AND DETECTION. [$ 24.
Amyl.–In dogs the narcotic action was much smaller.
From this latter series the conclusion is drawn that the maximum
of narcotic action is obtained by the introduction of methyl, and the
maximum antipyretic action by the introduction of methyl or ethyl.
The ethyl substitution is, as before, the less toxic. *
The effect of the entrance of an alkyl into the molecule of a substance
is not constant ; sometimes the action of the poison is weakened, some-
times strengthened. Thus, according to Stolnikow, dimethyl resorcin,
CoPI,(OCH3)2, is more poisonous than resorcin, CaFI,(OH)2. Anisol
C6H50CHg, according to Loew, is more poisonous to algae, bacteria, and
infusoria than phenol, C.H.OH. On the other hand, the replacement
by methyl of an atom of hydrogen in the aromatic oxyacids weakens
O.CH,
their action ; methyl salicylic acid ch,< is weaker than
COOH
OH
salicylic acid C.H.K.
- COOH.
Arsen-methyl chloride, As(CH3)Cl3, is strongly poisonous, but the
introduction of a second methyl As (CHA), Cl makes a comparatively
weak poison.
These results admit, however, of a different interpretation, for
Overton's f researches show that the effect of narcotic substances depends
on their greater or smaller power of penetrating into the nerve or other
cells, and that this penetrating power has a direct relationship to the
solubility of the substance in oil : those substances that are not soluble
in oil do not enter into the nerve cells, those that are soluble easily
penetrate. In the living cells there are not only oily matters, but
also lecithin and cholesterin and their derivatives. The brain cells
are especially rich in such ; to the fatty mixtures in the brain cells the
name of brain lipoids has been given (Autos = fat). Alcohol or chloroform,
after absorption by the blood, are practically in aqueous solution; and
when this aqueous solution is carried to the brain lipoids there is a
partition of the alcohol between the lipoids and the serum, the value of
, the degree
- - - º º oil
which is capable of being expressed by the coefficient Water
of penetration being dependent on the magnitude of the resulting figure,
which is obviously the larger the more soluble the substance is in oil.
* Ueber die physiologische Wirkung des p-amido-phenol w. einiger Derivate
desselben. O. Hinsberg u. G. Treupel, Archiv f. eaſp. Pathol, w, Pharm., xxxiii. 216.
† Overton, Studien über die Warkose, Jena, 1901. f
H. Meyer, “Zur theorie der Alcohol Narkose,” Arch. f. eaſper. Pharmac., xlii.
H. Meyer, Der Einfluss wechselnder Temperature auf WirkungStarke w. Teilungs-
coefficient, op. cit. xlvi.
$ 24.] TOXIC ACTION AND CHEMICAL COMPOSITION. 37
Limit of concentration
necessary to produce Partition coefficient
narcosis in A-molecules olive oil.
- per litre.
Trional, G. º g º e ſº 0-0018 4 '46
Tetronal, . tº e e g º 0 0013 4 °04
Butyl chloral hydrate, . t & º 0-002 1°59
Triacetin, . e & * * g 0 °010 0.30
Diacetin, . Ç * ſe º & 0 °015 0.23
Chloral hydrate, . tº g e g 0-02 0 °22
Aethyl-urethane, g tº g & 0 °025 0 °14
Monacetin, . e e g te º 0.0125 0-06
Methyl urethane, . . g e tº 0 °40 0 °04
With a trifling exception, which future research may explain, the
greater the solubility in oil of the above substances, the greater the
marcotic effect ; thus trional, with a coefficient of 4:46, is active in a
concentration of 1.8 mgrm. (molecules) per litre, while methyl urethane
with a coefficient of only 0.04 must be dissolved in the proportion of
400 mgrms. per litre.
By the same process Meyer has shown that in the alkyl substitutions
it is not, as formerly held, the ethyl group which is the specific carrier
of narcotic properties, but that the activity is strictly parallel to the
partition coefficient.
Coefficient.
Dimethyl-sulphon dimethyl-methane (CH3)2 - C - (SO2CH3),
very weak, . tº ſº tº º tº º & * 0 106
Diethyl-sulphon-methane CH3(SO2C3H5)2 very weak, . ſº 0 °1514
Tertiary butylal (CH3)3COH weak, ſº e gº 0.176
,, amylal (CH3)2
COH strong, . * * d g I •0
C2H5
Sulphonal (CH3)2 - C – (SO2C2H5)3 strong, ſº & ſº 1 *115
Tetronal (C2H5)2–C– (SO2C3H5)2 much stronger than
sulphonal, tº e º * g * * 4 °039
Trional CHs.
C h XCSO.C.H.), much stronger than sulphonal, . 4°458
2++5
H. Meyer lays down the following deductions from the various
experiments on narcotics:— -
(1) All chemical indifferent matters which are soluble in fat and
fatty bodies must act as narcotics on living protoplasm so far as they
enter into the same.
(2) The action will be the stronger and the earlier on those cells
in which the fatty components are essential to the function of the cell.
(3) The proportionate activity of such narcotic must be dependent,
on the one hand, to the chemical activity of the fat-like substance; on
the other, to the remaining constituents of the body, especially water.
The activity has, therefore, a direct relation to the partition coefficient
38 POISONS : THEIR EFFECTS AND DETECTION. [$ 24.
which determines the distribution of the substance between water and
the fatty substance.
The action of a pure narcotic is, therefore, not chemical; it forms no
definite chemical compound with the cell, nor does it alter its structure;
it simply interferes for the time being with its function. If the amount
of narcotic in the serum diminishes, the partition coefficient alters its
value; and if ever new narcotic free serum leaves the brain cells, the
narcotic dialyses out and the cell resumes its function : e.g. ethyl-alcohol
is soluble in oil and in water, and 2 per cent. marcotises tadpoles in water
in a few minutes; but if the tadpoles are now transferred to 1 per cent.
alcohol, within five minutes their vivacity is restored, as the alcohol has
dialysed out of the nerve cells.
The partition coefficient can be estimated chemically or physiologically
by the following simple methods.
(a) Non-volatile solid substances soluble in water.—Dissolve 1 grn. in
50 c.c. of water; add an equal bulk of olive oil; shake; then allow the
oil to separate, and take of the aqueous solution a known volume, say
10 c.c., and evaporate to dryness; weigh the residue.
If the original strength of the aqueous solution be designated as
a, and after shaking with oil the concentration be represented as b,
then the partition coefficient is equal to *;”.
Eacample.—A solution had a strength of 2 per cent. before shaking
and of 0.2 per cent. after shaking; partition coefficient equals ;= 9.
(b) Solid substances more soluble in oil than in water.—In this case
only 1 volume of oil is taken to 10, 50, or 100 of water, the ultimate
result being multiplied accordingly.
(c) Fluid substances soluble in oil and in water, and not too volatile.—
10 c.c. of the fluid are shaken with 50 c.c. of oil and water in a
graduated burette and the increase in volume of the oil noted. The
volume of the water is noted ; the increase of volume of the oil divided
oil
water -
by that of the water gives the coefficient
(d) Physiological method.—Tadpoles as compared with leeches or
species of worms belonging to the genus Nais are used. As a rule, a
leech requires double the dose necessary to narcotise a tadpole. An
aqueous solution of the substance is made of such strength that it will
just marcotise tadpoles = 8; another which will narcotise leeches, say
28. If the original concentration of the liquid equals a, and after
shaking with oil = b ; if this b solution narcotises tadpoles but does
not marcotise leeches, the concentration evidently lies between £8 and 28;
the solution is now diluted with a measured quantity of distilled water
§ 25, 26.] Toxic ACTION AND CHEMICAL COMPOSITION. 39
until the tadpoles show signs of recovery. From the amount of added
water the concentration b is calculated, and the partition coefficient
obtained. That the narcotic action to a great extent is parallel with
the solubility in oil is well shown by a research of H. Meyer on tadpoles,
in which the coefficient of each of the substances experimented with
was also ascertained.
* $ 25. In some cases the increase of CO groups weakens the action
of a poison; thus, in allantoin there are three carbonyl (CO) groups;
this substance does not produce excitation of the spinal cord, but it
heightens muscular irritability and causes, like xanthin, muscular
rigidity; alloxantin, with a similar structure but containing six car-
bonyl groups, does not possess this action.
NH-CH-NH NH –CO CO – HN
| | | | O | |
º CO CO {- C co
| | |
NH-CO NH, NH-CO CO—HN
Allantoin. Alloxantin.
§ 26. A theory of general application has been put forward and
supported with great ability by Oscar Loew * which explains the action
of poisons by presuming that living has a different composition to dead
albumin; the albumin of the chemist is a dead body of a definite
composition and has a stable character; living albumin, such as circu-
lates in the blood or forms the protoplasm of the tissues, is not “stable"
but “labile.” Loew says:—“If the old idea is accepted that living
albumin is chemically the same substance as that which is dead,
numerous toxic phenomena are inexplicable. It is impossible, for
instance, to explain how it is that diamide NºH, and hydroxylamine
NH3OH are toxic, even with great dilution, on all living animals; whilst
neither of those substances have the smallest action on dead plasma or
the ordinary dissolved passive albumin, there must therefore be present
in the albumin of the living plasma a grouping of atoms in a ‘labile'
condition (Atomgruppirungen labile, Art) which are capable of entering
into reactions; such, according to our present knowledge, can only
be the aldehyde and the ketone groups. The first mentioned groups
are more labile and react in far greater dilution than the latter
groups.”
Loew considers that all substances which enter into combination
with aldehyde or ketone groups must be poisonous to life generally.
For instance, hydroxylamine, diamide and its derivatives, phenylhy-
drazine, free ammonia, phenol, prussic acid, hydric sulphide, sulphur
dioxide and the acid sulphites all enter into combination with
aldehyde.
* Ein naturliches System der Gift-wirkwngen, Munchen, 1893.
4O POISONS : THEIR EFFECTS AND DETECTION. [$ 26.
So again the formation of imide groups in the aromatic ring increases
any poisonous properties the original substance possesses, because the
imide group easily enters into combination with aldehyde: thus piperi-
dine (CH2)4NH is more poisonous than pyridine (CH),N ; coniine NH
(CH3),CH – CH, -CH2CHs is more poisonous than collidine N(CH),
C – CH – (CHA), ; pyrrol (CH), NH than pyridine (CH),N ;
C.H. —CH-NH
and amarin * | XCH-CH. than hydrobenzamide
C.H. – C = N
If the theory is true, then substances with “labile” amido groups,
on the one hand, must increase in toxic activity if a second amido group
is introduced ; and, on the other, their toxic qualities must be diminished
if the amido group is changed into an imido group by the substitution
of an atom of hydrogen for an alkyl.
Observation has shown that both of these requirements are satisfied;
phenylenediamine is more poisonous than aniline; toluylenediamine
more poisonous than toluidine. Again, if an atom of hydrogen in the
amido (NH2) group in aniline be replaced by an alkyl, e.g. methyl or
ethyl, the resulting substance does not produce muscular spasm; but if
the same alkyl is substituted for an atom of hydrogen in the benzene
nucleus, the convulsive action remains unaffected.
If an acidyl, as for example the radical of acetic acid, enter into the
amido group, then the toxic action is notably weakened; thus, acetani-
lide is weaker than aniline, and acetylphenylhydrazine is weaker than
phenylhydrazine. If the hydrogen of the imido group be replaced by
an alkyl or an acid radical, and therefore tertiary bound nitrogen
restored, the poisomous action is also weakened.
In xanthin there are three imido groups; the hydrogen of two of
these groups is replaced by methyl in theobromine; and in caffeine the
three hydrogens of the three imido groups are replaced by three methyls,
thus:–
NH-CH N. CH3–CH s . CHs—CH
| | | | |
CO C–NH CO C–N . CHA CO C–N . CHA
| | >co || || >co || || >00
NH–C–N NH C–N N. CH3–C=N
Xanthine. Theobromine. Caffeine.
* Th. Weyl (Lehrbuch der organischen Chemie) states (p. 385) that amarin is not
poisonous, but Baccheti (Jahr. d. Chemie, 1855) has shown that 250 mgrms, of the
acetate will kill a dog, 80 mgrms, a guinea-pig; and that it is poisonous to fishes,
birds, and frogs: hydrobenzamide in the same doses has no effect.
§ 26.] Toxic ACTION AND CHEMICAL COMPOSITION. 4 I
—and experiment has shown that theobromine is weaker than xanthime,
and caffeine still weaker than theobromine.*
Loew f makes the following generalisations:—
1. Entrance of the carboxyl or sulpho groups weakens toxic
action.
2. Entrance of a chlorine atom exalts the toxic character of the
catalytic poisons (Loew's catalytic poisons are alcohols, ether, chloroform,
chloral, carbon tetrachloride, methylal, carbon disulphide and volatile
hydrocarbons).
3. Entrance of hydroxyl groups in the catalytic poisons of the
fatty series weakens toxic character; on the other hand, it exalts the
toxicity of the substituting poisons. (Examples of Loew's class of
“substituting” poisons are hydroxylamine, phenylhydrazine, hydric
cyanide, hydric sulphide, aldehyde, and the phenols.)
4. A substance increases in poisonous character through every
influence which increases its power of reaction with aldehyde or amido
groups. If, for example, an amido or imido group in the poison
molecule be made more “labile,” or if thrice linked nitrogen is converted
into nitrogen connected by two bands, whether through addition of
water or transposition (umlagerung), or if a second amido group enters,
the poisonous quality is increased. Presence of a negative group may
modify the action.
5. Entrance of a nitro group strengthens the poisonous character.
If a carboxyl or a sulpho group is present in the molecule, or if, in
passing through the animal body, negative groups combine with the
poison molecule, or carboxyl groups are formed in the said molecule; in
such cases the poisonous character of the nitro group may not be
apparent.
6. Substances with double carbon linkings are more poisonous than
the corresponding saturated substances. Thus neurime with the double
linking of the carbon of CH, is more poisonous than choline;
vinylamine than ethylamine.
* W. Lusini (L’orsos?, 1898, xxi. 257) gives the following lethal doses for frogs per
100 grms. body weight :—
Monomethylxanthine, . g te e te tº; tº 0-03
Theobromine, . º * ge * g te & 0-02
Caffeine, . & e tº * ſº © º ge 0 °012
—successive introduction of methyl groups being accompanied by an increased toxic
action.
J. T. Cash and W. R. Dunstan (Proc. Roy. Soc., xviii. 384, 1901) have shown
that withdrawal of the acetyl group both in pyraconitine and in benzaconine almost
destroys their toxicity; by substituting methyl for acetyl in aconitine there is also a
reduction of toxicity.
f En naturliches System der Gift-wirkungen, Munchen, 1893.
42 POISONS: THEIR EFFECTS AND DETECTION. [$ 27, 28.
CH=CH, CH2—CH2OH
chosó (OHonó
OH OH
Neurine. Choline.
CH, º
|
CH.N.H., CH.N.H.,
Vinylamine. Ethylamine.
§ 27. M. Ch. Michet * has investigated the comparative toxicity of
the metals by experiments on fish, using species of Serranus, Crenolabrus,
and Julius. The chloride of the metal was dissolved in water and
diluted until just that strength was attained in which the fish would
live 48 hours; this, when expressed in grammes per litre, he called
“the limit of towicity.”
The following is the main result of the inquiry, by which it will be
seen that no relation was found between “the limit of toxicity” and the
atomic weight.
TABLE SHOWING THE RESULTS OF EXPERIMENTS ON FISH.
No. Of - Limit of
Experiments. Metal. * Toxicity.
20. Mercury, . e e e e e g •00029
7. Copper, e e - º g - º •0033
20. Zinc, . & - º º º -> © •0084
10. Iron, . o º º º g - e •014
7. Cadmium, . º º & & e e -017
6. Ammonium, . º º g e º º *064
7. Potassium, . º • & tº - e “10
10. Nickel, . g º o e & - º '126
9. Cobalt, . e e e º e - e •126
11. Lithium, e º e e º - º •3
20. Manganese, . º tº º º º tº •30
6. Barium, º e c º º o e •78
4. Magnesium, . º - e º e . 1'5
20. Strontium, . tº e g º º . 2-2
5. Calcium, e º e w º º . 2'4
6. Sodium, tº º º g º - , 24*17
W.—Life-Tests: The Action of Poisons on the Lower
Forms of Life.
§ 28. The progress of synthetic chemistry places annually a large
number of more or less toxic substances in commerce, and it may often
be necessary to ascertain whether a given extract is poisonous at all, and
if so, what is its action. Similarly, the action of poison on life forms
generally will assist the toxicological chemist in the identification of a
substance.
* “De la Toxicité comparée des différents Métaux.” Note de M. Ch. Michet
Compt. Rend., t. xciii. p. 649, 1881.
§ 28.] LIFE-TESTS. 43
The chief methods of experiment are the following:—
(1) Action on the red blood corpuscles.
(2) Action on unicellular organisms.
(3) Cephalopoda.
(4) Insects.
(5) Fffect of poisons on the heart of cold-blooded animals.
(1) Action on the red blood corpuscles (erythrocytes).
Any blood may be used, but Heinz “ has proposed that rabbit's blood
should be taken as a standard.
The blood is defibrinated and several test tubes are charged, each with
10 drops of the defibrinated blood. A solution of the substance in
various strengths is now added to the blood, adding also common salt to
each solution so as to bring the concentration equal to 0.9 per cent. of
common Salt ; such a solution, with regard to rabbit's blood, is osmotic.
If the red blood corpuscles dissolve, it shows the substance has a
hamolytic poisonous action on the red blood corpuscles. -
Examples of poisons which dissolve the red blood corpuscles are—
arseniuretted hydrogen, the poison of the bee, snake poison generally,
Saponin, phallin.
(2) Action on Infusoria.-The infusoria are extremely sensitive to
the poisonous alkaloids and other chemical agents. Strong doses of the
alkaloids cause a contraction of the cell contents, and somewhat rapid
disintegration of the whole body; moderate doses at first quicken the
movements, then the body gets perceptibly larger, and finally, as in the
first case, there is disintegration of the animal substance.
The most suitable for the research are the larger kinds, such as
paramaecia: these are easily obtained by steeping hay in water and
incubating at blood heat for about 24 hours. Among a number of species
will be observed several paramaecia, such as Paramaecium caudatum
and others. Still more suitable organisms are, however, the opalinae.
Opalina ranarum.—The opalinae are ciliated organisms which are
found in the rectum of almost every frog at all times of the year.
They are oval, can just be seen with unaided sight as white points, con-
tain a number of clear nuclei, and are capable of active movement by
reason of the numbers of cilia which clothe the surface.
They are usually obtained from the frog by first paralysing the
brain so as to destroy sensibility to pain, cutting out the intestine and
the lower part of the caecum, and slitting it up while immersed in a 0-6
per cent. solution of common salt.
The inner lining may now be stroked by means of a camel's hair
brush and the opalinae thus detached. Two drops of water containing
* Handbuch der experimentelle Pathologie w. Pharmakologie, Jena, 1904.
44 POISONS : THEIR EFFECTS AND DETECTION. [$ 28.
opalinae substances are added in aqueous solution of known but varying
strength, and the behaviour of the organisms observed as compared with
one or more “controls” contained in watch-glasses or shallow dishes. A
weak magnifying power is alone required. The chief changes are either
swelling or shrinking, alterations in form, and often the appearance of
several vacuoles; sometimes, again, the contents become granular.
Rossbach * gives the following intimations of the proportion of the
toxic principle necessary to cause death :—Strychnine 1 part dissolved
in 1500 of water; veratrine 1 in 8000; quinine 1 in 5000; atropine 1
in 1000; the mineral acids 1 in 400–600; salts 1 in 200–300.
(3) Cephalopoda.-The action of a few poisons on the cephalopoda
has been investigated by M. E. Yung.f Curara placed on the skin had
no effect, but on the branchiae led to general paralysis. If given in even
fifteen times a greater dose than necessary to kill a rabbit, it was not
always fatal. Strychnine, dissolved in sea-water, in the proportion of
1 to 30,000, causes most marked symptoms. The first sign is relaxation
of the chromataphore muscle and the closing of the chromataphores;
the animal pales, the respiratory movements become more powerful,
and at the end of a notable augmentation in their number, they fall
rapidly from the normal number of 25 to 5 a minute. Then tetanus
commences after a time, varying with the dose of the poison ; the arm
stiffens and extends in fan-like form, the entire body is convulsed, the
respiration is in jerks, the animal empties his pouch, and at the end of
a few minutes is dead, in a state of great muscular rigidity. If at this
moment it is opened, the venous heart is found still beating. Nicotine
and other poisons were experimented with, and the cephalopoda were
found to be generally sensitive to the active alkaloids, and to exhibit
more or less marked symptoms.
(4) Insects.-The symptoms which may be distinguished in poisoned
flies are dulness or vivacity of movement, loss of power of progression,
paralysis of legs or wings or both, protrusion of the fleshy proboscis,
disorderly movements, and so forth.
Flies are caught without injury by swiftly placing over them a
watch-glass on the window-pane; a card is then inserted under the watch-
glass and the fly or flies transferred to a table in a good light. Powders,
extracts, liquids can now be easily introduced into the watch-glass, or
the first watch-glass may be placed on another; in either case, owing to
the confined space, the insect becomes soiled with the substances placed
under the watch-glass, and also usually sucks some up in the efforts to
cleanse itself. -
As controls may be used a fly untreated and one submitted to a
* N. J. Rossbach, Pharm. Zeitschr, für Russland, xix. 628.
f Compt. Rend., t. Xci. p. 306.
§ 29.] LIFE-TEST.S. 45
little of the powder of the Pyrethrum rosea, one of the most powerful of
the insecticides.
In the presence of pyrethrum powder, within four minutes there is
much excitement, in from two to three minutes longer, disordered move-
ments, loss of balancing power, paralysis of the wings occur, and the fly
generally lies on its back, death taking place in from two to three hours.
In poisoning by sausages, bad meat, curarine, and in obscure cases
generally, in the present state of Science, experiments on living animals
are absolutely necessary. In this, and in this way only, in very many
instances, can the expert prove the presence of zymotic, or show the
absence of chemical poison.
The Wivisection Act, however, effectually precludes the use of life-
tests in England save in licensed institutions. Hence the “methods” of
applying life-tests described in former editions will be omitted.
§ 29. Effect of poisons on the heart of Cold-blooded Animals, —The Vivisection
Act does not, however, interfere with
the use of certain living tests, such,
for instance, as the testing of the
action of poisons upon the recently
extirpated hearts of cold-blooded
animals.
The heart of the frog, of the
turtle, of the tortoise, and of the
shark will beat regularly for a long
time after removal from the body, if
supplied with a regular stream of
nutrient fluid. The fluids used for
this purpose are the blood of the
herbivora diluted with common salt
solution, or a serum albumin solution,
or a 2 per cent. Solution of gum arabic
in which red blood corpuscles are sus-
pended. The simplest apparatus to ,”
use is that known as “Williams’.” Y.”
Williams' apparatus consists of two
glass bulbs (see diagram), the one, P,
containing nutrient fluid to which a
known quantity of the poison has been
added; the other, N, containing the
same fluid but to which no poison has
been added; these bulbs are connected
by caoutchouc tubing to a three-way * *
tube, T, and each piece of caoutchouc
tubing has a pressure screw clip, W’
and V ; the three-way tube is con-
nected with a wider tube containing a
valve float, F, which gives free passage
of fluid in one direction only, that is,
in the direction of the arrow; this last wide tube is connected with a Y piece
of tubing, which again is connected with the aorta of the heart under examination,
l
.
Re-
*-
Williams’ Apparatus.





46 POISONS : THEIR EFFECTS AND DETECTION. [$ 29.
the other leg of the Y tube is connected with another wide tube, X, having a float
valve, Fº: the float containing a drop of mercury and permitting (like the float valve
F) passage in one direction only of fluid, it is obvious that if the clip communicating
with N is opened and the clip communicating with P is closed, the normal fluid
will circulate alone through the heart; if, on the other hand, the P clip is open
and the N clip closed, the poisoned blood will alone feed the heart. It is also clear
that by raising or depressing the bulbs, the circulating fluid can be delivered at any
pressure, high or low. Should a bubble of air get into the tubes, it can be got rid of
by removing the cork at S and bringing the fluid up to the level of the top of the
aperture. The observation is made by first ascertaining the number and character of
the beats when the normal fluid is circulating, and then afterwards when the normal
is replaced by the poisoned fluid. A simpler but less accurate process is to pith two
frogs, excise their respective hearts, and place the hearts in watch-glasses contain-
ing either serum or a solution of common Salt (strength 0.75 per cent.); to the one
heart is now added a solution of the poison under examination, and the difference in
the behaviour and character of the beats noted.
The phenomena to be specially looked for are the following:—
1. The heart at the height of the poisoning is arrested in diastole.
2. The heart at the height of the poisoning is arrested in systole.
Arrest in diastole.—The arrest may be preceded by the contractions becoming
weaker and weaker, or after the so-called heart peristalsis ; or it may be preceded by
a condition in which the auricle shows a different frequency to the ventricle.
The final diastole may be the diastole of paralysis or the diastole of irritation.
The diastole of irritation is produced by a stimulus of the inhibitory ganglia, and
only occurs after poisoning by the muscarine group of poisons. This condition may
be recognised by the fact that contraction may be excited by mechanical and electrical
stimuli or by the application of atropine solution ; the latter paralyses the inhibitory
nervous centres, and therefore sets the mechanism going again. The diastole of para-
lysis is the most frequent form of death. It may readily be distinguished from the
muscarine diastole ; for in muscarine diastole the heart is full of blood and larger
than normal, but in the paralytic form the heart is not fully extended, besides which,
although, if normal blood replace that which is poisoned, the beats may be restored
for a short time, the response is incomplete, and the end is the same ; besides which
atropine does not restore the beats. The diastole of paralysis may depend on para-
lysis of the so-called excito-motor ganglia (as with iodal), or from paralysis of the
muscular structure (as with copper).
The heart at the height of the poisoning stops in systole.
2. Arrest in systole.—The systole preceding the arrest is far stronger than
normal, the ventricle often contracting up into a little lump. Contraction of this
kind is specially to be seen in poisoning by digitalis. In poisoning by digitalis the
ventricle is arrested before the auricle ; in muscarine poisoning the auricle stops
before the ventricle. If the reservoir of Williams' apparatus is raised so as to
increase the pressure within the ventricle the beat may be restored for a time, to
again cease.
A frog's heart under the influence of any poison may be finally divided into
pieces so as to ascertain if any parts still contract ; the significance of this is, that
the particular ganglion supplying that portion of the heart has not been affected : the
chief ganglia to be looked for are Remak's, on the boundary of the sinus and auricle :
Ludwig's, on the auricle and the septum of the auricle; Bidder's, on the atrioventri-
cular border, especially in the valves ; and Dogiel's ganglion, between the muscular
fibres. According to Dogiel, poisons acting like muscarine affect every portion of the
heart, and atropine restores the contractile power of every portion.
Jacobi's apparatus.-Glass canulas are introduced into the left vena cava and
aorta respectively, the other big vessels being ligatured ; the arrangement is as in the
§ 29.] LIFE-TESTS. 47
figure. The one canula is connected with an india-rubber tube a, attached to Mar-
riott's flasks by means of a Y-piece ; the other to a T-piece T, connected on the one
side to a small mercury manometer ; the limb of the manometer nearest the T-piece
is connected with a pressure tube S ; the other limb of the manometer is, as shown,
provided with a recording apparatus which draws a curve in the revolving cylinder C ;
the other side of the T-piece consists of a tube, connected with a wider tube W ; into
this fits a glass rod, which can be pushed in and out; the glass rod is so arranged as
to leave a fine capillary slit ; the farther this rod is pulled out the easier the fluid
drops into V, the farther it is pushed in the slower the liquid drops, and therefore
the greater the pressure. The tube with the glass rod is horizontal, and a few mms.
higher than the level of the fluid in R; the zero point of the manometer is carefully
adjusted to this level. If, in the manner stated, the pressure is raised, the pressure
tube S begins to fill with the nutrient fluid, and the heart is compelled to work at a
gradually increasing pressure, and this pressure may be registered on the kymograph
by comparison of the tracing with that of the “time curve” Z.
*
ºf Aſſ
ºfºº ºf Aº ‘
Jacobi's Apparatus.
Jacobi has experimented with the pressures in the aorta and the auricle of large
frogs, and has been able to nearly imitate the natural pressure in the isolated heart.
If the latter works with a difference in level of 10–20 mm. the ventricle drives the
fluid into the pressure tube 50–66 cm. and the fluid drops into the little syphon V
regularly with each systole, two or three drops escaping, that is, with ten pulsations
from 1.0–1.5 grims., which with a height of 50 cm. corresponds to work of 50–75
grms. ~.
Jacobi ingeniously registers graphically the amount of fluid flowing in relation
to time, pressure, and pulse as follows:—Around the little glass rod is wound a moist
shred of wool, leading the liquid into a small glass vessel syphon shaped, W, which is
balanced at one end of a slender rod g, equilibrium being obtained by a counterpoise ;
the little vessel when full rapidly empties itself by syphon action, and hence is in
intermittent vibration ; these vibrations are recorded graphically by breaking and
making contact at p with a galvanic battery arrangement, and by means of the
magnet at M the attached marker draws a line on the revolving cylinder C, at the
same moment lines are drawn by the markers A and Z. By means of this instrument
either normal or poisoned fluid may be put into the isolated heart, and the effects
thus graphically registered.



48 POISONS: THEIR EFFECTS AND DETECTION. [$ 30, 31.
§ 30. The effect of poisons on the iris.-Several poisons affect the pupil, causing
either contraction or dilatation. The most suitable animal is the cat, the pupil of
the cat readily showing either state.
Toxic myosis, or toxic contraction of the pupil.—There are two forms of toxic
myosis, one of which is central in its origin. In this form, should the poison be
applied to the eye itself, no marked contraction follows; the poison must be swallowed
or injected subcutaneously to produce an effect. The contraction remains until
death. -
The contraction in such a case is considered to be due to a paralysis of the dilata-
tion centre; it is a “myosis paralytica centralis; the best example of this is the
contraction of the pupil caused by morphine.
In the second case the poison, whether applied direct to the eye or entering the
circulation by subcutaneous injection, contracts the pupil ; the contraction persists if
the eye is extirpated, but in all cases the contraction may be changed into dilatation
by the use of atropine. An example of this kind of myosis is the action of muscarine.
It is dependent on the stimulation of the ends of the nerves which contract the pupil,
especially the ends of the nervus oculomotorius supplying the sphincter iridis; this
form of myosis is called myosis spastica periphera. A variety of this form is the myosis
Spastica muscularis, depending on stimulation of the musc. sphincter iridis, seen in
poisoning by physostigmine. This causes strong contraction of the pupil when locally
applied ; the contraction is not influenced by small local applications of atropine, but
it may be changed to dilatation by high doses. Subcutaneous injection of small doses
of physostigmine does not alter the pupil, but large poisonous doses contract the pupil
in a marked manner.
Toxic mydriasis, or toxic dilatation of the pupil.-The following varieties are
to be noticed:—
1. Toxic doses taken by the mouth or given by subcutaneous injection give rise
to strong dilatation ; this vanishes before death, giving place to moderate contraction.
This form is due to stimulation of the dilatation centre, later passing into paralysis.
An example is found in the action of aconite.
2. After subcutaneous or local application, a dilatation neutralised by physostig-
mine in moderate doses. This is characteristic of 8-tetrahydronaphthylamine.
3. After subcutaneous injection, or if applied locally in very small doses, dilatation
occurs persisting to death. Large doses of physostigmine neutralise the dilatation, but
it is not influenced by muscarine or pilocarpine: this form is characteristic of atropine,
and it has been called mydriasis paralytica periphera.
WI.-General Method of Procedure in Searching
for Poison. .
§ 31, Mineral substances, or liquids containing only inorganic
matters, can cause no possible difficulty to any one who is practised
in analytical investigation; but it is otherwise with organic fluids or
solids.
The first thing to be done is to note accurately the manner in which
the samples have been packed, whether the seals have been tampered
with, whether the vessels or wrappers themselves are likely to have
contaminated the article sent; and then to make a very careful observa-
§ 3 I.] PROCEDURE IN SEARCHING FOR POISON. 49
tion of the appearance, smell, colour, and reaction of the matters, not
forgetting to take the weight, if solid—the volume, if liquid. All these
are obvious precautions, requiring no particular directions.
If the object of research is the stomach and its contents, the contents
should be carefully transferred to a tall conical glass; the organ cut
open, spread out on a sheet of glass, and examined minutely by a lens,
picking out any suspicious-looking substance for closer observation.
The mucous membrane should now be well cleansed by the aid of a
wash-bottle, and if there is any necessity for destroying the stomach, it
may be essential in important cases to have it photographed. The
washings having been added to the contents of the stomach, the sedi-
ment is separated and submitted to inspection, for it must be remembered
that, irrespective of the discovery of poison, a knowledge of the nature
of the food last eaten by the deceased may be of extreme value.
If the death has really taken place from disease, and not from
poison, or if it has been caused by poison, and yet no definite hint of the
particular poison can be obtained either by the symptoms or by the
attendant circumstances, the analyst has the difficult task of endeavour-
ing to initiate a process of analysis which will be likely to discover any
poison in the animal, vegetable, or mineral kingdom. For this purpose
the following process has been devised, which differs from those published
at an earlier date mainly in the prominence given to operations in a
high vacuum, and the utilisation of biological experiment as a matter of
routine. Taking one of the most difficult cases that can occur—viz.,
one in which a small quantity only of an organic solid or fluid is available
—the best method of procedure is the following:—
1. Distillation in a vacuum at a low temperature.
2. Collecting the volatile products.
3. Dehydrating the organic substances.
4. Dissolving out from the dry mass fatty matters and alkaloids,
glucosides, etc., by ethereal and alcoholic solvents.
5. Destroying organic matter and searching for metals.
A small portion is reserved and examined microscopically, and, if
thought desirable, submitted to various “cultivation” experiments.
The greater portion is at once examined for volatile matters, and having
been placed in a strong flask, and, if neutral or alkaline, feebly acidulated
with tartaric acid, connected with a second or receiving flask by glass
tubing and caoutchouc corks. The caoutchouc cork of the receiving-
flask has a double perforation, so as to be able, by a second bit of angle
tubing, to be connected with the mercury-pump described in the author's
work on “Foods,” the figure of which is here repeated (see the
accompanying figure). With a good water-pump having a sufficient
length of fall-tube, a vacuum may be also obtained that for practical
4
5O POISONS : THEIR EFFECTS AND DETECTION. [$ 31.
purposes is as efficient as one caused by mercury; if the fall-tube
delivers outside the laboratory over a drain, no offensive odour is
Dr ing Tube
filled with
fused calcic
chloride
* N
N - | NS º
N |NºN R º
N §§
§§§ :
§ N § N t
º - §§§
N | § † º
D º N N
§
§ w
> SºS º
§§ º
sº • *N NS
ſ N N
Nº N. N. R
D NS §§ N
at air
experienced when dealing with putrid, stinking liquids. A vacuum
having been obtained, and the receiving-flask surrounded with ice, a
distillate for preliminary testing may be generally got without the

§ 3 I.] IPROCEDURE IN SEARCHING FOR POISON, 5 I
action of any external heat; but if this is too slow, the flask containing
the substances or liquid under examination may be gently heated by a
water-bath: water, volatile oils, a variety of volatile substances, such as
prussic acid, hydrochloric acid, phosphorus, etc., if present, will distil
over. It will be well to free in this way the substance, as much as
possible, from volatile matters and water. When no more will come
over, the distillate may be carefully examined by redistillation and the
various appropriate tests.
The next step is to dry the sample thoroughly. This is best effected
also in a vacuum by the use of the same apparatus, only this time the
receiving-flask is to be half filled with strong sulphuric acid. By now
applying very gentle heat to the first flask, and cooling the sulphuric
acid receiver, even such substances as the liver in twenty-four hours
may be obtained dry enough to powder.
Having by these means obtained a nearly dry
friable mass, it is reduced to a coarse powder, and
extracted with petroleum ether, and treated as under
the special section for Alkaloids and Glucosides (see
Index).
It must also be remembered that there are a few “à 2.2.2
metallic compounds (as, for example, corrosive sub- This figure is from
limate) which are soluble in alcohol and ethereal “Foods,”, B, is a
bell-jar, which can
solvents, and must not be overlooked. be adapted by a cork
The residue, after being thus acted upon succes- to a condenser; R is
sively by petroleum, by alcohol, and by ether, is both ..., º:
water-free and fat-free, and also devoid of all organic immersed , in mer-
# e ſº º ;..., cury, which the deep
poisonous bases and principles, and it only remains ...
to treat it for metals, various processes for which are
as follows. These processes have been devised chiefly for the detection
of arsenic and antimony, but evidently may be used, with obvious
limitations, for most mineral matters.
A very fair and complete analysis may be made from a small amount
of material. The process is, however, somewhat faulty in reference to
phosphorus, and also to oxalic acid and the oxalates; these poisons, if
suspected, should be specially searched for in the manner to be more
particularly described in the sections treating of them. In most cases
there is sufficient material to allow of division into three parts—one for
organic poisons generally, one for inorganic, and a third for reserve in
case of accident. When such is the case, although, for organic principles,
the process of vacuum distillation just described still holds good, it will
be very much the most convenient way not to use that portion for
metals, but to operate on the portion reserved for the inorganic poisons
as follows, by destruction of the organic matter.

52 POISONS : THEIR EFFECTS AND DETECTION. [$ 32.
METHODS OF DESTROYING ORGANIC MATTER, WHEN
SEARCHING FOR MINERAL POISONS (ESPECIALLY
ARSENIC).
§ 32. (A) Destruction by heat.—Of all methods, destroying by heat
alone or in a current of oxygen is the most perfect ; always provided
that the apparatus is so arranged that volatile metallic vapours can be
condensed or otherwise recovered.
G. Bertrand, * in researches on the presence of arsenic in the animal
tissues, burns the organic matter by means of compressed oxygen in
Berthelot's calorimetric bomb. From 1–2 grms. of the substance,
previously dried, is placed in the bomb; and the combustion is initiated
by a very small shred of fulminating cotton in a platinum loop, through
which is passed an electric current.
Where necessary, the product of several combustions is accumulated
in the same bomb. The bomb is then washed out with water. The
water contains traces of nitric acid produced in the combustion, which
it is usually best to evaporate off.
The objection to the process is the expense of the apparatus, the
cheaper enamelled bombs in commerce, according to Bertrand, always
containing traces of arsenic ; besides which, only a very small quantity
of the substance can be dealt with at one operation. On the other hand,
the advantages are obvious. The combustion is complete, and a solution
can be readily obtained suitable for treatment by hydric sulphide or by
Marsh's apparatus.
Werryken f places 5–10 grms, of the previously dried organic matter
in a combustion tube, into which is led dry oxygen by three small tubes
of different length, in order to distribute the gas equally ; the tube is
connected with a series of bulbs charged with water. The tube is very
carefully heated to a dull red heat on each side of the substance; then
the substance itself is heated very carefully, in such a way as to
avoid brisk inflammation of the mass; on cooling, the tube is washed
out with hot nitric acid, the water in the bulbs added, and thus a nitric
acid solution obtained. -
In the method of Woehler and Siebold, the matters, suitably divided,
are heated in a porcelain dish with their weight of nitric acid until
an homogeneous mass has been obtained, then the acid is neutralised,
by soda, potash, ammonia, or lime, and evaporated to dryness. The
product is now cast in small portions at a time into a porcelain crucible
brought to a dull red heat. The ultimate mass, which should be of a
* G. Bertrand, “Emploi de la bombe calorimetrique pour demontrer l'existence
de l’arsenic dans l'organisme,” Comptes Rend., 1903.
† Journ. de pharm. d’Anvers, 1872.
§ 32.] PROCEDURE IN SEARCHING FOR MINERAL POISONs. 53
pure white colour, is then dissolved in boiling water and a solution
obtained absolutely free from organic matter. According to A. Gautier,
this method should not be used in researches on arsenic, the loss of
arsenic being considerable.
Basic method.—In this method the organic matters, intimately mixed
with half their weight of pure lime or pure magnesia, are burned up in
a muffle, and the product treated with nitric or hydrochloric acid until
dissolved. The process has been used in researches on malt and on
coal, and it is stated no arsenic is lost ; but it has not been used in
other toxicological investigations.
J. Ogier's method.*—The organic matter (viscera, e.g.) is finely
divided and made into a soupy mass by the addition of water, and
introduced into a large flask ; about fºr of the weight of the organic
substance of potassic chlorate is added. Hydrochloric acid gas produced
by the action of pure sulphuric acid on pure hydrochloric acid is passed
through the liquid, the gas finally escaping being led through a little
water to arrest possible traces of arsenic chloride. As soon as yellow
vapours are seen above the liquid the current of gas is stopped, the
process of destruction going on now without farther assistance. The
end of the reaction is indicated by the yellow colour of the liquid. The
insoluble matters are filtered off, and, if desired, may be treated by one
or other of the dry methods; but it can be shown that, as a rule, they
are destitute of poisonous metals. The destruction is rapid, 500 to
1000 grims. of organic matter being destroyed within the hour.
A. Williers' f method.—Williers uses the salts of manganese. The
substances, made into the consistence of porridge by the addition of
hydrochloric acid diluted with from 2–3 times its volume of water, are
introduced into a suitable flask, which has a cork carrying a funnel
provided with a stopcock and a tube, the end of which dips into water.
Through the funnel is gradually introduced a solution of a manganese
salt and a little nitric acid, a regulated heat being at the same time
applied; the gases evolved are nitrogen and carbon dioxide, hence the
products are without odour; the process is even more rapid than that
of Ogier. In researches for arsenic it is obviously necessary to take
accurately weighed or measured quantities of the reagents, and, if arsenic
is found, to make with equal quantities of the reagents a blank
experiment for the purpose of ascertaining their freedom from arsenic.
Process of Armand Gautier, i-Gautier has revived the old process
of destruction of organic matter by sulphuric and nitric acids, with
improvements in detail.
* Traité de chimie toacicologique, Paris, 1899.
t Comptes Rendus, 1896.
† A. Gautier, Bull. Soc. chim., 1903.
54 POISONS : THEIR EFFECTS AND DETECTION. [$ 32
Four grims. of pure sulphuric acid and 40 grims. of nitric acid
(1°42 sp. gr.) are added to 100 grms, of the organic matter in a
porcelain dish. This is carefully heated until the entire mass assumes
a chocolate colour; 30 additional grims. of nitric acid are added little
by little, taking care that before the addition of a fresh quantity the
matters have a brown tint; after the addition of the final quantity,
the heat is continued until the contents are almost black, with
commencing carbonisation.
Next, 12 more grims, of nitric acid, three successive times are added,
after each addition pushing the carbonisation still farther. The operation
is finished when no more fumes are evolved and the carbon detaches itself
from the dish. The mass is now rubbed to a powder in the dish itself
by means of a pestle, and exhausted with from 250 to 300 c.c. of boiling
water. This, after being filtered, contains the metals; some sulphurous
acid is added, and the whole is submitted to a current of SH, for 3
hours, first at a temperature of 100°C, and then at ordinary temperatures.
100 grms, of muscle leave from 2-5 to 3 grims. of carbon. The quantity
of acid used in ordinary cases is therefore 4 grms, of sulphuric acid
and 106 of nitric acid; but should the matters be very fatty, more
nitric acid is recommended.
According to Gautier, the nitric acid acts on the chlorides,
forming a nitro-hydrochloric acid, very poor in the latter (hydro-
chloric) acid, so that the chlorine is expelled with the nitrous
products without a trace of arsenic chloride being formed. The
excess of nitric acid also effectually prevents the formation of
arsenic sulphide.
Pagel's process.-The older processes in which arsenic is distilled
over as chloride of arsenic, according to the researches of Gautier, do
not yield good results. Schlagdenkaufen and Pagel have, however,
elaborated a process in which they state that in all cases the total
amount of arsenic may be recovered in the form of chloride.
The suspected organic matters are placed in a tubulated retort
with a mixture of two parts of pure sodium chloride and one part of
potassium bichromate; by means of a funnel tube provided with stopcock,
pure sulphuric acid is allowed to drop little by little on to the mixture.
A violent reaction occurs, chromous chloride (CrO2Cl2) gas being pro-
duced ; the vapours are caused to pass first into a flask cooled with
water, then through bulbs or other apparatus, the final portion of which
is charged with a weak solution of potash. The action is aided by
heat; the addition of sulphuric acid is continued until no more yellow
vapours are produced and the carbon disappears. The gas is decom-
posed by the first washing of water into hydrochloric acid and chromic
acid, CrO2Cl2 + H2O = CrO3 + 2HCl. The heat being continued, sulphur
§ 32.] PROCEDURE IN SEARCHING FOR MINERAL POISONS. 55
dioxide is produced, which, in its turn, reduces the chromic acid. The
final green solution, with the various washing waters, are freed from
sulphur dioxide and submitted to hydric sulphide, while the non-
volatile metals are tested for in the residue remaining in the flask,
the residue for this purpose being exhausted with hot water, and the
solution filtered.
In all cases the amount of acidity of the solution of the inorganic
salts should be ascertained by titrating with normal soda an aliquot
part of the same.
The liquid is now saturated with a current of gaseous sulphuretted
hydrogen until it smells strongly of the gas. The flask should now be
corked and set aside for at least twelve hours, any precipitate is filtered
off, the liquid is shaken and warmed to expel the excess of sulphuretted
hydrogen. Sodic acetate is now added in slight excess of the acidity,
as determined by the titration above mentioned, so as to replace the
mineral acid by acetic acid. For every 10 c.c. of normal soda 1:36
grm. of sodic acetate in theory would exactly replace the mineral acid.
For example, supposing that the original liquid measured 510 c.c.,
10 c.c. of which was neutralised by 5 c.c. of normal soda, then the
proper quantity to add of sodic acetate to the 500 c.c. would be 34
grms, to exactly replace the acid, and an extra couple of grms. So as to
ensure an excess; in all 36 grims. The liquid is now again saturated
with sulphuretted hydrogen in order to throw down any zinc as
sulphide.
Should a precipitate occur, this is filtered off, and the filtrate
Saturated with ammonium sulphide.
(a) Precipitate from acid H2S solution.—From the acid solution,
the sulphide of a large number of substances may theoretically be
present in the precipitate, e.g. arsenic, antimony, tin, germanium,
molybdenum, selenium, tellurium, gold, platinum, iridium, silver,
mercury, lead, bismuth, copper, cadmium, palladium, osmium, rhodium,
and ruthenium ; but it is obvious that many of the above substances
are not likely to occur in a routine toxicological investigation. These
sulphides are treated with ammonium sulphide, which dissolves the
members of the above group up to and including iridium, and leaves
insoluble the remainder, which may be searched for in the ordinary
manner (see Lead, Mercury, etc.).
With regard to the sulphides soluble in ammonium sulphide, we
need only here consider tim, antimony, and arsenic, and these are best
separated by Carnot's method.* The ammonium sulphide solution is
made acid by means of HCl, and the dissolved sulphides (with sulphur)
are thrown down; these are collected on a filter, and dissolved by
* Traité d'amalyse des substances minérales, Paris, 1898.
56 POISONS : THEIR EFFECTS AND DETECTION. [$ 33.
means of either HCl and potassic chlorate or HCl with a little nitric
acid ; to the solution is added ammonium oxalate and ammonia, but
not in sufficient quantity to form a precipitate. The clear solution is
meated to ebullition and a solution of sodic hyposulphite added; this
throws down (with sulphur) the red sulphide of antimony, should
antimony be present. On separating the precipitate by filtration the
filtrate is made acid by hydrochloric acid, and a current of hydric
sulphide passed through, and well boiled to get rid of sulphur dioxide;
any arsenic is precipitated as yellow sulphide, and any tin remains in
solution ; the latter may be separated as bisulphide by Saturating the
filtrate with ammonia, then adding ammonium sulphide, and after a few
minutes, acetic acid.
(b) Precipitate from acetic H.S Solution. See Zinc.
(c) Precipitate from ammonium sulphide. See Chromium, Nickel,
Cobalt, etc.
(d) Examine the filtrate for alkalies and alkaline earths. Any
residue remaining after destroying organic matter and dissolving in
acids may be specially treated for the detection of silver and barium
salts, should these be present in an insoluble form.
The residue is dried and intimately mixed with three times its
weight of a mixture containing two parts of sodic nitrate and one part
of sodium hydrate. This is placed, little by little, in a red-hot porcelain
crucible and melted. The melted mass is cooled, dissolved in a little
water, a current of CO2 passed through the solution to convert
any caustic soda into carbonate, and the solution boiled. The
insoluble portion consists of carbonates of lead and baryta, and
of metallic silver. The mixture is filtered ; the insoluble residue on
the filter is warmed for some time with dilute nitric acid ; the solution
of nitrates of silver, lead and barium are concentrated on the water-
bath nearly to dryness so as to get rid of any excess of acid, and the
mitrates dissolved in water ; then the silver is precipitated by hydro-
chloric acid, the lead by SH2, and the barium by sulphuric acid.
VII.-The Spectroscope as an Aid to the Identification
of certain Poisons.
§ 33. The spectra of many of the metals, of phosphine, of arsine,
and of several other inorganic substances, are characteristic and easily
obtained.
It is, however, from the employment of the micro-spectroscope that
the toxicologist is likely to get most assistance.
§ 33.] SPECTROSCOPIC APPEARANCES OF BLOOD. 57
Oscar Brasch * has within the last few years studied spectroscopy in
relation to the alkaloids and organic poisons. Some of these, when
mixed with Froehde's reagent, or with sulphuric acid, or with sulphuric
acid and potassic dichromate, or with nitric acid, give characteristic
colours, and the resulting solutions, when examined by a spectroscope,
for the most part show absorption bands; these bands may, occasion-
ally, assist materially in the identification of a poison. By far the best
apparatus is a micro-spectroscope of the Sorby and Browning type, to
which is added an apparatus for measuring the position on a scale of
the lines and bands. Seibert and Kraft of Wetzlar make an excellent
instrument, in which a small bright triangle is projected on the
spectrum ; this can be moved by a screw, so that the apex may be
brought exactly in the centre of any line or band, and its position
read on an outside scale. The first
thing to be done with such an instru-
ment is to determine the position on
the scale of the chief Fraunhofer
lines, or of the more characteristic
lines of the alkalies and alkaline
earths,f the wave lengths of which
are accurately known. If, now, the
scale divisions are set out as abscissae,
and the wave lengths in millionths of
a millimetre are made the ordinates
of a diagram, and an equable curve
plotted out, as fully explained in the
author's work on “Foods,” it is easy
to convert the numbers on the scale
into wave lengths, and so make the readings applicable to any spectro-
scope. For the purpose of graphical illustration the curve method is
convenient, and is adopted in the preceding diagrams, all taken from
Oscar Brasch's monograph. Where the curve is highest, the absorption
band is thickest ; where the curve is lowest, there the band is weak.
The fluid to be examined is simply placed in a watch-glass, the watch-
glass resting on the microscope stand.
* Ueber Verwendbarkeit der Spectroscopie zur Unterscheidung der Farben reac-
tionen der Gifte im Interesse der forensischen Chemie, Dorpat, 1890.
f The alkalies and earths used for this purpose, with their wave lengths, are as
follows: KCl, a line in the red A 770, in the violet x 404. Lithium chloride, red
line, 670°5; sodium chloride, yellow, 589; strontium chloride, line in the blue, 461.
It is also useful to measure the green line of thallium chloride = 535.
Collie, Proc. Roy. Soc., lxxi, 25, 1902, recommends a vacuum tube charged with
hydrogen, helium, and mercury vapour; this gives no less than 15 lines from the red
He (706'53) to H in the violet (434-1).

CURVES INDICATING THE POSITION OF ABSORPTION BANDS
i
;
:
3 5 3 *
e Veratine, Furfurol reaction (blue-violet).
... Weratroidine, j 5 y
. Jervine, Furfurol reaction (blue).
. Sabadine , , 3. (blue).
ON TREATING CERTAIN ALKALOIDS WITH REAGENTS.
H G F bR D GB A H G F bR D GB A
1 ====Zºº ſ s . . . . .” . . . 14
* I Li iſ Ilºilº
s|| || H-Hº.
“I I IL iſ I I II. In
*|| || || || | | | | | ||
*Is A iſ M | | ||
7| || All | | || ||º
|-|--|--|--|| ||
*|| || || | || 22
| | | || ºff-
11 | | ||A | | || | |2.
*|| || || || || || || ||
ºn ºn
F bF D CB A H G F bF. D. CB A
NOTES TO CURVES INDICATING ABSORPTION BANDS.
H
. Strychnine, treated with sulphuric acid and potasssic dichromate (violet).
. Brucine, treated with potassic nitrate and sulphuric acid (clear red).
. Quebrachine, treated with vanadium sulphate (dark blue).
. Quinine, Vogel's reaction (red).
. Caffeine, Murexid reaction (violet-red).
. Delphinoidin, Froehde's reagent (cherry-red).
. Weratrine, treated with sulphuric acid (straw-yellow).
2 3 9 } 3 y (cherry-red).
(carmine-red).
Sabadillin, treated with sulphuric acid (red).
(brown-red).
3.
Sabadine, treated with sulphuric acid (cherry-red).
. Physostigmine, , , 5 § (grass-green).
. Morphine, treated with Froehde's reagent and sugar (dark green).
. Narcotine, treated with a mixture of sulphuric acid and nitric acid (30 drops of
sulphuric to 1 drop of nitric), (red).
. Codeine, treated with Froehde's reagent and sugar (dark violet).
. Papaverine, treated with Froehde's reagent (green-blue).
. Sanguinarin, 2 3
(violet-red).
Chelidonin, 2 3 sulphate of vanadium (dark green).
. Solanin, 2 3 sulphuric acid and allowed to stand 4 hours (brown-red).
. Digitalin, 3 3 Erdmann’s reagent (red).
. Aniline, 5 y sulphuric acid and potassic dichromate (blue).

§ 34.] SPECTROSCOPIC APPEARANCES OF BLOOD. 59
The wave lengths corresponding to the numbers on the scale in the
diagram are as follows:—
W.L. W.L.
0 732 4 510-2
1 656 5 480 °0
2 589.2 6 458
3 549°8 7 4.38
Examination of Blood, or of Blood-Stains.
§ 34. Spots, supposed to be blood—whether on linen, walls, or
weapons—should, in any important case, be photographed before any
chemical or microscopical examination is undertaken. Blood-spots,
according to the nature of the material to which they are adherent,
have certain naked-eye peculiarities—e.g. blood on fabrics, if dry, has
at first a clear carmine-red colour, and part of it soaks into the tissue.
If, however, the tissue has been worn some time, or was originally
soiled, either from perspiration, grease, or filth, the colour may not be
obvious or very distinguishable from other stains; nevertheless, the
stains always impart a certain stiffness, as from starch, to the tissue.
If the blood has fallen on such substances as wood or metal, the spot is
black, has a bright glistening surface, and, if observed by a lens,
exhibits radiating fissures and a sort of pattern, which, according to
some, is peculiar to each species; so that a skilled observer might
identify occasionally, from the pattern alone, the animal whence the
blood was derived. The blood is dry and brittle, and can often be
detached, or a splinter of it, as it were, obtained. The edges of the
splinter, if submitted to transmitted light, are observed to be red.
Blood upon iron is frequently very intimately adherent; this is specially
the case if the stain is upon rusty iron, for haematin forms a compound
with iron oxide. Blood may also have to be recovered from water in
which soiled articles have been washed, or from walls, or from the soil,
etc. In such cases the spot is scraped off from walls, plaster, or masonry,
with as little of the foreign matters as may be. It is also possible to
obtain the colouring-matter of blood from its solution in water, and
present it for farther examination in a concentrated form, by the use of
certain precipitating agents.
In the following scheme for the examination of blood-stains, it is
presumed that only a few spots of blood, or, in any case, a small quantity,
is at the analyst's disposal.
(1) The dried spot is submitted to the action of a cold saturated
solution of borax. This medium (recommended by Dragendorff) *
* Untersuchungen von Blutspuren in Maschka's Handbuch, Bd. i. Halfband 2.
6O POISONS : THEIR EFFECTS AND DETECTION. [$ 35.
does certainly dissolve out of linen and cloth blood-colouring matter
with great facility. The best way to steep the spots in the solution is
to scrape the spot off the fabric, and to digest it in about a cubic
centimetre of the borax solution, which must not exceed 40”; the
coloured solution may be placed in a little glass cell, with parallel walls,
‘5 centimetre broad and 1 deep, and submitted to spectroscopic
examination, either by the ordinary spectroscope or by the micro-
spectroscope; if the latter is used, a very minute quantity can be
examined, even a single drop. A better solvent is Riegler's reagent,
to be described later. In order to interpret the results of this examina-
tion properly, it will be necessary to be intimately acquainted with the
spectroscopic appearances of both ancient and fresh blood.
§ 35. Spectroscopic Appearances of Blood.—Fresh blood defibrin-
ated, filtered, and examined in a test tube or in a suitable absorption
cell by a prism spectroscope shows, when diluted sufficiently with water,
two absorption bands, the one near the sodium line well defined, the
maximum shadow being at wave length 578:1; the other in the green
with somewhat fluffy edges, therefore less definite in the green, the
centre of the band being at 54 l'7; this two-banded spectrum is that
of oxyhaemoglobin. The spectrum is graphically represented in fig. 1,
taken from J. Formanek's paper.”
On exposure of the same solution to air, new bands make their
appearance; these new bands are those of methaemoglobin ; the older
the solution, the more the bands of methaemoglobin tend to intensify,
the more those of oxyhaemoglobin fade. The spectrum is, however,
with blood weeks or even months old, always a mixture of oxyhaemo-
globin and methaemoglobin ; the wave lengths of the two methaemo-
globin bands centres are respectively 634, and a weak band in the
green 500.8 (see fig. 2).
By adding ammonium sulphide to blood the spectrum of haemoglobin
(fig. 3) is obtained; it shows a weak absorption band (619.8) and a
broad, somewhat diffuse band (554?7). .
Oxyhaemoglobin solutions treated with alkalies suffer change; the
oxyhaemoglobin is separated into hamatin and an albuminous body.
The haematin is soluble in strong soda lye, and shows a single band in
alcoholic solution, which is situated about A 598.8 (see fig. 6). If this
alkaline solution of haematin is now treated with a reducing substance, a
third colouring substance makes its appearance, called by Hoppe-Seyler,
who discovered it, by the name of haemochromogen ; this shows two
absorption bands very similar to hamoglobin, but both bands are shifted
towards the violet end of the spectrum (A 559°1 and A 529'2) (fig. 7).
* “Ueber die Absorption Spectra des Blutfarbstoffe,” Zeit. f. anal. Chemie,
1901, 505.
§ 35.]
SPECTROSCOPIC APPEARANCES OF BLOOD. 61
*
By utilising the properties of hydrazin, which dissolves the red
blood corpuscles, and at the same time is a powerful reducing agent,
Riegler * has suggested the best general test for blood at present known.
Riegler's reagent is prepared as follows: 10 grims. of sodium hydroxide
are dissolved in 100 c.c. of water; to this 5 grims of hydražin are
added, and the whole shaken; lastly, alcohol of 96–97 per cent. is
added in equal volume, the mixture shaken, allowed to stand for two
hours and filtered; the filtrate is used as the reagent.
B C oc D
---
1 HTTTTTH } * Ż, Oxyhaemoglobin.
700 650 600
2 TTIII | TT % Methaemoglobin and
700 0 600 Oxyhaemoglobin.
3 H-H II H rº %. , Haemoglobin.
700 650 600
4. [TI TT TTTTT I ++ ++ # s * I 2%. Acid Haematin.
700 650 6. 30 500 450
5 • e e
[TTTTTTTTTI f I -H+ IT I Ž, Alkaline Haematin
700 650 600 550 (aqueous solution).
6 - ~~!-- , u_*: g
[TTTTTTTTTTTTU-I-T-I-T- <--~. Alkaline Haematin
700 650 600 550 500 450 (alcoholic solution).
7 ^ - *.
TTTTTTTTTTTT T- T-I- I Haemochromogen
700 650 600 550 500 (reduced Haematin).
8 %2. --~~~º. --~~~~ e
| I I I T I I I T TI T I I I f T | r zº,…, z'ſ ...g. zazz.”, º, . . . . . . . . . . . a. *.*.*.*.xyzzz...' ...,’, , ºrz (...' ... . . .”…,' . . . . - Haematoporphyrin
700 650 || 600 550 500 450 (acid solution).
9 º, ſº? Žižºzº.”
| I I | IIITT | I | I I H- I A , , ºr ; ; A ºž% %%º...?'. Haematoporphyrin
700 650 600 550 500 450 (alkaline solution).
10 z - * sº - - - º %%//, //;...º.º.º.º.º. ZººZºº,”
| TTI | III ITT | I-I-I | I I I | 7.7% º Sulphaemoglobin.
700 6 600 - 550 500 450
11 II ITTTTTTTTT T.I.T.T.T., r—r-Hazºº.…&#2:… Carbon-monoxide-
700 º 600 ,550 500 450 haemoglobin.
The reagent can be added to one or two drops of blood in a test
tube, or be used as a solvent for stains on wood, iron, and so forth.
It may also be used as a reagent for blood in urine, milk, and other
fluids, if the blood is small in quantity. In non-albuminous fluids, it
is advisable to add a little albumin, acidify with acetic acid, heat to
boiling, and treat the separated coagulum with the reagent.
The solution is of a fine purple-red colour; and whether the colouring
* “Ein neues Reagens zum Nachweis der verschiedenen Blutfarbstoffe oder der
Zersetzungsprodukte derselben,” Zeit f. analytische Chemie, 1904, 539.




62 POISONS: THEIR EFFECTS AND DETECTION. [$ 35.
matter be derived from blood, oxyhaemoglobin, methaemoglobin, or
haematin, the two bands of haemochromogen can be seen in the suitably
diluted solution; if the solution is shaken up with air, the spectrum
changes into the one-banded alkaline hamatin (fig. 6), as seen in an
alcoholic solution, but on standing the two-banded spectrum of haemo-
chromogen slowly comes back; these changes can be traced with the
naked eye, for the red solution, on shaking with air, takes a greenish
tint, and then slowly returns back into purple-red. There is no dye
which possesses similar properties, hence this naked-eye change is
almost sufficient to identify a red organic substance as blood. Haemato-
porphyrin (figs. 8 and 9) is obtained by heating blood carefully for a
short time with sulphuric acid of a certain concentration. -
Sulphaemoglobin (fig. 10) is obtained by treating diluted blood with
sulphuretted hydrogen in the presence of air; it gives a very definite
band (619-8); at the same time the oxyhaemoglobin bands fade ; this
is the appearance which may be seen in the blood of persons poisoned
by hydric sulphide.
The spectrum of carbon monoxide hamoglobin (fig. 11) is that of
oxyhaemoglobin with the bands slightly displaced towards the violet
end.
Formanek, in researches on guinea-pigs, has shown that the maximum
displacement only occurs when the blood has attained a certain amount
of Saturation with the gas.
In four animals the blood was examined during life, when the
convulsions began, and after death, with the following results:—
In convulsive stage. After death.
Centre of Centre of Centre of Centre of
chief band. subsidiary chief band. subsidiary
band. band.
(1) A 576 A 540 A 572°5 A 538-3
(2) A 576 A 540 X 572-7 A 538°5
(3) A 576 A 540 A 573°0 A 538-7
(4) * * * - - - A 572.7 A 538°5
The blood in CO poisoning has also other characteristics. It is of a
peculiar florid vermilion colour, a colour that is very persistent, lasting
for days and even weeks. -
Normal blood mixed with 30 per cent. potash solution forms greenish
streaky clots, while blood charged with CO forms red streaky clots.
Normal blood diluted to 50 times its volume of water, and then
treated successively with yellow ammonium sulphide in the proportion
of 2 to 25 c.c. of blood, followed by 3 drops of acetic acid, gives a
grey colour, while CO blood remains bright red. CO blood shaken with
4 times its volume of lead acetate remains red, but normal blood becomes
brown.”
* M. Rubner, Arch. Hyg., x. 397.
§ 35.] SPECTROSCOPIC APPEARANCES OF BLOOD. 63
Solutions of platinum chloride or zinc chloride give a bright red
colour with CO blood; normal blood is coloured brown or very dark
brown.
Phospho-molybdic acid or 5 per cent. phenol gives a carmine-coloured
precipitate with CO blood, but a reddish-brown precipitate with normal
blood (sensitive to 16 per cent.).
A mixture of 2 c.c. of dilute acetic acid and 15 c.c. of 20 per cent.
potassic ferrocyanide solution added to 10 c.c. of CO blood produces an
intense bright red; normal blood becomes dark brown.
Four parts of CO blood, diluted with 4 parts of water and shaken
with 3 vols. of 1 per cent. tannin solution, become at first bright red
with a bluish tinge, and remain so persistently. Normal blood, on the
other hand, also strikes bright red at first, but with a yellowish tinge;
at the end of 1 hour it becomes brownish, and finally in 24 hours grey.
This is stated to be delicate enough to detect 0-0023 per cent. in air.
If blood be diluted with 40 times its volume of water, and 5 drops
of phenylhydrazin solution be added, CO blood strikes rose-red; normal
blood grey-violet.*
Gustave Piotrowski f has experimented on the length of time blood
retains CO. The blood of dogs poisoned by this agent was kept in
flasks, and then the gas pumped out by means of a mercury-pump on
the following dates:—
Date. Content of gas in CO.
Jan. 12, 1892, G & * e * e e 24-7 per cent.
3 j . 20, 3 y º g ſe & * te e 23 °5 5 3
,, 28, , , º tº * * * tº * : 22*2 5 5
Feb. 8, , , wº & * e tº e tº 20-3 3 3
,, 16, , , tº te tº º ſº tº gº 15-5 3 y
, 26, , e & ſº & e * * 10°2 9 3
March 3, 3 3 e e & & ë * tº 6°3 5 3
3, 14, , , tº º º & e * § 4°6 3 2
3 J 22, , , e e © § g & & 1°2 y 5
The same dog was buried on the 12th of January, and exhumed on
March 28th, and the gas pumped out from some of the blood; this gas
gave 11.7 per cent. of CO; hence it is clear that burial preserves CO
blood from change to a certain extent.
N. Grehant f treated the poisoned blood of a dog with acetic acid,
and found it evolved 14.4 c.c. CO from 100 c.c. of blood.
Stevenson, in one of the cases detailed at p. 72, found the blood in
the right auricle to contain 0.03 per cent. by weight of CO.
(2) Preparation of Haematin Crystals—(Teichmann's crystals).-A
* A. Welzel, Centr, med. Wiss., xxvii. 732–734.
t Compt. Rend. Soc. de Biol., v. 433.
# Compt, Rend., cvi. 289.
64 POISONS : THEIR EFFECTS AND DETECTION. [$ 35.
portion of the borax solution is diluted with 5 or 6 parts of water, and
one or more drops of a 5 or 6 per cent. solution of zinc acetate added,
so long as a brownish-coloured precipitate is thrown down. The
precipitate is filtered off by means of a miniature filter, and then
removed on to a watch-glass. The precipitate may now be dissolved
in 1 or 2 c.c. of acetic acid, and examined by the spectroscope it will
show the spectrum of haematin. A minute crystal of sodium chloride
being then added to the acetic acid solution, it is allowed to evaporate
to dryness at the ordinary temperature, and crystals of haematin hydro-
chlorate result. There are other methods of obtaining the crystals.
When a drop of fresh blood is simply boiled with glacial acetic acid,
on evaporation, prismatic crystals are obtained. i
Haematin is insoluble in water, alcohol, chloroform, and in cold dilute
acetic and hydrochloric acids. It may, however, be dissolved in an
alcoholic solution of potassic carbonate, in solutions of the caustic
alkalies, in boiling acetic and hydro-

2. & A/ chloric acids, and in Riegler's re-
X - agent. Hoppe-Seyler ascribes to
Z the crystals the formula Cashiro Ns
A/ Fe,002HCl. Thudichum considers
that the pure crystals contain no
chlorine, and are therefore those of
// º —b haematin. It is the resistance of
\/
Q----
the haematin to decomposition and
* to ordinary solvents that renders it
C º e e e tº
possible to identify a certain stain
to be that of blood, after long periods of time. Dr. Tidy seems to have
been able to obtain blood reactions from a stain which was supposed to
be 100 years old. The crystals are of a dark red colour, and present
themselves in three forms, of which that of the rhombic prism is the
most common (see fig.). But crystals like b, having six sides, also
occur, and also crystals similar to c.
If the spot under examination has been scraped off an iron implement
the haematin is not so easily extracted; but Dragendorff states that borax
solution at 50° dissolves it, and separates it from the iron. Felletar has
also extracted blood in combination with iron rust, by means of warm
solution of caustic potash, and, after neutralisation with acetic acid, has
precipitated the haemin by means of tannin, and obtained from the
tannin precipitate, by means of acetic acid, Teichmann's crystals. A
little of the rust may also be placed in a test tube, powdered ammonium
chloride added, also a little strong ammonia, and after a time filtered ;
a small quantity of the filtrate is placed on a slide with a crystal of
sodium chloride and evaporated at a gentle heat, then glacial acetic acid
§ 36.] SPECTROSCOPIC APPEARANCES OF BLOOD. 65
added and allowed to cool; in this way hamin crystals have been
obtained from a crowbar fifty days after having been blood-stained.*
(3) Guaiacum Test.—This test depends upon the fact that a solution
of haemoglobin develops a beautiful blue colour if brought into contact
with fresh tincture of guaiacum and peroxide of hydrogen. The simplest
way to obtain this reaction is to moisten the suspected stain with distilled
water; after allowing sufficient time for the water to dissolve out some
of the blood constituents, moisten a bit of filter-paper with the weak
solution thus obtained ; drop on to the moist space a single drop of
tincture of guaiacum which has been prepared by digesting the inner
portions of guaiacum resin in alcohol, and which has been already tested
on known blood, so as to ascertain that it is really good and efficient for
the purpose; and, lastly, a few drops of peroxide of hydrogen. Dragen-
dorff uses his borax solution, and, after a little dilution with water, adds
the tincture and then Heunefeld's turpentine solution, which is composed
of equal parts of absolute alcohol, chloroform, and French turpentine,
to which one part of acetic acid has been added. The chloroform
separates, and, if blood was present, is of a blue colour.
§ 36. To prove by chemical and physical methods that a certain
stain is that of blood is often only one step in the inquiry, the next
question being whether the blood is that of man or of animals. The
blood corpuscles of man are larger than those of any domestic animal
inhabiting Europe. The diameter of the average red blood corpuscle is
about the Hºg of a millimetre, or 7-9 p.t The corpuscles of man and
of mammals, generally speaking, are round, those of birds and reptiles
oval, so that there can be no confusion between man and birds, fishes
or reptiles; if the corpuscles are circular in shape the blood will be
that of a mammal. By careful measurements, Dr. Richardson, of
Pennsylvania, affirms that it is quite possible to distinguish human
blood from that of all common animals. He maintains, and it is true,
that, by using very high magnifying powers and taking much trouble,
an expert can satisfactorily identify human blood if he has some half-
dozen drops of blood from different animals—such as the sheep, goat,
horse, dog, cat, etc., all fresh at hand for comparison, and if the human
blood is normal. However, when we come to the blood of persons
suffering from disease, there are changes in the diameter and even the
form of the corpuscles which much complicate the matter; while, in
blood-stains of any age, the blood corpuscles, even with the most
artfully-contrived solvent, are so distorted in shape that he would be a
bold man who should venture on any definite conclusion as to whether
* Brit. Med. Journ., Feb. 17, 1894.
t sºws of an inch ; the Greek letter u is the micro-millimetre, or 1000th of a
millimetre, '00003937 inch.
5
66 POISONS : THEIR EFFECTS AND DETECTION. [$ 36.
the blood was certainly human, more especially if he had to give evi-
dence in a criminal case.
Neumann affirms that the pattern which the fibrin or coagulum of
the blood forms is peculiar to each animal, and Dr. Day, of Geelong,
has independently confirmed his researches: this very interesting
observation perhaps has not received the attention it merits.
When there is sufficient of the blood present to obtain a few milligrms.
of ash, it may be possible to distinguish human blood from that of other
common mammals by estimating the relative amounts of potassium
and sodium in the blood. In the blood of the cow, sheep, fowl, pig,
and horse, the sodium very much exceeds the potassium in the ash ;
thus the proportion of potassium oxide to that of sodium oxide in the
blood of the sheep is as K2O : Na,0::1:6; in that of the cow, as 1:8;
in that of the domestic fowl, as 1: 16 ; while the same substances in
human blood are sometimes equal, and vary from 1 : 1 to 1:4 as
extremes, the mean numbers being as 1:2-2. The potassium is
greater in quantity in the blood corpuscles than in the blood serum;
but, even in blood serum, the same marked differences between the
blood of man and that of many animals is apparent. Thus, the pro-
portion of potash to soda being as 1:10 in human blood, the proportion
in sheep's blood is 1 to 15.7; in horse's serum as 1 to 16°4; and in the
ox as 1 to 17. Since blood, when burnt, leaves from 6 to 7 per
thousand of ash, it follows that a quantitative analysis of the relative
amounts of potassium and sodium can only be satisfactorily effected
when sufficient of the blood is at the analyst's disposal to give a weigh-
able quantity of mineral matter. On the other hand, much work
requires to be done before this method of determining that the blood is
either human, or, at all events, not that of an herbivorous animal, can
be relied on. We know but little as to the effect of the ingestion of
sodium or potassium salts on either man or animals, and it is possible—
may, probable—that a more or less entire substitution of the one for
the other may, on certain diets, take place. Bunge seems in some
experiments to have found no sodium in the blood of either the cat or
the dog. .
The source from which the blood has emanated may, in a few cases,
be conjectured from the discovery, by microscopical examination, of
hair, or of buccal, nasal, or vaginal epithelium, etc., mixed with the
blood-stain.
Biological Test for Human Blood.—A test for distinguishing human
from animal blood has been devised by Jules Ogier and Herscher.”
The blood-spot is dissolved in water, and two or three cubic centimetres
of the solution are placed in test tubes 10 to 12 cm. long and 4 to 5
* Amm. Chim. Anal., 1902, vii. 241.
§ 36.] SPECTROSCOPIC APPEARANCES OF BLOOD. 67
cm. diameter. In similar tubes is placed the same quantity of control
solutions of human, pigs, oxen, dogs, or other animals' blood, of
approximately the same strength.
To each tube is now added 10 drops of serum from rabbits which
have been repeatedly subcutaneously injected with human blood.
The tubes are placed in water at 37–40° C.; after 10 minutes
human blood will show a precipitate, which will be copious after half an
hour. A slight precipitate may be neglected. This test may be also
applied to old blood-stains. A precipitate is also said to be obtained
with blood from monkeys. Care should be taken to neutralise the blood
if it be acid, as it will, if acid, always give a precipitate. When blood
has been dried on certain materials, such for instance as thick polished
yellow leather, it has been found impossible to get the reaction.
PART III.—POISONOUS GASES: CARBON MONOXIDE—
CHLORINE—HYDRIC SULPHIDE.
I. Carbon Monoxide.
§ 37. Carbon monoxide, CO, is a colourless, odourless gas of 0.96709
sp. gravity. A litre weighs 1 25133 grm. It is practically insoluble
in water. It unites with many metals, forming gaseous or volatile
compounds, e.g. nickel carbon oxide, Ni(CO), is a fluid volatilising
at 40°. These compounds have, so far as is known, the same effects
as CO.
Whenever carbon is burned with an insufficient supply of air, CO
in a certain quantity is produced. It is always present in ordinary
domestic products of combustion, and must be exhaled from the
various chimneys of a large city in considerable volumes. A “smoky’”
chimney or a defective flue will therefore introduce carbon monoxide
into living-rooms. The vapour from burning coke or burning char-
coal is rich in carbon monoxide. It is always a constituent of coal
gas; in England the carbon monoxide in coal gas amounts to about
8 per cent. Poisoning by coal gas is practically poisoning by carbon
monoxide. Carbon monoxide is also the chief poisonous constituent
in water gas.
Carbon monoxide poisoning occurs far more frequently in France
and Germany than in England; in those countries the vapour evolved
from burning charcoal is a favourite method of suicide, on account of
the supposed painlessness of the death. It has also occasionally been
used as an instrument of murder. In this country carbon monoxide
poisoning mainly takes place accidentally as the effect of breathing coal
gas; possibly it is the secret and undetected cause of ill-health where
chimneys “smoke’: and it may have something to do with the sore
throats and debility so often noticed when persons breathe for long
periods air contaminated by small leakages of coal gas.
The large gas-burners (geysers) emit in burning under certain con-
ditions much carbon monoxide. It has been proved by Grehant * that
* Compt. Rend. Soc. de Biol, , ix. 779–780.
68
§ 38.] CARBON MONOXIDE. 69
a bunsen burner “lit below ’’ also evolves large quantities of the same
poisonous gas.”
§ 38. Symptoms.-Nearly all the experience with regard to the
symptoms produced by carbon monoxide is derived from breathing not
the pure gas, but the gas diluted by air, by hydrogen or by carburetted
hydrogen, as in coal gas, or mixed with large quantities of carbon
dioxide. Two assistants of Christison breathed the pure gas: the one
took from two to three inhalations; he immediately became giddy,
shivered, had headache, and then became unconscious. The second
took a bigger dose, for, after emptying his lungs as much as possible,
he took from three to four inhalations; he fell back paralysed, became
unconscious, and remained half an hour insensible and had the appear-
ance of death, the pulse being almost extinguished. He was treated
with inhalations of oxygen, but he remained for the rest of the day
extremely ill; he had convulsive muscular movements, stupor, headache,
and quick irregular pulse ; on this passing away he still suffered from
nausea, giddiness, alternate feeling of heat and chilliness, with some
fever, and in the night had a restless kind of sleep. The chemist
Chenot was accidentally poisoned by the pure gas, and is stated to have
fell as if struck by lightning after a single inspiration, and remained
for a quarter of an hour unconscious. Other recorded cases have shown
very similar symptoms.
The pulse is at the onset large, full and frequent ; it afterwards
becomes small, slow and irregular. The temperature sinks from 1° to 3°
C. The respiration at first slow, later becomes rattling. As vomiting
occurs often when the sufferer is insensible, the vomited matters have
been drawn by inspiration into the trachea and even into the bronchi,
so that death takes place by suffocation.
The fatal coma may last, even when the person has been removed from
the gas, from hours to days. Coma for three, four and five days from
carbon monoxide has been frequently observed. The longest case on
record is that of a person who was comatose for eight days, and died on
the twelfth day after the fatal inhalation. Consciousness in this case
returned, but the patient again fell into the stupor and died.
The slighter kinds of poisoning by carbon monoxide, as in the
Staffordshire case recorded by Dr. Reid (p. 73), in which for a long time
a much diluted gas has been breathed, produce pronounced headache
and a feeling of ill-health and malaise, deepening, it may be, into a fatal
slumber unless the person is removed from the deadly atmosphere. To
the headache generally succeeds nausea, a feeling of oppression in the
* Thorpe (J. Chem. Soc., xxxiii. 318, 1903) has shown that an ordinary bunsen
burner heating a sand tray evolves about 0.022 of a cubic foot of carbon monoxide
per hour.
7o POISONS : THEIR EFFECTS AND DETECTION. [$ 39.
temples, a noise in the ears, feebleness, anxiety, and a dazed condition
deepening into coma. It is probably true that charcoal vapour is com-
paratively painless, for when larger amounts of the gas are breathed the
insensibility comes on rapidly and the faces of those who have suc-
cumbed as a rule are placid. Womiting, without being constant, is a
frequent symptom, and in fatal cases the faeces and urine are passed in-
voluntarily. There are occasional deviations from this picture; tetanic
Strychnine-like convulsions have been noticed, and a condition of excite-
ment in the non-fatal cases as if from alcohol; in still rarer cases tem-
porary mania has been produced.
In non-fatal but moderately severe cases of poisoning sequelae follow,
which in some respects imitate the sequelae seen on recovery from the
infectious fevers. A weakness of the understanding, incapacity for
rational and connected thought, and even insanity have been noticed.
There is a special liability to local inflammations, which may pass into
gangrene. Various paralyses have been observed. Eruptions of the
skin, such as herpes, pemphigus and others. Sugar in the urine is an
almost constant concomitant of carbon monoxide poisoning.
§ 39. The poisonous action of carbon monoxide is, without doubt,
due to the fact that it is readily absorbed by the blood, entering into a
definite chemical compound with the haemoglobin ; this combination is
more stable than the similar compound with oxygen gas, and is therefore
slow in elimination.
Hence the blood of an animal remaining in an atmosphere containing
carbon monoxide is continually getting poorer in oxygen, richer in carbon
monoxide. Grehant has shown that if an animal breathes for one hour
a mixture of 0-5 carbon monoxide to 1000 oxygen, the blood contains at
the end of that time one-third less oxygen than normal, and contains
152 times more carbon monoxide than in the mixture. An atmosphere
of 10 per cent. carbon monoxide changes the blood so quickly, that
after from 10 to 25 seconds the blood contains 4 per cent. of carbon mon-
oxide, and after from 75 to 90 seconds 18.4 per cent. Breathing even
for half an hour an atmosphere containing from 0-07 to 0-12 per cent,
carbon monoxide renders a fourth part of the red corpuscles of the blood
incapable of uniting with oxygen.
The blood is, however, never saturated with carbon monoxide, for
the animal dies long before this takes place.
The characteristics of the blood and its spectroscopic appearances
are described at p. 62.
Besides the action on the blood there is an action on the nervous
system. Kobert,” in relation to this subject, says:—“That CO has a
direct action on the nervous system is shown in a marked manner when
* Lehrbuch der Intoaxicationem, 526.
$ 40.] CARBON MONOXIDE. 71
an atmosphere of oxygen, with at least 20 per cent. carbon oxide, is
breathed; for in the first minute there is acute cramp or total paralysis
of the limbs, when the blood in no way attains the saturation sufficiently
great to account for such symptoms. Geppert has, through a special
research, shown that an animal suffocated by withdrawal of oxygen
increases the number and depth of the respirations; but when the
animal is submitted to CO, in which case there is quite as much a with-
drawal of oxygen as in the former case, yet the animal is not in a condition
to strengthen its respiratory movements; Geppert hence rightly concludes
that CO must have a primary specific injurious action on the nerve
centres. I (Kobert) am inclined to go a step further, and, on the ground
of unpublished researches, to maintain that CO mot only affects in-
juriously the ganglion cells of the brain, but also the peripheral nerves
(e.g. the phrenic), as well as divers other tissues, as muscles and glands,
and that it causes so rapidly such a high degree of degeneration as not
to be explained through simple slow suffocation ; even gangrene may be
- caused.”
It is this rapid degeneration which is the cause of the enormous
increase of the products of the decomposition of albumin, found experi-
mentally in animals.
$ 40. Post-mortem. Appearances.—The face, neck, chest, abdomen
are frequently covered with patches of irregular form and of clear rose-
red or bluish-red colour; these patches are not noticed on the back, and
thus do not depend upon the gravitation of the blood to the lower or
most dependent part of the body; similar red patches have been noticed
in poisoning by prussic acid ; the cause of this phenomenon is ascribed
to the paralysis of the small arteries of the skin, which, therefore,
become injected with the changed blood. The blood throughout is
generally fluid, and of a fine peculiar red colour, with a bluish tinge.
The face is mostly calm, pale, and there is seldom any foam about the
lips. Putrefaction is mostly remarkably retarded. There is nearly
always a congestion of some of the internal organs; sometimes, and
indeed usually, the membranes of the brain are strongly injected ;
sometimes the congestion is mainly in the lungs, which may be
oadematous with effusion ; and in a third class of cases the congestion is
most marked in the abdominal cavity.
The right heart is commonly filled with blood, and the left side
contains only a little blood.
A rabbit that Kionka poisoned twelve times in as many days with
carbon monoxide, and through artificial respiration restored, was two
days later killed and examined : there were haemorrhages in both lungs
occlusion of vessels and haemorrhagic infarcti in the intestines, and
haemorrhages in the liver. In some cases there have been noticed,
72 POISONS : THEIR EFFECTS AND DETECTION. [$ 41.
small areas of softening in the human brain in cases of CO poisoning :
these may be explained by the light of the appearances just described
as caused by small thrombi in the brain vessels.
Poisoning by a small dose of carbon monoxide may produce but few
striking changes, and then it is only by a careful examination of the
blood that evidence of the real nature of the case will be obtained.
§ 41. Mass poisonings by Carbon Monoxide.—An interesting series
of cases of poisoning by water gas occurred at Leeds in 1889, and have
been recorded by Dr. Thos. Stevenson.*
Water gas is made by placing coke in a vertical cylinder and heating
the coke to a red heat. Through the red-hot coke, air is forced up
from below for ten minutes; then the air is shut off and steam passes
from above downwards for four minutes; the gas passes through a
scrubber, and then through a ferric oxide purifier to remove SH3. It
contains about 50 per cent. of hydrogen and 40 per cent. of carbon
monoxide, that is, about five times more carbon monoxide than coal
gaS.
On November 20, 1889, two men, R. French and H. Fenwick, both
intemperate men, occupied a cabin at the Leeds Forge Works; the
cabin was 540 c. feet in capacity, and was lighted by two burners, each
burning 5-5 c. feet of water gas per hour ; the cabin was warmed by a
cooking stove, also burning water gas, the products of combustion
escaping into the cabin. Both men went into the cabin after breakfast
(8.30 A.M.). French was seen often going to and fro, and Fenwick was
seen outside at 10.30 A.M. At 11.30 the foreman accompanied French
to the cabin, and found Fenwick asleep, as he thought. At 12.30 P.M.
French's son took the men their dinner, which was afterwards found
uneaten. At that time French also appeared to be asleep ; he was
shaken by his son, upon which he nodded to his son to leave. The
door of the cabin appears to have been shut, and all through the morn-
ing the lights kept burning; no smell was experienced. At 2.30 P.M.
both the men were discovered dead. It was subsequently found that
the stove was unlighted, and the water gas supply turned on.
What attracted most attention to this case was the strange incident
at the post-mortem examination. The autopsies were begun two days
after the death, November 22, in a room of 39,000 c. feet capacity.
There were present Mr. T. Scattergood (senior), Mr. Arthur Scattergood
(junior), Mr. Hargreaves, three local surgeons, Messrs. Brown, Loe and
Jessop, and two assistants, Pugh and Spray. Arthur Scattergood first
fainted; Mr. Scattergood, senior, also had some peculiar sensations, viz.,
tingling in the head and slight giddiness; then Mr. Pugh became faint
and staggered; and Mr. Loe, Mr. Brown, and Mr. Spray all complained.
* Guy's Hospital Reports, 1889.
§ 4 I.] CARBON MONOXIDE. 73
These symptoms were not produced, as was at first thought, by some
volatile gas or vapour emanating from the bodies of the poisoned men,
but, as subsequently discovered, admitted of a very simple explanation;
eight burners in the room were turned partly on and not lighted, and
each of the eight burners poured water gas into the room.
In 1891 occurred some cases of poisoning * by CO which are probably
unique. The cases in question happened in January in a family at
Darlaston. The first sign of anything unusual having happened to the
family most affected was the fact that up to 9 A.M., Sunday morning,
January 18, none of the family had been seen about. The house was
broken into by the neighbours; and the father, mother, and three
children were found in bed apparently asleep, and all efforts to rouse
them utterly failed. The medical men summoned arrived about 10 A.M.
and found the father and mother in a state of complete unconsciousness,
and two of the children, aged 11 and 14 years, suffering from pain and
sickness and diarrhoea ; the third child had by this time been removed
to a neighbouring cottage.
Dr. Partridge, who was in attendance, remained with the patients three
hours, when he also began to suffer from headache; while others, who
remained in the house longer, suffered more severely and complained of
an indefinite feeling of exhaustion. These symptoms pointed to some
exciting cause associated with the surroundings of the cottage ; conse-
quently, in the afternoon the two children were removed to another
cottage, and later on the father and mother also. All the patients, with
the exception of the mother, who was still four days afterwards suffering
from the effects of an acute attack, had completely recovered. The
opinion that the illness was owing to some local cause was subsequently
strengthened by the fact that two canaries and a cat had died in the
night in the kitchen of the cottage; the former in a cage and the latter
in a cupboard, the door of which was open. Also in a house on the
opposite side of the same road, the occupants of which had for some time
suffered from headache and depression, two birds were found dead in
their cage in the kitchen. It is important to notice that all these animals
died in the respective kitchens of the cottages, and, therefore, on the
ground floor, while the families occupied the first floor.
The father stated that for a fortnight or three weeks previous to the
serious illness, he and the whole family had complained of severe frontal
headache and a feeling of general depression. This feeling was continuous
day and night in the case of the rest of the family, but in his case,
during the day, after leaving the house for his work, it gradually passed
* “Notes on cases of poisoning by the inhalation of carbon monoxide,” by Dr.
George Reid, Medical Officer of Health, County of Stafford. Public Health, vol. iii.
364.
74 POISONS : THEIR EFFECTS AND DETECTION. [$ 42.
off, to return again during the night. The headaches were so intense
that the whole family regularly applied vinegar rags to their heads, on
going to bed each night during this period, for about three weeks.
About 2 o'clock on Sunday morning the headaches became so severe
that the mother got out of bed and renewed the application of vinegar
and water all round, after which they all fell asleep, and, so far as the
father and mother were concerned, remained completely unconscious
until Monday morning. •
A man who occupied the house opposite the house tenanted by the
last-mentioned family informed the narrator (Dr. Reid) that on Sunday
morning the family, consisting of four, were taken seriously ill with a
feeling of sickness and depression accompanied by headache ; and he
also stated that for some time they had smelt what he termed a “fire
stink” issuing from the cellar.
The cottage in which the family lived that had suffered so severely
was situated about 20 or 30 yards from the shaft of a disused coal mine,
and was the end house of a row of cottages. It had a cellar opening
into the outer air, but this opening was usually covered over by means of
a piece of wood. The adjoining house to this, the occupants of which
had for some time suffered from headache, although to a less extent, had
a cellar with a similar opening, but supplied with an ill-fitting cover.
The house on the opposite side of the road, in which the two birds were
found dead, had a cellar opening both at the front and the back; but
both these openings, until a little before the occurrence detailed, had
been kept closed. The cellars in all cases communicated with the houses
by means of doors opening into the kitchens. According to the general
account of the occupants, the cellars had smelled of “fire stink,” which,
in their opinion, proceeded from the adjoining mine.
The shaft of the disused mine communicated with a mine in working
order, and, to encourage the ventilation in this mine, a furnace had for
some weeks been lit and suspended in the shaft. This furnace had set
fire to the coal in the disused mine and smoke had been issuing from
the shaft for four weeks previously. Two days previous to the inquiry
the opening of the shaft had been closed over with a view to extinguish
the fire.
Dr. Reid considered, from the symptoms and all the circumstances of
the case, that the illness was due to carbon monoxide gas penetrating into
the cellars from the mine, and from thence to the living and sleeping
rooms. A sample of the air yielded 0-015 per cent. of carbon monoxide,
although the sample had been taken after the cellar windows had been
open for twenty-four hours. |
§ 42. Penetration of Carbon Monoxide.—It is not always sufficient
to detect carbon monoxide in the blood to establish death from that
§ 43.] CARBON MONOXIDE. 75
gas, for circumstances may arise under which a corpse is exposed to
either coal gas or carbon monoxide gas. Wachholz and Lemberger *
placed the bodies of still-born infants in glass vessels and passed CO
through the vessels; in half an hour the blue cadaverous spots became
bright red, and the blood exhibited the spectrum of carbon monoxide
haemoglobin.
Domenic Mirto made some experiments of a like nature and
concluded—
(1) That in post-mortem flusion the anterior part of the liver
was rich in carbon monoxide, but in poisoning the gas is
equally diffused.
(2) In post-mortem diffusion the pia mater scarcely ever contains
carbon monoxide, the choroid plexus never.
(3) The deep parts of the body contain less than the superficial in
the case of diffusion, the reverse is the case in poisoning.
Straussmann and Schulz, in a research on seven adult bodies, fairly
well agree with Mirto, save that they believe that, given sufficient
time, there is no part of the body into which carbon monoxide will not
penetrate.
§ 43. Detection of Carbon Monoxide.—It may often be necessary to
detect carbon monoxide in air and to estimate its amount. The detection
in air, if the carbon monoxide is in any quantity, is easy enough ; but
traces of carbon monoxide are difficult. Where amounts of carbon
monoxide in air from half a per cent. upwards are reasonably presumed to
exist, the air is measured in a gas measuring apparatus and passed into an
absorption pipette charged with alkaline pyrogallic acid, and when all the
oxygen has been abstracted, then the residual nitrogen and gases are
submitted to an ammoniacal solution of cuprous chloride.
The solution of cuprous chloride is prepared by dissolving 10.3 grms.
of copper oxide in 150 c.c. of strong hydrochloric acid and filling the flask
with copper turnings; the copper reduces the cupric chloride to cuprous
chloride; the end of the reduction is known by the solution becoming
colourless. The colourless acid solution is poured into some 1500 c.c. of
water, and the cuprous chloride settles to the bottom as a precipitate.
The supernatant fluid is poured off as completely as possible and the
precipitate washed into a quarter litre flask, with 100 to 150 c.c. of dis-
tilled water and ammonia led into the solution until it becomes of a pale
blue colour. The solution is made up to 200 c.c. so as to contain about
7-3 grns. per cent. of cuprous chloride.
Such a solution is an absorbent of carbon monoxide; it also absorbs
ethylene and acetylene.
* “De la pénétration de l'oxyde de Carbon,” Anviv. d’Hygiene publique, 49me
ser., iii. 175.
76 POISONS : THEIR EFFECTS AND DETECTION. [$ 44.
A solution of cuprous chloride which has absorbed CO gives it up on
being treated with potassic bichromate and acid. It has been proposed
by Wanklyn to deprive large quantities of air of oxygen, then to absorb
any carbon monoxide present with cuprous chloride, and, lastly, to
free the cuprous chloride from the last gas by treatment with acid
bichromate, so as to be able to study the properties of a small quantity
of pure gas.
A more reliable method to detect small quantities of carbon monoxide
is, however, as proposed by Hempel, to absorb it in the lungs of a living
animal.
A mouse is placed between two funnels joined together at their
mouths by a band of thin rubber; one of the ends of the double funnel
is connected with an aspirator, and the air thus sucked through, say for
half an hour or more; the mouse is then killed by drowning, and a
control mouse, which has not been exposed to a CO atmosphere, is also
drowned ; the bodies of both mice are cut in two in the region of the
heart, and the blood collected. Each sample of blood is diluted in the
same proportion and spectroscopically examined in the manner detailed
at p. 60. The limit of the test lies at about 0.03 per cent. when large
volumes of the gas are used.
A more delicate reaction, and one which may be used for the estima-
tion of CO, is that of Nicloux and Gautier. The gas to be examined is
freed from unsaturated hydrocarbon by shaking with fuming sulphuric
acid, and from carbon dioxide by passing over soda-lime; it is then
passed over iodine pentoxide heated by means of an oil-bath to a
temperature of from 150°–200°. The iodine pentoxide is decomposed in
accordance with the equation I,0s + 5CO = I2 + 5C02, the liberated iodine
is caught in 10 per cent. potassium iodide, and may be determined by
º sodium thiosulphate. Thorpe,” using this method, has obtained
good results with as little as ‘0025 per cent. of carbon monoxide.
II.-Chlorine.
§ 44. Chlorine is a yellow-green gas, which may, by cold and pressure,
be condensed into a liquid. Its specific gravity is, as compared with
hydrogen, 35-37; as compared with air, 2.45; a litre under standard
conditions weighs 3.167 grims. It is soluble in Water.
The usual method of preparation is the addition of hydrochloric acid
to bleaching powder, which latter substance is hypochlorite of lime
mixed with calcic chloride and, it may be, a little caustic lime. Another
* J.C.S., lxxxiii. 318, 1903.
$45,46.] CHLORINE. 77
method is to treat manganese dioxide with hydrochloric acid or to act
on manganese dioxide and common salt with sulphuric acid.
Accidents are liable to occur with chlorine gas from its extensive use
as a disinfectant and also in its manufacture. In the “Weldon” process
of manufacturing bleaching powder, a thick layer of lime is placed on
the floor of special chambers; chlorine gas is passed into these chambers
for about four days; then the gas is turned off; the unabsorbed gas is
drawn off by an exhaust or absorbed by a lime distributor and the doors
opened. Two hours afterwards the men go in to pack the powder.
The packers, in order to be able to work in the chambers, wear a
respirator consisting of about thirty folds of damp flannel; this is tightly
bound round the mouth with the nostrils free and resting upon it. The
men are obliged to inhale the breath through the flannel and exhale
through the nostril, otherwise they would, in technical jargon, be
“gassed.” Some also wear goggles to protect their eyes. Notwith-
standing these precautions they suffer generally from chest complaints.
§ 45. Effects.-Free chlorine, in the proportion of 0.04 to 0-06 per
thousand, taken into the lungs is dangerous to life, since directly
chlorine attacks a moist mucous membrane, hydrochloric acid is formed.
The effects of chlorine can hardly be differentiated from hydrochloric
acid gas, and Lehmann found that 1.5 per thousand of this latter gas
affected animals, causing at once uneasiness, evidence of pain with great
dyspnoea, and, later, coma. The eyes and the mucous membrane of the
nose were attacked. Anatomical changes took place in the cornea, as
evidenced by a white opacity.
In cases that recovered, a purulent discharge came from the nostrils
with occasional necrosis of the mucous membrane. The symptoms in
man are similar ; there is great tightness of the breath, irritation of the
nose and eyes, cough and, with small repeated doses, bronchitis with all
its attendant evils. Bleaching powder taken by the mouth is not so
deadly. Hertwig has given 1000 grns. to horses, 30 grms. to sheep and
goats, and 15 grms, to dogs without producing death. The symptoms
in these cases were quickening of the pulse and respiration, increased
peristaltic action of the bowels, and a stimulation of the kidney secretion.
The urine smelt of chlorine.
Post-mortem Appearances.—Hyperaemia of the lungs, with ecchy-
moses and pneumonic patches, with increased secretion of the bronchial
tubes. In the mucous membrane of the stomach, ecchymoses. The
alkalescence of the blood is diminished and there may be external signs
of bleaching. Only exceptionally has any chlorine smell been perceived
in the internal organs.
§ 46. Detection of Free Chlorine.—The usual method of detection is
to prepare a solution of iodide of potassium and starch and to soak strips
78 POISONs: THEIR EFFECTS AND DETECTION. [$47, 48.
of filter-paper in this solution. Such a strip, when moistened and
submitted to a chlorine atmosphere, is at once turned blue, because
chlorine displaces iodine from its combination with potassium. Litmus-
paper, indigo blue or other vegetable colours are at once bleached.
To estimate the amount of chlorime, a known volume of the air is
drawn through a solution of potassium iodide, and the amount of iodine
set free determined by titration with sodic hyposulphite, as detailed
at p. 80.
III.-Hydric Sulphide (Sulphuretted Hydrogen).
§ 47. Hydric sulphide, SH2, is a colourless transparent gas of sp.
gravity 1-178. It burns with a blue flame, forming water and sulphur
dioxide, and is soluble in water; water absorbing about three volumes
at ordinary temperatures. It is decomposed by either chlorine gas or
sulphur dioxide.
It is a common gas as a constituent of the air of sewers or cesspools,
and emanates from moist slag or moist earth containing pyrites or
metallic sulphides; it also occurs whenever albuminous matter putre-
fies; hence it is a common constituent of the emanations from corpses of
either man or animals. It has a peculiar and intense odour, generally
compared to that of rotten eggs; this is really not a good comparison,
for it is comparing the gas with itself, rotten eggs always producing
SH, ; it is often associated with ammonium sulphide,
§ 48. Effects.-Pure hydric sulphide is never met with out of the
chemist's laboratory, in which it is a common reagent either as a gas or
in solution ; so that the few cases of poisoning by the pure gas, or
rather the pure gas mixed with ordinary air, have been confined to
laboratories.
The greater number of cases have occurred accidentally to men
working in sewers, or cleaning out cesspools and the like. In small
quantities it is always present in the air of towns, as shown by the
blackening of any silver ornament not kept bright by frequent use.
In the construction of a graving dock at Hebburn-on-Tyne, July 1902,
three workmen lost their lives through breathing SH2. They had to
enter a large iron caisson, the excavation at the bottom of which had
reached some old alkali waste, and the water, as subsequent analysis
showed, contained 12.2 volumes per cent. of SH2. The first workman
had been in twenty minutes when screams were heard; a second man
went to his assistance, shouted and fell to the bottom ; the same fate
befell a third. The post-mortem examination showed the heart normal,
right side flaccid and empty, left hard and firmly contracted. No
odour of hydric sulphide in the body. Lungs pale and oedematous.
§ 49.] HYDRIC SULPHIDE. 79
Liver dark. Blood dark and liquid. The spectroscope showed no
carbon monoxide bands.”
It is distinctly a blood poison, the gas uniting with the alkali of the
blood, and the sulphide thus produced partly decomposing again in the
lung and breathed out as SH2. In one sense it acts as a reducing
agent, for it robs cells of loosely bound O, and therefore kills them by
deprivation of oxygen; it also attacks labile groups, as it substitutes in
the aldehyde group sulphur.
It is a poison for all organisms, even the bacteria of putrefaction
only bearing up to # per cent. Lehmanni has studied the effects on
animals; an atmosphere containing from 1 to 3 per thousand of SH,
kills rabbits and cats within ten minutes; the symptoms are mainly
convulsions and great dyspnoea. An atmosphere containing from 0-4 to
0.8 per thousand produces a local irritating action on the mucous mem-
branes of the respiratory tract, and death follows from an inflammatory
oedema of the lung preceded by convulsions; there is also a paralysis of
the nervous centres. Lehmann has recorded the case of three men who
breathed 0.2 per thousand of SH2 : within from five to eight minutes
there was intense irritation of the eyes, nose, and throat, and after
thirty minutes they were unable to bear the atmosphere any longer.
Air containing 0.5 per thousand of SH2 is, according to Lehmann, the
utmost amount that can be breathed; this amount causes in half an
hour smarting of the eyes, nasal catarrh, dyspnoea, cough, palpitation,
shivering, great muscular weakness, headache and faintness with cold
sweats. 0-7 to 0.8 per thousand is dangerous to human life, and from
1 to 1-5 per thousand destroys life rapidly. The symptoms may occur
some little time after the withdrawal of the person from the poisonous
atmosphere; for example, Cahn records the case of a student who pre-
pared SH, in a laboratory and was exposed to the gas for two hours;
he then went home to dinner and the symptoms first commenced in
more than an hour after the first breathing of pure air. Taylor j re-
cords an unusual case of poisoning in 1857 at Cleator Moor. Some
cottages had been built upon iron slag, the slag contained sulphides of
calcium and iron; a heavy storm of rain washed through the slag and
considerable volumes of SH2 with, no doubt, other gases diffused dur-
ing the night through the cottages and killed three adults and three
children.
§ 49. Post-mortem Appearances.—The so-called apoplectic form of
SH2 poisoning, in which the sufferer dies within a minute or two, shows
* “Fatalities to workmen breathing sulphuretted hydrogen,” by Thos. Oliver,
M.D., Lancet, Jan. 26, 1903.
t K. B. Lehmann, Arch. f. Hygiène, xiv., 1892, 135.
† Principles and Practice of Medl. Jurisp., vol. ii. 122.
8O POISONS : THEIR EFFECTS AND DETECTION. [$ 50.
no special change. The most frequent change in slower poisoning is,
according to Lehmann, oedema of the lungs. A green colour of the
face and of the whole body is sometimes present, but not constant. A
spectroscopic examination of the blood may also not lead to any con-
clusion, the more especially as the spectrum of sulphur methaemoglobin
may occur in any putrid blood. The pupils in some cases have been
found dilated; in others not so.
Chronic poisoning.—Chronic poisoning by SH, is of considerable
interest in a public health point of view. The symptoms appear to be
conjunctivitis, headache, dyspepsia and anaemia. A predisposition to
boils has also been noted.
§ 50. Detection.—Both ammonium and hydric sulphides blacken
silver and filter-paper moistened with acetate of lead solution. To test
for hydric sulphide in air, a known quantity may be aspirated through a
little solution of lead acetate. To estimate the quantity a decinormal
solution of iodine in potassium iodide * solution is used, and its exact
strength determined by d.m. sodic hyposulphite solution; t the hypo-
sulphite is run in from a burette into a known volume, e.g. 50 c.c., of
the d.n. iodine solution, until the yellow colour is almost gone; then a
drop or two of fresh starch solution is added and the hyposulphite run
in carefully, drop by drop, until the blue colour of the starch dis-
appears. If now a known volume of air is drawn through 50 c.c. of the
d.n. iodine solution, the reaction I, + SH2=2HI+ S will take place, and
for every 127 parts of iodine which have been converted into hydriodic
acid 17 parts by weight of SH, will be necessary; hence on titrating
the 50 c.c. of d.n. iodine solution, through which air containing SH, has
been passed, less hyposulphite will be used than on the previous occa-
sion, each c.c. of the hyposulphite solution being equal to 1'll c.c. or
to 1.7 mgrm. of SH2.
* 12*7 grms, of iodine, 16-6 grms, of potassium iodide, dissolved in a litre of
water.
f 24'8 grms, of sodic hyposulphite, dissolved in a litre of water.
PART IV.-ACIDS AND ALKALIES.
SULPHURIC ACID–HYDROCHLORIC ACID—NITRIC ACID—
ACETIC ACID—AMMONIA—POTASH-SODA—NEUTRAL
SODIUM, POTASSIUM, AND AMMONIUM SALTS.
I.—Sulphuric Acid.
§ 51. Sulphuric acid (hydric sulphate, oil of vitriol, H. SO) occurs
in commerce in varying degrees of strength or dilution; the strong sul-
phuric acid of the manufacturer, containing 100 per cent. of real acid
(H2SO4), has a specific gravity of 1:850. The ordinary brown acid of
commerce, coloured by organic matter and holding in solution metallic
impurities, chiefly lead and arsenic, has a specific gravity of about
1:750; and contains 67-95 of anhydrous SOA = 85:42 of hydric sulphate.
There are also weaker acids used in commerce, particularly in manu-
factories in which sulphuric acid is made, for special purposes without
rectification. The British Pharmacopoeia sulphuric acid is directed
to be of 1843 specific gravity, which corresponds to 78.6 per cent.
sulphuric anhydride, or 98.8 per cent. of hydric sulphate. The dilute
sulphuric acid of the Pharmacopoeia should have a specific gravity of
1-094, and is usually said to correspond to 10:14 per cent. of anhydrous
sulphuric acid ; but according to the tables of Lunge and Isler this
density corresponds to 11:05 per cent. SOs. -
The general characters of sulphuric acid are as follows:—When
pure, it is a colourless, or, when impure, a dark brown to black, oily
liquid, without odour at common temperatures, of an exceedingly acid
taste, charring most organic tissues rapidly, and, if mixed with water,
evolving much heat. If 4 parts of the strong acid are mixed with 1
part of water at 0°, the mixture rises to a heat of 100”; a still greater
heat is evolved by mixing 75 parts of acid with 27 of water.
Sulphuric acid is powerfully hygroscopic—3 parts will, in an
ordinary atmosphere, increase to nearly 4 in twenty-four hours; in
81 6
82 POISONS: THEIR EFFECTS AND DETECTION. [$ 52–54.
common with all acids, it reddens litmus, yellows cochineal, and changes
all vegetable colours. There is another form of sulphuric acid, ex-
tensively used in the arts, known under the name of “Nordhausen
sulphuric acid,” “fuming acid,” formula H.S,04. This acid is produced
by the distillation of dry ferrous sulphate, at a nearly white heat—
either in earthenware or in green glass retorts; the distillate is received
in sulphuric acid. As thus manufactured, it is a dark fuming liquid,
of 19 specific gravity, and boiling at 53°. When artificially cooled
down to 0°, the acid gradually deposits crystals, which consist of a
definite compound of 2 atoms of anhydrous sulphuric acid and 1 atom
of water. There is some doubt as to the molecular composition of
Nordhausen acid; it is usually considered as hydric sulphate Saturated
with sulphur dioxide. This acid is manufactured chiefly in Bohemia,
and is used, on a large scale, as a solvent for alizarine.
§ 52. Sulphur Trioxide, or Sulphuric Anhydride (SOA), itself may
be met with in scientific laboratories, but is not in commerce. Sulphur
trioxide forms thin needle-shaped crystals, arranged in feathery groups.
Seen in mass, it is white, and has something the appearance of asbestos.
It fuses to a liquid at about 18", boils at 35°, but, after this operation
has been performed, the substance assumes an allotropic condition, and
then remains solid up to 100”; above 100° it melts, volatilises, and
returns to its normal condition. Sulphuric anhydride hisses when it
is thrown into water, chemical combination taking place and sulphuric
acid being formed. Sulphur trioxide is excessively corrosive and
poisonous. -
Besides the above forms of acid, there is an officinal preparation
called “Aromatic Sulphuric Acid,” made by digesting sulphuric acid,
rectified spirit, ginger, and cinnamon together. It contains 10:19 per
cent of SOs, alcohol, and principles extracted from cinnamon and
ginger.
§ 53. Sulphuric acid, in the free state, may not unfrequently be found
in nature. The senior author has had under examination an effluent
water from a Devonshire mine, which contained more than one grain
of free sulphuric acid per gallon, and was accused, with justice, of
destroying the fish in a river. It also exists in large quantities in
volcanic springs. In a torrent flowing from the volcano of Parcé, in
the Andes, Boussingault calculated that 15,000 tons of sulphuric acid
and 11,000 tons of hydrochloric acid were yearly carried down. In the
animal and vegetable kingdom, sulphuric acid exists, as a rule, in
combination with bases, but there is an exception in the saliva of the
Dolium galea, a Sicilian mollusc.
§ 54. Statistics.—When something like 900,000 tons of sulphuric
acid are produced annually in England alone, and when it is considered
§ 55.] SULPHURIC ACID. 83
that sulphuric acid is used in the manufacture of most other acids, in
the alkali trade, in the manufacture of indigo, in the soap trade, in the
manufacture of artificial manure, and in a number of technical processes,
there is no cause for surprise that it should be the annual cause of
many deaths.
The number of deaths from sulphuric acid will vary, other things
being equal, in each country, according to the manufactures in that
country employing sulphuric acid. The number of cases of poisoning
in England and Wales for the ten years ending 1903 was as follows:—
DEATHS FROM SULPHURIC ACID IN ENGLAND AND WALES FOR
THE TEN YEARS ENDING 1903.
ACCIDENT OR NEGLIGENCE. SUICIDE.
Males, . e e tº e . 34 || Males, . g : . e º . 30
Females, e g g * . 9 || Females, tº & º * . 22
Total, . 43 Total, . 52
During the ten years, two cases of murder through sulphuric acid
are on record; hence the total deaths, as detailed in the tables, amount
to 97, or nearly 10 a year.
Falck,” in comparing different countries, considers the past statistics
to show that in France sulphuric acid has been the cause of 4-5 to 5-5
per cent. of the total deaths from poison, and in England 5.9 per cent.
In England, France, and Denmark, taken together, 10-8, Prussia 10-6 ;
while in certain cities, as Berlin and Vienna, the percentages are much
higher—Vienna showing 43.3 per cent., Berlin 90 per cent.
§ 55. Accidental, Suicidal, and Criminal Poisoning.—Deaths from
sulphuric acid are, for the most part, accidental or suicidal, rarely
criminal. In 53 out of 113 cases collected by Bohm, in which the
cause of the poisoning could, with fair accuracy, be ascertained, 45.3
per cent. were due to accident, 30-2 were suicidal, and 24.5 per cent.
were cases of criminal poisoning, the victims being children.
The cause of the comparatively rare use of sulphuric acid by the
poisoner is obvious. First of all, the acid can never be mixed with food
without entirely changing its aspect ; next, it is only in cases of
insensibility or paralysis that it could be administered to an adult,
unless given by force, or under very exceptional circumstances; and
lastly, the stains on the mouth and garments would at once betray, even
to uneducated persons, the presence of something wrong. As an agent
of murder, then, sulphuric acid is confined in its use to young children,
more especially to the newly born.
* Lehrbuch der praktischen Toaricologie, p. 54.
84 POISONS : THEIR EFFECTS AND DETECTION. [$ 56.
There is a remarkable case related by Haagan,” in which an adult
man, in full possession of his faculties, neither paralysed nor helpless,
was murdered by sulphuric acid. The wife of a day-labourer gave her
husband drops of sulphuric acid on sugar, instead of his medicine, and
finally finished the work by administering a spoonful of the acid. The
Spoon was carried well to the back of the throat, so that the man took
the acid at a gulp. 11 grms. (171 grains) of sulphuric acid, partly in
combination with soda and potash, were separated from his stomach.
Accidental poisoning is most common among children. The oily,
syrupy-looking sulphuric acid, when pure, may be mistaken for glycerine
or for syrup; and the dark commercial acid might, by a careless person,
be confounded with porter or any dark-looking medicine.
Serious and fatal mistakes have not unfrequently arisen from the use
of injections. Deutsch f relates how a midwife, in error, administered
to mother and child a sulphuric acid clyster; but little of the fluid could
in either case have actually reached the rectum, for the mother recovered
in eight days, and in a little time the infant was also restored to health.
Sulphuric acid has caused death by injections into the vagina. H. C.
Lombard f observed a case of this kind, in which a woman, aged 30,
injected half a litre of sulphuric acid into the vagina, for the purpose of
procuring abortion. The result was not immediately fatal, but the sub-
Sequent inflammation and its results so occluded the natural passage
that the birth became impossible, and a Caesarean section extracted a
dead child, the mother also dying.
An army physician prescribed for a patient an emollient clyster.
Since it was late at night, and the apothecary in bed, he prepared it
himself; but not finding linseed oil, woke the apothecary, who took a
bottle out of one of the recesses and placed it on the table. The bottle
contained sulphuric acid; a soldier noticed a peculiar odour and effer-
vescence when the syringe was charged, but this was unheeded by the
doctor. The patient immediately after the operation suffered the most
acute agony, and died the following day; before his death, the bed-
clothes were found corroded by the acid, and a portion of the bowel
itself came away. §
$ 56. Fatal Dose.—The amount necessary to kill an adult man is
not strictly known ; fatality so much depends on the concentration of
the acid and the condition of the person, more especially whether the
stomach is full or empty, that it will be impossible ever to arrive at an
* Gross: Die Strafrechtspflege in Deutschland, 4, 1861, Heft i. S. 181.
+ Preuss. Med. Vereims-Zeitung, 1848, No. 13.
: Jourm, de Chim. Méd., tom. vii., 1831. .
§ Maschka's Handbuch, p. 86; Journal de Chimie Médicale, t. i. No. 8, 405,
1835. -
§ 57.] SULPHURIC ACID. 85
accurate estimate. Christison's case, in which 38 grns. (60 grains) of
concentrated acid killed an adult, is the smallest lethal dose on record.
Supposing that the man weighed 68% kilo. (150 lbs.), this would be in
the proportion of '05 grn. per kilo. There is also the case of a child of
one year, recorded by Taylor, in which 20 drops caused death. If,
however, it were asked in a court of law what dose of concentrated
sulphuric acid would be dangerous, the proper answer would be : so
small a quantity as from 2 to 3 drops of the strong undiluted acid
might cause death, more especially if conveyed to the back of the throat;
for if it is improbable that on such a supposition death would be sudden,
yet there is a possibility of permanent injury to the gullet, with the
result of subsequent contraction, and the usual long and painful
malnutrition thereby induced. It may be laid down, therefore, that all
quantities, even the smallest, of the strong undiluted acid come under
the head of hurtful, noxious, and injurious.
§ 57. Local Action of Sulphuric Acid.—The action of the acid on
living animal tissues has been studied by C. Ph. Falck and L. Vietor.”
Concentrated acid precipitates albumen, and then redissolves it ; fibrin
swells and becomes gelatinous; but if the acid is weak (e.g. 4 to 6 per
cent.) it is scarcely changed. Muscular fibre is at first coloured amber-
yellow, swells to a jelly, and then dissolves to a red-brown turbid fluid.
When applied to the mucous membrane of the stomach, the mucous
tissue and the muscular layer beneath are coloured white, swell, and
become an oily mass.
When applied to a rabbit's ear, f the parenchyma becomes at first
pale grey and semi-transparent at the back of the ear; opposite the
drop of acid appear spots like grease or fat drops, which soon coalesce.
The epidermis with the hair remains adherent ; the blood-vessels are
narrowed in calibre, and the blood, first in the veins, and then in the
arteries, is coloured green and then black, and fully coagulates. If the
drop, with horizontal holding of the ear, is dried in, an inflammatory
Zone surrounds the burnt spot in which the blood circulates; but there is
complete stasis in the part to which the acid has been applied. If the
point of the ear is dipped in the acid, the cauterised part rolls inwards;
after the lapse of eighteen hours the part is brown and parchment-like,
with scattered points of coagulated blood ; then there is a slight swelling
in the healthy tissues, and a small zone of redness; within fourteen
days a bladder-like greenish-yellow scab is formed, the burnt part it-
self remaining dry. The vessels from the surrounding zone of redness
* Deutsche Klinik, 1864, Mo. 1–32, and Vietor's Inaugur-Dissert., Marburg,
1803.
+ Samuel, Entziindwng w. Brand, in Virchow's Archiv f. Path. Amat., li. Hft.
1 u. 2, S. 41, 1870.
86 POISONS : THEIR EFFECTS AND DETECTION. [$ 58.
gradually penetrate towards the cauterised spot, the fluid in the bleb
becomes absorbed, and the destroyed tissues fall off in the form of a
Crust.
The changes that sulphuric acid cause in blood are as follows: the
fibrin is at first coagulated and then dissolved, and the colouring matter
becomes of a black colour. These changes do not require the strongest
acid, being seen with an acid of 60 per cent.
§ 58. The action of the acid on various non-living matters is as
follows: poured on all vegetable earth, there is an effervescence, arising
from decomposition of carbonates; any grass or vegetation growing on
the spot is blackened and dies; an analysis of the layer of earth, on
which the acid is poured, shows an excess of sulphates as compared with
a similar layer adjacent; the earth will only have an acid reaction if
there has been more than sufficient acid to neutralise all alkalies and
alkaline earths.
Wood almost immediately blackens, and the spot remains moist.
Spots on paper become quickly dark, and sometimes exhibit a play
of colours, such as reddish-brown; ultimately the spot becomes very
black, and holes may be formed ; even when the acid is dilute, the
course is very similar, for the acid dries in, until it reaches a sufficient
degree of concentration to attack the tissue. Small drops of sulphuric
acid on a Brussels carpet, which had a red pattern on a dark green ground
with light green flowers, were found to act as follows: the spots on the
red at the end of a few hours were of a dark maroon colour, the green
was darkened, and the light green browned ; at the end of twenty-four
hours but little change had taken place, nor could any one have guessed
the cause of the spots without a close examination. Spots of the strong
acid on thin cotton fabrics rapidly blackened, and actual holes were
formed in the course of an hour; the main difference to the naked eye,
between the stains of the acid and those produced by a red-hot body,
lay in the moistuess of the spots. Indeed, the great distinction,
without considering chemical evidence, between recent burns of clothing
by sulphuric acid and by heat, is that in the one case—that of the
acid—the hole or spot is very moist; in the other very dry. It is easy
to imagine that this distinction may be of importance in a legal
investigation.
Spots of acid on clothing fall too often under the observation of all
those engaged in practical chemical work. However quickly a spot of
acid is wiped off, unless it is immediately neutralised by ammonia, it
ultimately makes a hole in the cloth; the spot, as a rule, whatever the
colour of the cloth, is of a blotting-paper red.
Sulphuric acid dropped on iron, attacks it, forming a sulphate, which
may be dissolved out by water. If the iron is exposed to the weather
$ 59.] SULPHURIC ACID. 87
the rain may wash away all traces of the acid, save the corrosion ; but
it would be under those circumstances impossible to say whether the
corrosion was due to oxidation or a solvent.
To sum up briefly : the characters of sulphuric acid spots on organic
matters generally are black, brown, or red-coloured destructions of tissue,
moisture, acid-reaction (often after years), and lastly the chemical evi-
dence of sulphuric acid or sulphates in excess.
Caution necessary in judging of Spots, etc.—An important case,
related by Maschka, shows the necessity of great caution in interpreting
results, unless all the circumstances of a case be carefully collated. A
live coal fell on the bed of a weakly infant, five months old. The child
screamed, and woke the father, who was dozing by the fire ; the man, in
terror, poured a large pot of water on the child and burning bed. The
child died the following day.
A post-mortem examination showed a burn on the chest of the infant
2 inches in length. The tongue, pharynx, and gullet were all healthy;
in the stomach a patch of mucous Imembrane, about half an inch in
extent, was found to be brownish, friable, and very thin. A chemical
examination showed that the portion of the bed adjacent to the burnt
place contained free sulphuric acid. Here, then, was the following
evidence : the sudden death of a helpless infant, a carbonised bed-cover
with free sulphuric acid, and, lastly, an appearance in the stomach
which, it might be said, was not inconsistent with sulphuric acid
poisoning. Yet a careful sifting of the facts convinced the judges that
no crime had been committed, and that the child's death was due to
disease. Afterwards, experiment showed that if a live coal fall on to
any tissue and be drenched with water, free sulphuric acid is constantly
found in the neighbourhood of the burnt place.
§ 59. Symptoms.—The symptoms may be classed in two divisions,
viz.:-1. External effects of the acid. 2. Internal effects and symptoms
arising from its interior administration.
1. External Effects.-Of late years several instances have occurred in
which the acid has been used criminally to cause disfiguring burns of the
face. The offence has in all these cases been committed by women, who,
from motives of revengeful jealousy, have suddenly dashed a quantity of
the acid into the face of the object of their resentment. In such cases,
the phenomena observed are not widely different from those attending
scalds or burns from hot neutral fluids. There is destruction of tissue,
not necessarily deep, for the acid is almost immediately wiped off; but
if any should reach the eye, inflammation, so acute as to lead to blind-
ness, is the probable consequence. The skin is coloured at first white,
at a later period brown, and part of it may be, as it were, dissolved. If
the tract or skin touched by the acid is extensive, death may result.
88 POISONS : THEIR EFFECTS AND DETECTION. [$ 59.
The inflammatory processes in the skin are similar to those noticed by
Falck and Vietor in their experiments, already detailed (p. 85).
Internal Effects of Acids generally.—It may not be out of place,
before speaking of the internal effects of sulphuric acid, to make a few
remarks upon the action of acids generally. This action differs accord-
ing to the kind of animal; at all events, there is a great difference
between the action of acids on the herb-eating animals and the carnivora ;
the latter bear large doses of acids well, the former ill. For instance,
the rabbit, if given a dose of any acid not sufficient to produce local
effects, but sufficient to affect its functions, will soon become paralysed
and lie in a state of stupor, as if dead ; the same dose per kilo. will not
affect the dog. The reason for this is that the blood of the dog is able
to neutralise the acid by ammonia, and that the blood of the rabbit is
destitute of this property. Man is, in this respect, nearer to the dog
than to the plant-eaters. Stadelmann has shown that a man is able to
ingest large relative doses of oxybutyric acid, to neutralise the acid by
ammonia, and to excrete it by means of the kidneys as ammonium
butyrate.
Acids, however, if given in doses too great to be neutralised, alike
affect plant- and flesh-eaters; death follows in all cases before the blood
becomes acid. Salkowski “ has, indeed, shown that the effect of lessen-
ing the alkalinity of the blood by giving a rabbit food from which it
can extract no alkali produces a similar effect to the actual dosing with
an acid.
2. Internal Effects of Sulphuric Acid.—When sulphuric acid is
taken internally, the acute and immediate symptom is pain. This,
however, is not constant, since, in a few recorded cases, no complaint of
pain has been made ; but these cases are exceptional; as a rule, there
will be immediate and great suffering. The tongue swells, the throat
is also swollen and inflamed, swallowing of saliva even may be im-
possible. If the acid has been in contact with the epiglottis and vocal
apparatus, there may be spasmodic croup and even fatal spasm of the
glottis.
The acid, in its passage down the gullet, attacks emergetically the
mucous membrane and also the lining of the stomach ; but the action
does not stop there, for Lesser found in eighteen out of twenty-six cases
(69 per cent.) that the corrosive action extended as far as the duodenum.
There is excessive vomiting and retching; the matters vomited are acid,
bloody, and slimy; great pieces of mucous membrane may be in this
way expelled, and the whole of the lining membrane of the gullet may
be thrown up entire. The bowels are, as a rule, constipated, but
exceptionally there has been diarrhoea; the urine is sometimes retained ;
* Virchow's Archiv, lviii. 1.
§ 60.] SULPHURIC ACID. 89
it invariably contains an excess of sulphates and often albumen, with
hyaline casts of the uriniferous tubes. The pulse is small and frequent,
the breathing slow, the skin very cold and covered with sweat; the
countenance expresses great anxiety, and the extremities may be affected
with cramps or convulsions. Death may take place within from twenty-
four to thirty-six hours, and be either preceded by dyspnoea or by con-
vulsions; consciousness is, as a rule, maintained to the end.
There are also more rapid cases than the above; a large dose of
sulphuric acid taken on an empty stomach may absolutely dissolve it,
and pass into the peritoneum; in such a case there is really no difference
in the symptoms between sudden perforation of the stomach from
disease, a penetrating wound of the abdomen, and any other sudden
fatal lesion of the organs in the abdominal cavity (for in all these
instances the symptoms are those of pure collapse); the patient is ashen
pale, with pulse quick and weak, and body bathed in cold sweat, and
he rapidly dies, it may be without much complaint of local pain.
If the patient live longer than twenty-four hours, the symptoms are
mainly those of inflammation of the whole mucous tract, from the mouth
to the stomach ; and from this inflammation the patient may die in a
variable period, of from three to eleven days, after taking the poison.
In one case the death occurred suddenly, without any immediately pre-
ceding symptoms rendering imminent death probable. If this second
stage is passed, then the loss of substance in the gullet and in the
stomach almost invariably causes impairment of function, leading to a
slow and painful death. The common sequence is stricture of the gullet,
combined with feeble digestion, and in a few instances stricture of the
pylorus. A curious sequel has been recorded by Mannkopf, viz.,
obstinate intercostal neuralgia; it has been observed on the fourth,
seventh, and twenty-second day.
§ 60. Treatment of Acute Poisoning by the Mineral Acids.—The
immediate indication is the dilution and neutralisation of the acid. For
this purpose, finely-divided chalk, magnesia, or sodic carbonate may be
used, dissolved or suspended in much water. The use of the stomach-
pump is inadvisable, for the mucous membrane of the gullet may be so
corroded by the acid that the passage of the tube down will do injury;
unless the neutralisation is immediate, but little good is effected ; hence
it will often occur that the bystanders, if at all conversant with the
matter, will have to use the first thing which comes to hand, such as the
plaster of a wall, etc.; and lastly, if even these rough antidotes are not
to be had, the best treatment is enormous doses of water, which will
dilute the acid and promote vomiting. The treatment of the after-effects
belongs to the province of ordinary medicine, and is based upon general
principles.
90 POISONS : THEIR EFFECTS AND DETECTION. [$ 61.
§ 61. Post-mortem Appearances.*—The general pathological ap-
pearances to be found in the stomach and internal organs differ
according as the death is rapid or slow ; if the death takes place
within twenty-four hours, the effects are fairly uniform, the differences
being only in degree ; while, on the other hand, in those cases which
terminate fatally from the more remote effects of the acid, there is some
variety. It may be well to select two actual cases as types, the one
patient dying from acute poisoning, the other surviving for a time, and
then dying from ulceration and contraction of the digestive tract.
A hatter, early in the morning, swallowed a large mouthful of
strong sulphuric acid, a preparation which he used in his work—
(whether the draught was taken accidentally or suicidally was never
known). He died within two hours. The whole tongue was sphace-
lated, parts of the mucous membrane being dissolved ; the inner surface
of the gullet, as well as the whole throat, was of a grey-black colour;
the mucous membrane of the stomach was coal-black, and so softened
that it gave way like blotting-paper under the forceps, the contents
escaping into the cavity of the abdomen. The peritoneum was also
blackened as if burnt; probably there had been perforation of the
stomach during life ; the mucous membrane of the duodenum was
swollen, hardened, and looked as if it had been boiled ; while the
blood was of a cherry-red colour, and of the consistence of a thin syrup.
The rest of the organs were healthy; a chemical research on the fluid
which had been collected from the stomach, gullet, and duodenum
showed that it contained 87.25 grains of free sulphuric acid.i
This is, perhaps, the most extreme case of destruction on record ;
the cause of the unusually violent action is referable to the acid acting
on an empty stomach. It is important to note that even with this
extensive destruction of the stomach, life was prolonged for two hours.
The case selected to serve as a type of a chronic but fatal illness
produced from poisoning by sulphuric acid is one related by Oscar
Wyss. A cook, 34 years of age, who had suffered many ailments,
drank, on the 6th of November 1867, by mistake, at 8 o'clock
in the morning, two mouthfuls of a mixture of 1 part of sul-
phuric acid and 4 of water. Pain in the stomach and neck, and
vomiting of black masses, were the immediate symptoms, and two
hours later he was admitted into the hospital in a state of collapse,
with cold extremities, cyanosis of the face, etc. Copious draughts of
milk were given, and the patient vomited much, the vomit still con-
* It has been observed that putrefaction in cases of death from sulphuric acid is
slow. Casper suggests this may be due to the neutralisation of ammonia; more
probably it is owing to the antiseptic properties all mineral acids possess.
i Casper, vol. ii. case 194.
§ 62.] SULPHURIC ACID. 9 I
sisting of black pultaceous matters, in which, on a microscopical ex-
amination, could be readily detected columnar epithelium of the
stomach and mucous tissue elements. The urine was of specific gravity
1-033, non-albuminous; on analysis it contained 3-388 grims, of
combined sulphuric acid.
On the second day there was some improvement in the symptoms;
the urine contained 1276 grm. of combined sulphuric acid; on the
third day 2,665 grims. of combined sulphuric acid; and on the tenth
day the patient vomited up a complete cast of the mucous membrane
of the gullet. The patient remained in the hospital, and became
gradually weaker from stricture of the gullet and impairment of the
digestive powers, and died, two months after taking the poison, on the
5th of January 1868.
The stomach was found small, contracted, with many adhesions to
the pancreas and liver; it was about 12 centimetres long (4-7 inches),
and from 2 to 2.5 centimetres (7 to 9 inch) broad, contracted to
somewhat the form of a cat's intestine ; there were several transverse
rugae; the walls were thickened at the small curvature, measurements
giving 5 mm. (19 inch) in the middle, and beyond about 2.75 mm.
('11 inch); in the upper two-thirds the lumen was so contracted as
scarcely to admit the point of the little finger. The inner surface was
covered with a layer of pus, with no trace of mucous tissue, and was
everywhere pale red, uneven, and crossed by cicatricial bands. In
two parts, at the greater curvature, the mucous surface was strongly
injected in a ring-like form, and in the middle of the ring was a deep
funnel-shaped ulcer; a part of the rest of the stomach was strongly
injected and scattered over with numerous punctiform, small, trans-
parent bladders. The gullet was contracted at the upper part (just
below the epiglottis) from 20 to 22 mm. (-78 to '86 inch) in diameter;
it then gradually widened to measure about 12 mm. (.47 inch) at the
diaphragm; in the neighbourhood of the last contraction the tissue was
scarred, injected, and ulcerated ; there were also small abscesses opening
into this portion of the gullet. -
E. Fraenkel and F. Reiche" have studied the effects of sulphuric
acid on the kidney. In rapid cases they find a widespread shedding
of the epithelium in the convoluted and straight urinary canaliculi,
with destruction of the kidney parenchyma, but no inflammation.
§ 62. The museums of the different London hospitals afford excellent
material for the study of the effects of sulphuric acid on the pharynx,
gullet, and stomach; and it may be a matter of convenience to students
if the more typical examples at these different museums be noticed in
detail, so that the preparations themselves may be referred to.
* Virchow's Archiv, czzxi. 130.
92 POISONS : THEIR EFFECTS AND DETECTION. [$ 63.
In St. Bartholomew's Museum, No. 1942, is an example of excessive destruction
of the stomach by sulphuric acid. The stomach is much contracted, and has a large
aperture with ragged edges; the mucous membrane is thickened, charred, and
blackened. -
No. 1941, in the same museum, is the stomach of a person who died from a large
dose of sulphuric acid. When recent, it is described as of a deep red colour, mottled
with black; appearances which, from long soaking in spirit, are not true at the
present time; but the rough, shaggy state of the mucous tissue can be traced; the
gullet and the pylorus appear the least affected.
St. George's Hospital, ser. ix. 146, 11 and 43, e.—The pharynx and Oesophagus of
a man who was brought into the hospital in a state of collapse, after a large but
unknown dose of sulphuric acid. The lips were much eroded, the mucous membrane
of the stomach, pharynx, and Oesophagus show an extraordinary shreddy condition ;
the lining membrane of the stomach is much charred, and the action has extended to
the duodenum ; the muscular coat is not affected.
Guy's Hospital, No. 1799. –A preparation showing the mucous membrane of the
stomach entirely denuded. The organ looks like a piece of thin paper.
No. 179999. The stomach of a woman who poisoned herself by drinking a wine-
glassful of acid before breakfast. She lived eleven days. The main symptoms were
vomiting and purging, but there was no complaint of pain. There is extensive
destruction of mucous membrane along the lesser curvature and towards the pyloric
extremity; a portion of the mucous membrane is floating as a slough.
No. 1799% is the gullet and stomach of a man who took about 3 drachms of
the strong acid. He lived three days without much apparent suffering, and died
unexpectedly. The lining membrane of the oesophagus has the longitudinal wrinkles
or furrows so often, may, almost constantly, met with in poisoning by the acids. The
mucous tissue of the stomach is raised in cloudy ridges, and blackened.
No. 1799% is a wonderfully entire cast of the gullet from a woman who swal-
lowed an ounce of sulphuric acid, and is said, according to the catalogue, to have
recovered.
University College.—In this museum will be found an exquisite preparation of the
effects of sulphuric acid. The mucous membrane of the oesophagus is divided into
small quadrilateral areas by longitudinal and transverse furrows: the stomach is very
brown and covered with shreddy and filamentous tissue ; the brown colour is without
doubt the remains of extravasated and charred blood.
No. 6201 is a wax cast representing the stomach of a woman who died after taking
a large dose of sulphuric acid. A yellow mass was found in the stomach ; there are
two perforations, and the mucous membrane is entirely destroyed.
§ 63. Chronic Poisoning by Sulphuric Acid. –Weiske * has experi-
mentally proved that lambs, given for six months small doses of sulphuric
acid, grow thin, and their bones, with the exception of the bones of the
head and the long bones, are poor in lime salts, the muscles also are
poor in the same constituents. Kobert f thinks that drunkards on the
Continent addicted to “Schnaps,” commonly a liquid acidified with sul-
phuric acid to give it a sharp taste, often show typical chronic sulphuric
acid poisoning.
* H. Weiske, Jowrm. f. Landwirthsch., 1887, 417.
+ Lehrbuch der Imtowicationem, S. 210.
§ 64.] SULPHURIC ACID. 93
Detection and Estimation of Free Sulphuric Acid.
§ 64. The general method of separating the mineral acids is as
follows: the tissues, or matters, are soaked in distilled water for Some time.
If no free acid is present, the liquid will not redden litmus-paper, or give
an acid reaction with any of the numerous tinctorial agents in use by the
chemist for the purposes of titration. After sufficient digestion in water,
the liquid extract is made up to some definite bulk and allowed to sub-
side. Filtration is unnecessary. A small fractional part (say, for example,
should the whole be 250 c.c., Tägth or 2.5 c.c.) is taken, and using as an
indicator cochineal or phenolphthalein, the total acidity is estimated by a
decinormal solution of soda. By this preliminary operation, some guide
for the conduct of the future more exact operations is obtained. Should
the liquid be very acid, a small quantity of the whole is to be now
taken ; but if the acidity is feeble, a larger quantity is necessary, and
sufficient quinine then added to fix the acid—100 parts of sulphuric acid
are saturated by 342 parts of quinine monohydrate. Therefore, on the
supposition that all the free acid is sulphuric, it will be found sufficient
to add 35 parts of quinine for every 1 part of acid, estimated as sul-
phuric, found by the preliminary rough titration ; and as it is inconvenient
to deal with large quantities of alkaloid, a fractional portion of the
liquid extract (representing not more than 50 mgrpms. of acid) should be
taken, which will require 175 mgrms. of quinine. -
On addition of the quinine, the neutralised liquid is evaporated to dry-
ness, or to approaching dryness, and then exhausted by strong alcohol.
The alcoholic extract is, after filtration, dried up, and the quinine sul-
phate, nitrate, or hydrochlorate, as the case may be, filtered off and ex-
tracted by boiling water, and precipitated by ammonia, the end result being
quinine hydrate (which may be filtered off and used again for similar
purposes) and a sulphate, nitrate, or chloride of ammonia in solution.
It therefore remains to determine the nature and quantity of the acids
now combined with ammonia. The solution is made up to a known
bulk, and portions tested for chlorides by nitrate of silver, for nitrates
by the copper or the ferrous sulphate test, and for sulphates by BaCl,
solution. If sulphuric acid is present there will be a precipitate of
barium sulphate, which, from its density and insolubility in nitric or
hydrochloric acids, is very characteristic. For estimating the sulphuric
acid thus found, a known bulk of the same liquid is heated to boiling
after acidifying by hydrochloric acid, and a sufficient quantity of baric
chloride solution added. Unless this exact process is followed, the
analyst is likely to get a liquid which refuses to filter clear; but if the
sulphate be precipitated from a hot liquid, it usually settles rapidly to
94. POISONS : THEIR EFFECTS AND DETECTION. [$ 65.
the bottom of the vessel, and the supernatant fluid can be decanted clear;
the precipitate is washed by decantation, and ultimately collected on a
filter, dried, removed from the filter and burnt up in the usual way.
The sulphate of baryta found, multiplied by 3434, equals the
sulphuric anhydride. -
The older process was to dissolve the free sulphuric acid out by alcohol.
As is well known, mineral sulphates are insoluble in, and are precipitated
by, alcohol, whereas sulphuric acid enters into solution. The most valid
objection, as a quantitative process, to the use of alcohol, is the tendency
which all mineral acids have to unite with alcohol in organic combination,
and thus, as it were, to disappear; and, indeed, results are found, by
experiment, to be below the truth when alcohol is used. This objection
does not hold good if either merely qualitative evidence, or a fairly
approximate quantation, is required. In such a case, the vomited matters,
the contents of the stomach, or a watery extract of the tissues, are evapo-
rated to a syrup, and then extracted with strong alcohol and filtered ; a
little phenolphthalein solution is added, and the acid alcohol exactly
neutralised by an alcoholic solution of clear decinormal or normal soda.
According to the acidity of the liquid, the amount used of the decinormal
or normal soda is noted, and then the whole evaporated to dryness, and
finally heated to gentle redness. The alkaline sulphate is next dissolved
in very dilute hydrochloric acid, and the solution precipitated by chloride
of barium in the usual way. The quantitative results, although low,
would, in the great majority of cases, answer the purpose sufficiently.
A test usually enumerated, Hilger's test for mineral acid, may be
mentioned. A liquid, which contains a very minute quantity of mineral
acid, becomes of a blue colour (or, if 1 per cent, or above, of a green) on
the addition of a solution of methyl aniline violet ; but this test, although
useful in examining vinegars (see “Foods”), is not of much value in
toxicology, and the quinine method for this purpose meets every conceiv-
able case, both for qualitative and quantitative purposes.
§ 65. The Urine.—Although an excess of sulphates is found constantly
in the urine of persons who have taken large doses of sulphuric acid, the
latter has never been found in that liquid in a free state, so that it will
be useless to search for free acid. It is, therefore, only necessary to add
HCl, to filter the fluid, and precipitate direct with an excess of chloride
of barium. It is better to operate in this manner than to burn the urine
to an ash, for in the latter case part of the sulphates, in the presence of
phosphates, are decomposed, and, on the other hand, any organic sulphur
combinations are liable to be estimated as sulphates.
It may also be well to pass chlorine gas through the same urine which
has been treated with chloride of barium, and from which the sulphate
has been filtered off. The result of this treatment will be a second
§ 65.] SULPHURIC ACID. 95
precipitate of sulphate derived from sulphur, in a different form of
combination than that of sulphate.
The greatest amount of sulphuric acid as mineral and organic
sulphate is separated, according to Mannkopf” and Schultzen,t within
five hours after taking sulphuric acid; after three days the secretion,
so far as total sulphates is concerned, is normal.
The normal amount of sulphuric acid excreted daily, according to
Thudichum, is from 1-5 to 2.5 grims., and organic sulphur up to 2 grn.
in the twenty-four hours, but very much more has been excreted by
healthy persons.
Lehmann made some observations on himself, and found that, on an
animal diet, he excreted no less than 10:399 grms. of sulphuric acid
per day, and on mixed food a little over 7 grms. ; as Thudichum
justly observes, this great amount must be referred to individual
peculiarity. The amount of sulphates has a decided relation to diet.
Animal food, although not containing sulphates, yet, from the oxidation
of the sulphur-holding albumen, produces a urine rich in sulphate.
Thus Vogel found that a person, whose daily average was 2.02 grms.,
yielded 7-3 on a meat diet. The internal use of sulphur, sulphides,
and sulphates, given in an ordinary medicinal way, is traceable in the
urine, increasing the sulphates. In chronic diseases the amount of
sulphates is decreased, in acute increased.
Finally, it would appear that the determination of sulphates in the
urine is not of much value, save when the normal amount that the indi-
vidual secretes is primarily known. On the other hand, a low amount
of sulphates in the urine of a person poisoned by sulphuric acid has not
been observed within three days of the taking of the poison, and one
can imagine cases in which such a low result might have forensic
importance.
The presence of albumen in the urine has been considered by some
a constant result of sulphuric acid poisoning, but although when looked
for it is usually found, it cannot be considered constant. O. Smoler, I
in eighteen cases of various degrees of sulphuric acid poisoning, found
nothing abnormal in the urine. Wyss Š found in the later stages of a
case indican and pus. E. Leyden and Ph. Munn always found blood
in the urine, as well as albumen, with casts and cellular elements.
Mannkopf'ſ found albuminuria in three cases out of five ; in two of the
cases there were fibrinous casts; in two the albumen disappeared at the
* “Toxicologie der Schwefelsåure,” Wiener med. Wochen., 1862, 1863.
t Archiv. f. Anatom. w. Physiol., 1864.
# Archiv der Heilkunde, ed. by E. Wagner, 1869, Hft. 2, S. 181.
§ Wiener Medicinal-Halle, 1861, Jahr. 6, No. 46.
| Virchow's Archiv f. path. Anat., 1861, Bd. xxii. Hft. 3 u. 4, S. 237.
"I Wien, med, Wochenschrift, 1862, Nro. 35; 1863, Nro. 5,
96 POISONs: THEIR EFFECTS AND DETECTION. [$ 66, 67.
end of the second or third day, but in one it continued for more than
twenty days. Bamberger * has observed an increased albuminuria,
with separation of the colouring matter of the blood. In this case it
was ascribed to the action of the acid on the blood.
$ 66. The Blood.—In Casper's case, No. 193, the vena cava of a
child, who died within an hour after swallowing a large dose of
sulphuric acid, was filled with a cherry-red, strongly acid-reacting blood.
Again, Casper's case, No. 200, is that of a young woman, aged 19, who
died from a poisonous dose of sulphuric acid. At the autopsy, four
days after death, the following peculiarities of the blood were thus
noted:—“The blood had an acid reaction, was dark, and had (as is
usual in these cases) a syrupy consistence, while the blood corpuscles
were quite unchanged. The blood was treated with an excess of
absolute alcohol, filtered, the filtrate concentrated on a water-bath, the
residue exhausted with absolute alcohol, etc. It yielded a small
quantity of sulphuric acid.”
Other similar cases might be noted, but it must not for a moment
be supposed that the mass of the blood contains any free sulphuric acid
during life. The acidity of the blood in the vena cava may be ascribed
to post-mortem endosmosis, the acid passing through the walls of the
stomach into the large vessel.
§ 67. Sulphates.—If the acid swallowed should have been entirely
neutralised by antidotes, such as chalk, etc., it becomes of the first
importance to ascertain, as far as possible, by means of a microscopical
examination, the nature of the food remaining in the stomach, and then
to calculate the probable contents in sulphates of the food thus known
to be eaten. It will be found that, with ordinary food, and under
ordinary circumstances, only small percentages of combined sulphuric
acid can be present.
As an example, take the ordinary rations of the soldier, viz.:-12 oz.
of meat, 24 oz. of bread, 16 oz. of potatoes, 8 oz. of other vegetables;
with sugar, salt, tea, coffee, and water. Now, if the whole quantity of
these substances were eaten at a meal, they would not contain more
than from 8 to 10 grains (5 to “6 grim.) of anhydrous sulphuric acid,
in the form of sulphates.
So far as the contents of the stomach are concerned, we have only
to do with sulphates introduced in the food, but when once the food
passes further along the intestinal canal, circumstances are altered, for
we have sulphur-holding secretions, which, with ordinary chemical
methods, yield sulphuric acid. Thus, even in the newly-born infant,
according to the analyses of Zweifler, the mineral constituents of
meconium are especially sulphate of lime, with a smaller quantity of
* Wien. Med.-Halle, 1864, Nro, 29, 30,
§ 68.] HYDROCHLORIC ACID. * 97
sulphate of potash. The amount of bile which flows into the whole
tract of the intestinal canal is estimated at about half a litre in the
twenty-four hours; the amount of sulphur found in bile varies from '89
to 3 per cent, so that in 500 c.c. we might, by oxidising the sulphur,
obtain from 2-2 to 7.5 grms. of sulphuric anhydride.
It is therefore certain that large quantities of organic sulphur-
compounds may be found in the human intestinal canal, for with indi-
viduals who suffer from constipation, the residues of the biliary secretion
accumulate for many days. Hence, if the analyst searches for sulphates
in excretal matters, all methods involving destruction of organic sub-
stances, whether by fire or by fluid-oxidising agents, are wrong in
principle, and there is nothing left save to separate soluble sulphates
by dialysis, or to precipitate direct out of an aqueous extract.
Again, sulphate of magnesia is a common medicine, and so is sodic
sulphate ; a possible medicinal dose of magnesia sulphate might amount
to 56.7 grns. (2 ozs.), the more usual dose being half that quantity.
Lastly, among the insane there are found patients who will eat plaster-
of-Paris, earth, and similar matters, so that, in special cases, a very
large amount of combined sulphuric acid may be found in the intestinal
tract, without any relation to poisoning by the free acid; but in such
instances it must be rare, indeed, that surrounding circumstances or
pathological evidence will not give a clue to the real state of affairs.
II.-Hydrochloric Acid.
§ 68. General Properties.—Pure hydrochloric acid is a gas, com-
posed of 97.26 per cent. of chlorine and 2.74 per cent. of hydrogen.
Commercial hydrochloric acid, muriatic acid, or spirit of salt is a solution
of this gas, with more or less impurity, in water.
Hydrochloric acid is made on an enormous scale in the United
Kingdom, the production being estimated at about a million tons
annually.
The toxicology of hydrochloric acid is modern, for we have no
evidence that anything was known of it prior to the middle of the
seventeenth century, when Glauber prepared it in solution, and, in
1772, Priestley, by treating common salt with sulphuric acid, isolated
the pure gas.
The common liquid hydrochloric acid of commerce has a specific
gravity of from 1'15 to 1:20, and contains usually less than 40 parts of
hydrochloric acid in 100 parts. The strength of pure samples of
hydrochloric acid can be told by the specific gravity, and a very close
approximation, in default of tables, may be obtained by simply multi-
7
98 POISONS: THEIR EFFECTS AND DETECTION. [$ 68.
plying the decimal figures of the specific gravity by 200. For example,
an acid of 120 gravity would by this rule contain 40 per cent. of real
acid, for 20 × 200 = 40.
The commercial acid is nearly always a little yellow, from the
presence of iron derived from metallic retorts, and may contain small
quantities of chloride of arsenic,” derived from the sulphuric acid; but
the colourless hydrochloric acid specially made for laboratory and
medicinal use is nearly always pure.
The uses of the liquid acid are mainly in the production of chlorine,
as a solvent for metals, and for medicinal and chemical purposes. Its
properties are briefly as follows:—
It is a colourless or faintly-yellow acid liquid, the absence or other-
wise of colour depending on its purity, and especially its freedom from
iron. The liquid is volatile, and can be separated from fixed matters
and the less volatile acids by distillation; it has a strong attraction for
water, and fumes when exposed to the air, from becoming saturated
with aqueous vapour. If exposed to the vapour of ammonia, extremely
dense clouds arise, due to the formation of the solid ammonium chloride.
The acid, boiled with a small quantity of manganese binoxide, evolves
chlorine. Dioxide of lead has a similar action; the chlorine may be
detected by its bleaching action on a piece of paper dipped in indigo
blue; a little zinc foil immersed in the acid disengages hydrogen.
These two tests—viz., the production of chlorine by the one, and the
production of hydrogen by the other—separate and reveal the con-
stituent parts of the acid. Hydrochloric acid, in common with
chlorides, gives a dense precipitate with silver nitrate. The precipitate
is insoluble in nitric acid, but soluble in ammonia ; it melts without
decomposition. Exposed to the light, it becomes of a purple or blackish
colour. Every 100 parts of silver chloride are equal to 25'43 of hydro-
chloric acid, HCl, and to 63-5 parts of the liquid acid of specific gravity
1.20.
The properties of pure hydrochloric acid gas are as follows:—Specific
gravity 1962, consisting of equal volumes of hydrogen and chlorine,
united without condensation. 100 cubic inches must therefore have a
weight of 39°36 grains. The gas was liquefied by Faraday by means of
a pressure of 40 atmospheres at 10"; it was colourless, and had a smaller
refractive index than water.
Water absorbs the gas with avidity, 100 volumes of water absorbing
* Some samples of hydrochloric acid have been found to contain as much as 4 per
cent. of chloride of arsenic, but this is very unusual. Glenard found as a mean 2:5
grammes, As2O5 per kilogramme ; but since the mass poisoning by arsenical beer
derived from glucose made by impure sulphuric acid, English manufacturers have
succeeded in putting on the market ordinary sulphuric and hydrochloric acids almost
arsenic-free,
§ 69–71.] HYDROCHLORIC ACID. 99
48,000 volumes of the gas, and becoming 142 volumes. The solution has
all the properties of strong hydrochloric acid, specific gravity 1-21. The
dilute hydrochloric acid of the Pharmacopoeia should have a specific
gravity of 1:052, and be equivalent to 10:58 per cent. of HC1.
§ 69. Statistics of Poisoning by Hydrochloric Acid.—The following
table gives the deaths and sex distribution due to hydrochloric acid for
ten years ending 1903 —
DEATHS FROM HYDROCHLORIC ACID IN ENGLAND AND WALES
DURING THE TEN YEARS ENDING 1903.
ACCIDENT OR NEGLIGENCE. SUICIDE.
Males, . e & sº * . 91 || Males, . e º º gº . 204
Females, & tº g e . 33 Females, g e & & . 165
Total, . 124 Total, º 369
In 1889 a solitary case of the murder of a child is on record from
hydrochloric acid. The total deaths from hydrochloric acid amount to
493 in the ten years, or about 49 a year.
§ 70. Fatal Dose.—The dose which destroys life is not known with
any accuracy. In two cases, adults have been killed by 14 grims. (half
an ounce) of the commercial acid ; but, on the other hand, recovery is
recorded when more than double this quantity has been taken. A girl,
15 years of age, died from drinking a teaspoonful of the acid.*
§ 71. Amount of Free Acid in the Gastric Juice.—Hydrochloric acid
exists in the gastric juice. This was first ascertained by Prouti in 1824;
he separated it by distillation. The observation was afterwards confirmed
by Gmelin, ; Children, Š and Braconnot. On the other hand, Lehmann'ſ
pointed out that, as the stomach secretion contained, without doubt,
lactic acid, the act of distillation, in the presence of this lactic acid,
would set free hydrochloric acid from any alkaline chlorides. Blondlot
and Cl. Bernard also showed that the gastric juice possessed no acid which
would dissolve oxalate of lime, or develop hydrogen when treated with
iron filings; hence there could not be free hydrochloric acid which, even
in a diluted state, would respond to both these tests. Then followed the
researches of C. Schmidt,” who showed that the gastric secretion of
men, of sheep, and of dogs contained more hydrochloric acid than would
* Brit. Med. Jowrm., March 1871.
t Philosophical Transactions, 1824, p. 45.
f P. Tiedmann and L. Gmelin, Die Verdawung mach Versuchen, Heidelberg u.
Leipsic, 1826, i.
§ Annals of Philosophy, July 1824.
| Amm. de Chim., t. lix. p. 348.
‘I Journal f. prakt. Chemie, Bd. xl. 47.
** Bidder u. Schmidt, Verdawungs-Säfte, etc.
IOO POISONS : THEIR EFFECTS AND DETECTION. [$ 72.
Satisfy the bases present ; and he propounded the view that the gastric
juice does not contain absolutely free hydrochloric acid, but that it is in
loose combination with the pepsin.
The amount of acid in the stomach varies from moment to
moment, and therefore it is not possible to say what the average
acidity of gastric juice is. It has been shown that in the total
absence of free hydrochloric acid digestion may take place, because
hydrochloric acid forms a compound with pepsin which acts as a
solvent on the food. The amount of physiologically active acid varies
with the food taken ; it is smallest when carbohydrates are con-
sumed, greatest with meat. The maximum amount that Jaksch found
in his researches, when meat was ingested, was '09 per cent. of hydro-
chloric acid. It is probable that anything above 0.2 per cent. of
hydrochloric acid is either abnormal or owing to the recent ingestion
of hydrochloric acid.
§ 72. Influence of Hydrochloric Acid on Vegetation.—Hydrochloric
acid fumes, if emitted from works on a large scale, injure vegetation
much. In former years, before any legal obligations were placed
upon manufacturers for the condensing of the volatile products, the
nuisance from this cause was great. In 1823, the duty on salt
being repealed by the Government, an extraordinary impetus was
given to the manufacture of hydrochloric acid, and since all the
volatile products at that time escaped through short chimneys into
the air, a considerable area of land round the works was rendered
quite unfit for growing plants. The present law on the subject is,
that the maximum quantity of acid escaping shall not exceed 2
grains per cubic foot of the air, smoke, or chimney gases; and,
according to the reports of the alkali inspectors, the condensation by
the improved appliances is well within the Act, and about as perfect
as can be devised.
It appears from the reports of the Belgian Commission in 1855, when
virtually no precautions were taken, that the gases are liable to injure
vegetation to the extent of 2000 metres (2187 yards) around any active
works; the more watery vapour the air contains, the quicker is the gas
precipitated and carried to the earth. If the action of the vapour is
considerable, the leaves of plants dry and wither; the chlorophyll be-
comes modified, and no longer gives the normal spectrum, while a
thickening of the rind of trees has also been noticed. The cereals suffer
much ; they increase in stalk, but produce little grain. The legumi-
nosae become spotted, and have an air of dryness and want of vigour;
while the potato, among plants utilised for food, appears to have the
strongest resistance. Wines are very sensitive to the gas. Among trees,
the alder seems, most sensitive; then come fruit-trees, and last, the
e wº
tº
§ 73, 74.] HYDROCHLORIC ACID. IOI
hardy forest-trees—the poplar, the ash, the lime, the elm, the maple,
the birch, and the oak.*
§ 73. Action upon Cloth and Manufactured Articles.—On black
cloth the acid produces a green stain, which is not moist and shows no
corrosion. On most matters the stain is more or less reddish ; after a
little time no free acid may be detected, by simply moistening the spot ;
but if the stain is cut out and boiled with water, there may be some
evidence of free acid. The absence of moisture and corrosion distin-
guishes the stain from that produced by sulphuric acid.
§ 74. Poisonous Effects of Hydrochloric Acid Gas.—Eulenberg f
has studied the effects of the vapour of this acid on rabbits and pigeons.
One of these experiments may be cited in detail. Hydrochloric acid gas,
prepared by heating together common salt and sulphuric acid, was passed
into a glass shade supported on a plate, and a rabbit was placed in the
transparent chamber thus formed. On the entrance of the vapour, there
was immediate blinking of the eyes, rubbing of the paws against the
nostrils, and emission of white fumes with the expired breath, while the
respiration was irregular (40 to the minute). After the lapse of ten
minutes, the gas was again introduced, until the atmosphere was quite
thick; the symptoms were similar to those detailed above, but more
violent; and in fourteen minutes from the commencement, the rabbit
sank down on its right side (respirations 32). When twenty-two minutes
had elapsed, the gas was again allowed to enter. The rabbit now lay
quiet, with closed eyes and laboured respiration, and finally, after half
an hour of intermittent exposure to the gas, the animal was removed.
The cornea were opalescent, and the eyes filled with water; there was
frequent shaking of the head and working of the forepaws. After three
minutes' exposure to the air, the respirations were found to be 128 per
minute; this quickened respiration lasted for an hour, then gave place to
a shorter and more superficial breathing. On the second day after the
experiment, the rabbit suffered from laboured respiration (28 to the
minute) and pain, and there was a rattling in the bronchial tubes. The
animal died on the third day, death being preceded by slow respiration
(12 to the minute).
The appearances twenty-four hours after death were as follows:—The
* Those who desire to study more closely the effect of acids generally on vegeta-
tion may consult the various papers of the alkali inspectors contained in the Local
Government Reports. See also Schubarth, Die Saueren Gase, welche Schwefelsåure
wºnd Soda-Fabriken verbreiten. Verhandlungen des Vereins zur Beforderung des
Gewerbefleisses in Preussen, 1857, S. 135. Dingler's Journal, Bd. cxlv. S. 374–427.
Christel, Ueber die Einwirkung von Săuren-Dāmpfen auf die Vegetation.
Arch. f. Pharmacie 1871, p. 252.
Vierteljahrsschrift für gerichtliche Medicin, xvii. S. 404, 1872.
t Gewerbe Hygiene, Berlin, 1876, S. 15.
IO2 POISONS : THEIR EFFECTS AND DETECTION. [$ 75.
eyes were coated with a thick slime, and both cornea were opalescent;
there was strong rigidity of the body. The pia mater covering the brain
was everywhere hyperaemic, and at the hinder border of both hemi-
spheres appeared a small clot, surrounded by a thin layer of bloody fluid.
The plea, venos. spin, was filled with coagulated blood, and there was also
a thin extravasation of blood covering the medulla and pons. The lungs
were mottled bright brown-red; the middle lobe of the right lung was
dark brown, solid, and sank in water; the lower lobe of the same lung
and the upper lobe of the left lung were nearly in a similar condition,
but the edges were of a bright red. The parenchyma in the darker places
on section did not crepitate. On the cut surface was a little dark fluid,
weakly-acid blood; the tracheal mucous membrane was injected. The
heart was filled with thick coagulated blood; the liver was congested, of
a reddish-brown colour, and rich in dark, fluid blood: in the vena cava
inferior was coagulated blood. The kidneys were not hyperaemic ; the
intestines were superficially congested.
There can be little doubt that the symptoms during life, and the
appearances after death, in this case are perfectly consistent with the
following view —The vapour acts first as a direct irritant, and is capable
of exciting inflammation in the lung and bronchial tissues; but besides
this, there is a secondary effect, only occurring when the gas is in sufficient
quantity, and the action sufficiently prolonged—viz., a direct coagulation
of the blood in certain points of the living vessels of the lungs. The
consequence of this, is a more or less general backward engorgement, the
right side of the heart becomes distended with blood, and the ultimate
cause of death is partly mechanical. The hyperaemia of the brain mem-
branes, and even the haemorrhages, are quite consistent with this view,
and occur in cases where the obstruction to the circulation is of a coarser
and more obvious character, and can therefore be better appreciated.
§ 75. Effects of the Liquid Acid.—There is one distinction between
poisoning by hydrochloric and the other mineral acids—namely, the
absence of corrosion of the skin. Ad. Lesser * has established, by direct
experiment, that it is not possible to make any permanent mark on the
skin by the application even of the strongest commercial acid (40 per
cent.). Hence, in any case of suspected poisoning by acid, should there
be stains on the lips and face as from an acid, the presumption will be
rather against hydrochloric. The symptoms themselves differ very little
from those produced by sulphuric acid. The pathological appearances
also are not essentially different, but hydrochloric is a weaker acid, and
the extensive disorganisation, solution, and perforation of the viscera,
noticed occasionally with sulphuric acid, have never been found in hydro-
chloric acid poisoning. We may quote here the following case:—
* Virchow's Archiv f. path. Amat., Bd. xxxiii. Hft, 2, S. 215, 1881.
§ 76.] HYDROCHLORIC ACID. Iö3
A woman, under the influence of great and sudden grief—not unmixed
with passion—drew a bottle from her pocket, and emptied it very
quickly. She immediately uttered a cry, writhed, and vomited a yellow-
green fluid. The abdomen also became enlarged. Milk was given her,
but she could not swallow it, and death took place, in convulsions, two
hours after the drinking of the poison.
The post-mortem appearances were briefly as follows:—Mouth and
tongue free from textural change: much gas in the abdomen, more espe-
cially in the stomach; the membranes of the brain congested; the lungs
filled with blood. The stomach was strongly pressed forward, of a dark
brown-red, and exhibited many irregular blackish spots, varying from
two lines to half an inch in diameter (the spots were drier and harder
than the rest of the stomach); the mucous membrane, internally, was
generally blackened, and changed to a carbonised, shaggy, slimy mass,
while the organ was filled with a blackish homogeneous pulp, which had
no odour. The gullet was also blackened. A considerable quantity of
hydrochloric acid was separated from the stomach.*
The termination in this instance was unusually rapid. In a case
detailed by Casper, f in which a boy drank an unknown quantity of acid,
death took place in seven hours. In Guy’s Hospital museum, the duo-
denum and stomach are preserved of a patient who is said to have died
in nine and a half hours from half an ounce of the acid. The same
quantity, in a case related by Taylor, caused death in eighteen hours.
From these and other instances, it may be presumed that death from
acute poisoning by hydrochloric acid will probably take place within
twenty-four hours. From the secondary effects, of course, death may
take place at a remote period; e.g., in a case recorded by Dr. Duncan
(Lancet, April 12, 1890), a man drank about 1 oz. of HCl accidentally,
was admitted to Charing Cross Hospital the same day, and treated with
small quantities of sodium carbonate, and fed by the rectum. On the
eighth day he brought up 34 oz. of blood; in a month he left apparently
perfectly well, but was admitted again in about six weeks, and died of
contraction of the stomach and stricture of the pylorus on the ninety-
fourth day. - -
§ 76. Post-mortem Appearances.—The pathological appearances are
very similar to those found in the case already detailed; though the
skin of the face may not be eroded in any way by the acid, yet the more
delicate mucous membrane of the mouth, gullet, etc., appears mostly to
be changed, and is usually white or whitish-brown. There is, however,
in the museum of the Royal College of Surgeons the stomach and gullet
* Preuss. Med. Vereinszeit, w. Friederich's Blatter f. gericht!. Anthropologie, 1858,
Hft. 6, S. 70.
+ Case 230.—Gerichtliche Medicin, 6th ed., Berlin, 1876.
IO4 12OISONS : THEIR EFFECTS AND DETECTION. [$ 76.
(No. 2386c.) of an infant 13 months old; the infant drank a teacupful
of strong hydrochloric acid, and died nine hours after the dose. The
pharynx and the upper end of the gullet is quite normal, the corrosive
action commencing at the lower end, so that, although the acid was con-
centrated, not the slightest effect was produced on the delicate mucous
membrane of the throat and upper part of the gullet. The lower end of
the gullet and the whole of the stomach were intensely congested ; the
rugae of the latter were ecchymosed and blackened by the action of
the acid. There were also small haemorrhages in the lungs, which were
aScribed to the action of the acid on the blood. Perforation of the
stomach has not been noticed in hydrochloric acid poisoning.
In Guy's Hospital museum (prep. 17991), the stomach and duodenum
of the case mentioned exhibit the mucous membrane considerably
injected, with extravasations of blood, which, at the time when the
preparation was first arranged, were of various hues, but are now some-
what altered, through long keeping in spirit. In St. George's Hospital
museum (ser. x. 43, d. 200) are preserved the stomach and part of the
duodenum of a person who died from hydrochloric acid. The case is
detailed in the Medical Times and Gazette for 1853, vol. ii. p. 513. The
whole inner surface appears to be in a sloughing state, and the larynx
and lung were also inflamed. In St. Bartholomew's Hospital museum
(1946, f. 1899) is preserved the oesophagus and stomach of an infant
aged 1 year who died from hydrochloric acid poisoning. The mucous
membrane of the gullet is white and shrivelled, that of the stomach
covered with large patches of a dark brown colour which represent
altered blood. The effect ceases at the pylorus.
A preparation, presented by Mr. Bowman to King's College Hospital
museum, exhibits the effects of a very large dose of hydrochloric acid.
The gullet has a shrivelled and worm-eaten appearance; the stomach is
injected with black blood, and was filled with an acid, grumous matter.*
Looking at these and other museum preparations illustrating the
effects of sulphuric and hydrochloric acids, it is difficult (in default of
the history of the cases) to distinguish between the two, by the naked-
eye appearances, Save in those cases in which the disorganisation was so
excessive as to render hydrochloric acid improbable. On the other hand,
the changes produced by nitric acid are so distinctive, that it is im-
possible to mistake its action for that of any other acid. The nitric
acid pathological preparations may be picked out at a glance.
* A drawing of parts of the gullet and stomach is given in Guy and Ferrier's
Foremsic Medicine.
§ 77.] HYDROCHLORIC ACID. IO5
Detection and Estimation of Free Hydrochloric Acid.
§ 77. (1) Detection.—A large number of colouring reagents have
been proposed as tests for the presence of free mineral acid. Among the
best is methyl-amiline violet decolorised by a large amount of hydrochloric
acid; the violet turns to green with a moderate quantity, and to blue
with a small quantity.
Tropaeolin (00), in the presence of free mineral acid, strikes a ruby-
red to a dark brown-red.
Congo-red is used in the form of paper dyed with the material;
large amounts of free hydrochloric acid strike blue-black, small quan-
tities blue.
Günzburg's test is 2 parts phloroglucin and 1 part vanillin, dissolved
in 100 parts of alcohol. Fine red crystals are precipitated on the
addition of hydrochloric acid. To test the stomach contents for free
hydrochloric acid by means of this reagent, equal parts of the fluid and
the test are evaporated to dryness in the water-bath in a porcelain dish.
If free hydrochloric acid be present, the evaporated residue shows a red
colour; 1 mgrm. of acid can by this test be detected. The reaction is
not interfered with by organic acids, peptones, or albumin.
Jaksch speaks highly of benzopurpurin as a test. Filter-paper is
soaked in a saturated aqueous solution of benzopurpurin 6 B (the variety
1 or 4 B is not so sensitive), and the filter-paper thus prepared allowed
to dry. On testing the contents of the stomach with the reagent, if
there is more than 4 parts per 1000 of hydrochloric acid the paper is
stained intensely blue-black; but if the colour is brown-black, this is
from butyric or lactic acids, or from a mixture of these acids with
hydrochloric acid. If the paper is washed with pure ether, and the
colour was due only to organic acid, the original hue of the paper is
restored; if the colour produced was due to a mixture of mineral and
organic acids, the brown-black colour is weakened; and, lastly, if due to
hydrochloric acid alone, the colour is not altered by washing with ether.
Acid salts have no action, nor is the test interfered with by large
amounts of albumins and peptones.
A. Williers and M. Favolle * have published a sensitive test for
hydrochloric acid. The test consists of a saturated aqueous solution of
colourless aniline, 4 parts; glacial acetic acid, 1 part ; 0°l mgrim. of
hydrochloric acid strikes with this reagent a blue colour, 1 mgrim, a
black colour. The liquid under examination is brought by evaporation,
or by the addition of water, to 10 c.c. and placed in a flask; to this is
added 5 c.c. of a mixture of equal parts of sulphuric acid and water,
* Comptes Rend., cxviii.
IO6 POISONS: THEIR EFFECTS AND DETECTION. [$ 77.
then 10 c.c. of a saturated solution of potassic permanganate, and heated
gently, conveying the gases into 3 to 5 c.c. of the reagent contained in
a test tube immersed in water. If, however, bromine or iodine (one or
both) should be present, the process is modified as follows:—The
hydracids are precipitated by silver nitrate; the precipitate is washed,
transferred to a small flask, and treated with 10 c.c. of water and 1 c.c.
of pure ammonia. With this strength of ammonia the chloride of silver
is dissolved easily, the iodide not at all, and the bromide but slightly.
The ammoniacal solution is filtered, boiled, and treated with SH3; the
excess of SH3 is expelled by boiling, the liquid filtered, reduced to 10
c.c. by boiling or evaporation, sulphuric acid and permanganate added
as before, and the gases passed into the aniline. The process is
inapplicable to the detection of chlorides or hydrochloric acid if
cyanides are present, and it is more adapted for traces of hydrochloric
acid than for the quantities likely to be met with in a toxicological
Inquiry.
(2) Quantitative estimation of Free Hydrochloric Acid.—The
contents of the stomach are diluted to a known volume, say 250 or 500
c.c. A fractional portion is taken, say 10 c.c., coloured with litmus or
phenolphthalein, and a decinormal solution of soda added drop by drop
until the colour changes; this gives total acidity. Another 10 c.c. is
shaken with double its volume of ether three times, the fluid separated
from ether and titrated in the same way; this last titration will give the
acidity due to mineral acids and acid salts; * if the only mineral acid
present is hydrochloric acid the results will be near the truth if reckoned
as such, and this method, although not exact for physiological research,
is usually sufficient for the purpose of ascertaining the amount of
hydrochloric acid or other mineral acids in a case of poisoning. It
depends on the fact that ether extracts free organic acids, such as
butyric and lactic acids, but does not extract mineral acids.
The free mineral acid, after extracting the organic acid by ether, can
also be saturated with cinchonine; this hydrochlorate of cinchomine is
extracted by chloroform, evaporated to dryness, and the residue dissolved
in water acidified by nitric acid and precipitated by silver nitrate; the
silver chloride produced is collected on a small filter, washed, and the
* To distinguish between acidity due to free acid and acid salts, or to acidity due
to the combined action of acid salts and free acids, the method of Leo and Uffelmann
is useful. A fractional portion of the contents of the stomach is triturated with pure
calcium carbonate ; if all the acidity is due to free acid, the fluid in a short time
becomes neutral to litmus; if, on the other hand, the acidity is due entirely to acid
salts, the fluid remains acid; or, if due to both acid and acid salts, there is a propor-
tionate diminution of acidity due to the decomposition of the lime carbonate by the
free acid. A quantitative method has been devised upon these principles. See Leo,
Diagnostik der Kramkheiten der Verdawwngsorgane, Hirschwald, Berlin, 1890.
§ 77.] HYDROCHLORIC ACID. Io/
filter, with its contents, dried and ignited in a porcelain crucible; the
silver chloride, multiplied by 0-25426, equals HCl.
The best method of estimating free hydrochloric acid in the stomach
is that of Sjokvist as modified by v. Jaksch; * it has the disadvantage
of its accuracy being interfered with by phosphates; it also does not
distinguish between actual free HCl and the loosely bound HCl with
albuminous matters, this in a toxicological case is of small importance,
because the quantities of HCl found are likely to be large.
The method is based upon the fact that if carbonate of baryta be
added to the contents of the stomach, the organic acids will decompose
the barium carbonate, forming butyrate, acetate, lactate, etc., of barium ;
and the mineral acids, such as hydrochloric acid, will combine, forming
salts of barium.
On ignition, chloride of barium will be unaffected, while the organic
Salts of barium will be converted into carbonate of barium, practically
insoluble in carbonic acid free water.
The contents of the stomach are coloured with litmus, and barium
carbonate added until the fluid is no longer acid (as shown by the dis-
appearance of the red colour); then the contents are evaporated to
dryness in a platinum dish, and ignited at a dull red heat ; complete
burning to an ash is not necessary. After cooling, the burnt mass is
repeatedly exhausted with boiling water and filtered ; the chloride of
barium is precipitated from the filtrate by means of dilute sulphuric
acid; the barium sulphate filtered off, washed, dried, and, after ignition,
weighed; 233 parts of barium sulphate equal 73 parts of HCl.
A method somewhat quicker, but depending on the same principles,
has been suggested by Braun.i. A fractional part, say 10 c.c., of
the fluid contents is coloured by litmus and titrated with decinormal
Soda. To the same quantity is added 2 or 3 more c.c. of decinormal
soda than the quantity used in the first titration; this alkaline
liquid is evaporated to dryness and ultimately ignited. To the ash
is now added exactly the quantity of decinormal sulphuric acid as the
decinormal Soda last used to make it alkaline—that is to say, if the
total acidity was equal to 3-6 d.m. soda, and 5-6 d.n. soda was added to
the 10 c.c. evaporated to dryness and burned, then 5-6 c.c. of d.n.
sulphuric acid is added to the ash. The solution is now warmed to get
rid of carbon dioxide, and, after addition of a little phenolphthalein,
titrated with d.m. soda solution until the change of colour shows satura-
tion, the number of c.c. used, multiplied by 0.00365, equals the HCl.
* Klömische Diagnostik, Dr. Rudolph v. Jaksch, Wien u. Leipzig, 1892. Clinical
Diagnosis. English translation. Fifth edition. London : Charles Griffin & Co.,
Limited.
+ Op. cit., S. 157.
fo8 POISONS: THEIR EFFECTS AND DETECTION. [$ 78, 79.
§ 78. In investigating the stains from hydrochloric acid on fabrics, or
the leaves of plants, any free hydrochloric acid may be separated by
boiling with water, and then investigating the aqueous extract. Should,
however, the stain be old, all free acid may have disappeared, and yet
some of the chlorine remain in organic combination with the tissue, or in
combination with bases. Dr. Angus Smith has found weighed portions
of leaves, etc., which had been exposed to the action of hydrochloric
acid fumes, richer in chlorides than similar parts of the plants not thus
exposed.
The most accurate method of investigation for the purpose of separat-
ing chlorine from combination with organic matters is to cut out the
stained portions, weigh them, and burn them up in a combustion tube,
the front portion of the tube being filled with caustic lime known to be
free from chlorides; a similar experiment must be made with the
unstained portions. In this way a considerable difference may often be
found ; and it is not impossible, in some instances, to thus detect, after
the lapse of many years, that certain stains have been produced by a
chlorine-holding substance.
III.-Nitric Acid.
§ 79. General Properties.—Nitric acid—commonly known in England
as aqua fortis, chemically as mitric acid, hydric nitrate, or nitric mono-
hydrate—is a mono-hydrate of nitrogen pentoxide (N2O), two equi-
valents, or 126 parts, of mitric acid containing 108 of N.O., and 18 of
H2O. Anhydrous mitric acid, or mitrogen pentoxide, can be obtained by
passing, with special precautions, dry chlorine over silver nitrate; the
products are free oxygen and nitrogen pentoxide, according to the fol-
lowing equation :--
Silver Nitrate. Chlorine. Silver Chloride. Nitrogen Pentoxide. Oxygen.
Ag30,N2O3 + 2Cl - 2AgCl + N2O3 + O
By surrounding the receiver with a freezing mixture, the acid is con-
densed in crystals, which dissolve in water, with emission of much heat,
forming nitric acid. Sometimes the crystals, though kept in sealed tubes,
decompose, and the tube, from the pressure of the liberated gases, bursts
with a dangerous explosion.
Pure mitric acid has a specific gravity of 1:52, and boils at 98°. Dr.
Ure examined the boiling point and other properties of nitric acid very
fully. An acid of 1:5 specific gravity boils at 98-8 ; of specific gravity
1:45, at 115-5°; specific gravity 1:40, at 118:8°; of specific gravity 1:42,
at 122.8°, 123°–124°. The acid of specific gravity 1:42 is the standard
acid of the British Pharmacopoeia. It can always be obtained by
§ 80–82.] NITRIC ACID. IO9
distilling either strong or moderately weak nitric acid; for, on the one
hand, the acid on distillation gets weaker until the gravity of 1:42 is
reached, or, on the other, it becomes stronger.
It has been held that acid of 1:42 gravity is a definite hydrate,
(2NOAH, 3H,0); it corresponds to 70 per cent. of the liquid acid HNO3.
There are also at least two other hydrates known—-one an acid of 1:484
specific gravity, 2NOah, H2O, b.p. 121*; the other an acid of specific
gravity 1-405, 4NO3H, 7H,0, b.p. 125°.
In Germany the officinal acid is of 1185 specific gravity, correspond-
ing to about 30 per cent. of HNO3. The dilute nitric acid of the
Pharmacopoeia is a colourless liquid, of specific gravity 1-101, and should
contain about 17.4 per cent. of acid. The acids used in various in-
dustries are known respectively as dyers' and engravers’ acid. Dyers'
acid has a specific gravity of 1:33 to 1:34 (66° to 68° Twad.), that is,
strength from 56 to 58 per cent. of HNO3, Engravers’ acid is stronger,
being of 1:40 specific gravity (80° Twad.), and contains 70 per cent. of
HNOs. Although the pure acid of commerce is (and should be) almost
colourless, most commercial specimens are of hues from yellow up to
deep red. An acid saturated with red oxides of nitrogen is often known
as “fuming nitric acid.”
§ 80. Use in the Arts.—Nitric acid is employed very extensively in
the arts and manufactures. The dyer uses it as a solvent for tin in the
preparation of valuable mordants for calico and other fabrics; the
engraver uses it for etching copper. It is an indispensable agent in the
manufacture of gun-cotton, nitro-glycerin, picric acid, and sulphuric
acid ; it is also used in the manufacture of tallow, in preparing the felt
for hats, and in the gilding trades. It is said to be utilised to make
yellowish or fawn-coloured spots on cigar leaves, so as to give them the
appearance of age and quality. It is also used as a medicine.
§ 81. Statistics of Poisoning by Nitric Acid.—In the ten years
ending 1903 one case of murder was ascribed to nitric acid, and it
caused accidentally 21 deaths, and was used in 69 cases of suicide.
The following table gives the sex distribution of these deaths:—
DEATHS IN ENGLAND AND WALES DURING THE TEN YEARS
ENDING 1903 FROM NITRIC ACID.
ACCIDENT OR NEGLIGENCE. . SUICIDE.
Males, . & tº tº e . 13 Males, . & * & & . 46
Females, tº e e º . 8 Females, g g e g . 23
Total, 21 | Total, . 69
$ 82. Fatal Dose.—The dose which causes death has not been ascer-
tained with any exactness. As in the case of sulphuric acid, we may go
I IO POISONS: THEIR EFFECTS AND DETECTION. [$ 83, 84.
so far as to say that it is possible for a few drops of the strong acid
to be fatal, for if brought into contact with the vocal apparatus, fatal
spasm of the glottis might be excited. The smallest dose on record is
7-7 grims. (2 drachms), which killed a child aged 13.
$83. Action of Nitric Acid on Vegetation.—Nitric acid acts on
plants injuriously in a twofold manner—viz., by direct corrosive action,
and also by decomposing the chlorides which all plants contain, thus
setting free chlorine, which decomposes and bleaches the chlorophyll.
The action is most intense on soft and delicate leaves, such as those of
clover, the cabbage, and all the cruciferae. The tobacco plant is particu-
larly injured by nitric acid. Next to all herbaceous plants, trees, such
as the apple, pear, and other fruit trees, generally suffer. The coniferae,
whether from their impregnation with resin, or from some other cause,
possess a considerable resisting-power against nitric acid vapours, and
the same is true as regards the cereals; in the latter case, their siliceous
armour acts as a preserving agent.
§ 84. Nitric Acid Vapour.—The action of nitric acid in a state of
vapour, as evolved by warming potassic nitrate and sulphuric acid
together, has been studied by Eulenberg. A rabbit was placed under a
shade into which 63 grammes of nitric acid in a state of vapour were in-
troduced. From the conditions of the experiment, some nitric peroxide
must also have been present. Irritation of the external mucous mem-
branes and embarrassment in breathing were observed. The animal in
forty-five minutes was removed, and suffered afterwards from a croupous
bronchitis, from which, however, it completely recovered in eleven days.
A second experiment with the same animal was followed by death. On
inspection, there was found strong injection of the cerebral membranes,
with small extravasations of blood; the lungs were excessively con-
gested ; the right middle lobe especially was of a liver-brown colour, and
empty of air: it sank in water.
O. Lassar * has also made a series of researches on the influence of
nitric acid vapour, from which he concludes that the acid is not absorbed
by the blood, but acts only by its mechanical irritation, for he could not
trace, by means of an examination of the urine, any evidence of such
absorption.
There are a few instances on record of the vapour having been fatal
to men; for example, the well-known case of Mr. Haywood, a chemist of
Sheffield, may be cited. In pouring a mixture of nitric and sulphuric
acids from a carboy of sixty pounds capacity, the vessel broke, and for
a few minutes he inhaled the mixed fumes. He died eleven hours after
the accident, although for the first three hours there were scarcely any
symptoms of an injurious effect having been produced. On inspection,
* Hoppe-Seyler's Zeitschrift f. physiol. Chemie, Bd. i. S. 165–173, 1877–78.
$ 85.] NITRIC ACID, I I I
there was found intense congestion of the windpipe and bronchial tubes,
with effusion of blood in the latter. The lining membrane of the heart
and aorta was inflamed; unfortunately, the larynx was not examined.*
A very similar case happened in Edinburgh in 1863.f Two young
men were carrying a jar of nitric acid; the jar broke, and they attempted
to wipe up the acid from the floor. The one died ten hours after the
accident, the other in less than twenty-four hours. The symptoms were
mainly those of difficult breathing, and it is probable that death was
produced from suffocation. Dr. Taylor relates also, that having accident-
ally inhaled the vapour in preparing gun-cotton, he suffered from severe
constriction of the throat, tightness in the chest, and cough, for more
than a week. ;
$ 85. Effects of Liquid Nitric Acid.—Criminal poisoning by nitric
acid, though still rare, is naturally more frequent than formerly. At
the beginning of the 19th century, Tartra Ś wrote a most excellent mono-
graph on the subject, and collated all the cases he could find, from the
first recorded instances related by Bembo || in Venetian history, down to
his own time. The number of deaths in those 400 years was but fifty-
five, while, in the 18th century, at least fifty can be numbered in England.
Most of these (74 per cent.) are suicidal, a very few homicidal, the rest
accidental. In one of Tartra's cases, some nitric acid was placed in the
wine of a drunken woman, with fatal effect. Osenbrüggen'ſ relates the
case of a father murdering his six children by means of nitric acid ; and
C. A. Buchner ** that of a soldier who poured acid into the mouth of his
illegitimate infant. A curious case is one in which a man poisoned his
drunken wife by pouring the acid into her right ear; she died after six
weeks' illness. All these instances prove again, if necessary, that the
acid is only likely to be used with murderous intent in the case of
young children, or of sleeping, drunken, or otherwise helpless people.
As an example of the way in which accidents are brought about by
heedlessness, may be cited the comparatively recent case of a woman
who bought a small quantity of aqua fortis for the purpose of allaying
toothache by a local application. She attempted to pour the acid
direct from the bottle into the cavity of the tooth ; the acid went down
her throat, and the usual symptoms followed. She threw up a very
* Lancet, April 15, 1854, p. 430.
t Chemical News, March 14, 1863, p. 132.
† Principles and Practice of Medical Jurisprudence, vol. i. p. 218, 1873.
§ Tartra, A. E., Dr., Traité de l'Empoisonnement par l'Acide Nitrique, Paris,
An. 10 (1802), pp. 300.
| Bembo Cardinalis, Rerum Venetarium. Historia, lib. i. p. 12, Paris Ed., 1551.
T Allgem.-Deutsche Strafrechtszeitung, herausgeg. v. Frz. v. Holtzendorff, 5
Jahrg., Hft. 5, S. 273, 1865.
** Friederich's Blätter f. ger. Med., 1866, Hft. 3, S. 187.
I I 2 POISONs: THEIR EFFECTS AND DETECTION. [$ 86, 87.
perfect cast of the gullet (preserved in University College museum),
and rapidly died. Nitric acid has been mistaken for various liquids,
and has also been used by injection as an abortive, in every
respect having a toxicological history similar to that of sulphuric
acid.
$ 86. Local Action.—When strong nitric acid comes in contact with
organic matters, there is almost constantly a development of gas. The
tissue is first bleached, and then becomes of a more or less intense
yellow colour. Nitric acid spots on the skin are not removed by
ammonia, but become of an orange-red when moistened with potash
and a solution of cyanide of potassium. The yellow colour seems to
show that picric acid is one of the constant products of the reaction ;
sulphide of ammonium forms a sort of soap with the epidermis thus
attacked, and detaches it.
§ 87. Symptoms.-The symptoms and course of nitric acid poison-
ing differ in a few details only from those of sulphuric acid. There
is the same instant pain and frequent vomiting, destruction of the
mucous membranes, and, in the less severe cases, after-contraction of
the gullet, etc.
One of the differences in the action of nitric and sulphuric acids is
the constant development of gas with the former. This, without doubt,
adds to the suffering. Tartra made several experiments on dead
bodies, and showed that very considerable distension of the intestinal
canal, by gaseous products, was the constant result ; the tissues were
corroded and almost dissolved, being transformed, ultimately, into a
sort of greasy paste. The vomited matters are of a yellow colour,
unless mixed with blood, when they are of a dirty brown hue, with
shreds of yellow mucus, and have the strong acid reaction and smell
of nitric acid. The teeth may be partially attacked from the solvent
action of the acid on the enamel. The fauces and tongue, at first
blanched, soon acquire a citron-yellow, or even a brown colour; the
whole cavity may swell and inflame, rendering the swallowing of liquids
difficult, painful, and sometimes impossible. The air-passages may
also become affected, and in one case tracheotomy was performed
for the relief of the breathing.” The stomach rejects all remedies;
there are symptoms of collapse; quick, weak pulse, frequent shivering,
obstinate constipation, and death (often preceded by a kind of stupor)
in from eighteen to twenty-four hours. The intellectual faculties
remain clear, save in a few rare instances. tº
C. A. Wunderlich has recorded an unusual case, in which the
symptoms were those of dysentery, and the large intestine was found
acutely inflamed, while the small one was little affected. The kidneys
* Arnott, Med. Gaz., vol. xii. p. 220. -
§ 88.] NITRIC ACID. II 3
had the same appearance as in Bright's disease.” Should the dose
of nitric acid be insufficient to kill at once, or, what amounts to
the same thing, should the acid be immediately diluted with water,
or in some way be neutralised, the patient, as in the case of
sulphuric acid, may yet die at a variable future time from stenosis
of the gullet, impaired digestion, etc. For example, in an interest-
ing case related by Tartra, f a woman, who had swallowed 42
grms. (15 oz.) of nitric acid, feeling acute pain, took immediately a
quantity of water, and three hours afterwards was admitted into
hospital, where she received appropriate treatment. At the end of a
month she left, believing herself cured ; but in a little while returned,
and was re-admitted, suffering from marasmus, extreme weakness, and
constant vomiting; ultimately she died. The post-mortem examination
revealed extreme contraction of the intestinal canal throughout. The
lumen would hardly admit a penholder. The stomach was no larger
than an ordinary intestine, and was adherent to adjacent organs; on its
internal surface there were spots, probably cicatrices; there were also
changes in the gullet, but not so marked. A somewhat similar case
is related by the same author in his thirteenth observation. In the
Middlesex Hospital there is preserved the stomach (No. 1363) of a
man who died forty days after swallowing 2 ozs. of nitric acid diluted
in a tumbler of water. The stomach is contracted, the mucous mem-
brane of the lower part of the gullet, the lesser curvature, and the
pyloric end of the stomach is extensively corroded, showing ulcerated
patches commencing to cicatrise.
§ 88. Post-mortem Appearances.—The pathological changes in
the tongue, gullet, and stomach can be readily studied from the
preparations in the different museums. The staining by the mitric
acid appears unchanged to the naked eye for many years; hence,
most of the nitric acid preparations are in an excellent state of pre-
servation. A very good example of the pathological changes is to be
found in Nos. 1049 and 1050, University College museum.
No. 1049 presents the tongue, pharynx, and larynx of a man who had swallowed
a teacupful of nitric acid. The epithelium of the desophagus is for the most part
wanting, and hangs in shreds; the dorsum of the tongue, in front of the circum-
vallate papillae, is excavated, and over its central part superficially ulcerated ; in
other places the tongue is encrusted with a thick, loose, fawn-coloured layer, formed
probably of desquamated epithelium. The whole of the mucous surface is stained a
dirty yellow:
No. 1050 is a preparation showing the tongue, gullet, and stomach of a person
who died from the effects of nitric acid. The tongue in places is smooth and glazed ;
* De Actionibus quibusdam Acidi Nitrici Cawstico in Corpus Humanum ion-
missi. Programma Academ., Lipsiae, 1857, 4.
f Op. cit. -
II.4. POISONS : THEIR EFFECTS AND DETECTION. [$ 88.
in others slightly depressed and excavated. On the anterior wall and upper portion
of the gullet two large sloughs exist.
Although perforation of the stomach is not so common with nitric as with sul-
phuric acid, such an accident may occur, as shown in a preparation at Guy's Hos-
pital, in which there is a perforation at the cardiac end. All the mucous membrane
has disappeared, and the inner surface is for the most part covered with flocculent
shreds. Three ounces of nitric acid are said to have been swallowed, and the
patient lived seventeen hours. There is the usual staining. There is also in the
Middlesex Hospital (No. 1364) the Cesophagus and stomach of a woman aged 30,
who died six hours after swallowing 2 to 3 ozs, of strong nitric acid. The inner
coats of the mucous membrane of the gullet and stomach are in part converted into
opaque yellow and black eschars, and in part to a shreddy pulpy condition. At
the most depending part of the stomach is a large ragged perforation, with pulpy
margins, which allowed the contents of the stomach to escape into the peritoneal
cavity.
In St. Bartholomew's museum there is a very good specimen (No. 1870) of the
appearances in the gullet and stomach after poisoning by nitric acid. The case is
detailed in St. Bartholomew's Hospital Reports, vol. v. p. 247. A male died in
fifteen hours after swallowing 1 oz. of nitric acid. The whole mucous membrane
is wrinkled, or rather ploughed, into longitudinal furrows, the yellow discoloration
stops abruptly, with an irregular border, at the commencement of the stomach, the
epithelial and mucous coats of which are wanting—its surface being rough and of a
brownish-red colour.
The following preparations are to be found in the museum of the London
Hospital:—A. b. 1. and A. b. 8.—A. b. 1. shows the pharynx, oesophagus, larynx,
and stomach of a young woman, who, after taking half an ounce of nitric acid, died
in eight hours. The staining is very intense ; as an unusual feature, it may be
noted that the larynx is almost as yellow as the oesophagus. The abrasion or solu-
tion of the epithelium on the dorsum of the tongue has dissected out the circumvallate
and fungiform papillae, so that they project with unusual distinctness. The lining
membrane of the gullet throughout is divided into minute squares by longitudinal
and transverse furrows. The mucous membrane of the stomach appears wholly
destroyed, and presents a woolly appearance.
A. b. 8. shows a very perfect cast of the oesophagus. The case was that of a
woman, aged 35, who swallowed half an ounce of nitric acid. The symptoms for the
first four days were the usual pain in the throat and stomach, which might be
expected ; the bowels were freely open, and the stools dark and offensive. On the
sixth day, there was constant vomiting with offensive breath ; on the ninth, the
appearance of the patient was critical, and she threw up the cast preserved. She died
on the tenth day after the taking of the acid. The gullet, stomach, trachea, and
larynx were found after death much inflamed.
The following preparations are in St. Thomas' Hospital:—P. 5. —A stomach with
gullet attached. The stomach is covered with yellowish-green patches of false mem-
brane and deposit ; the gullet has the usual longitudinal furrows so characteristic
of corrosive fluids.
P. 6. is also from a case of nitric acid poisoning. It shows the lining membrane
of the stomach partly destroyed and shreddy, yet but little discoloured, the hue being
a sort of delicate fawn.
To these may be added a case described and figured by Lesser ; to a baby, a few
days old, an unknown quantity of fuming nitric acid was given ; the child made a
gurgling, choking sound, and died in a few minutes. The corpse, nine days after
death, showed no signs of decomposition. The tongue and gums were yellow, the
gullet less so, the stomach still less, and the small intestine had no yellow tint; the
whole of the mouth, gullet, and stomach showed the corrosive action of the acid. The
§ 89.] NITRIC ACID. - II 5
graduation of tint, Lesser remarks, is what is not seen when the yellow colour is due
to poisoning by chromic acid or by strong solution of ferric perchloride ; in such
cases, wherever the liquid has gone, there is a yellowness.”
$89. Detection and Estimation of Nitric Acid.—The detection
either of free nitric acid or of its salts is not difficult. Free nitric acid,
after preliminary estimation of the total acidity by decinormal soda,
may be separated by the cinchonine process given at p. 106. On pre-
cipitation by ammonia or soda solution, the nitrate of ammonia or soda
(and, it may be, other similarly combined acids) remain in solution.
If free nitric acid is present in small quantity only, it may be necessary
to evaporate the filtrate from the cinchonine nearly to dryness, and to
test the concentrated liquid for nitric acid. The ordinary tests are as
follows:–
(1) Nitrates, treated with mercury or copper and strong sulphuric
acid, develop nitric oxide, recognised by red fumes, if mixed with air
or oxygen.
(2) A nitrate dissolved in a small quantity of water, with the addition
of a crystal of ferrous sulphate (allowed to partially dissolve), and then
of strong sulphuric acid—poured through a funnel with a long tube
dipping to the bottom of the test tube, so as to form a layer at the
bottom—strikes a brown colour at the junction of the liquid. When
the test is properly performed, there will be three layers—the upper-
most being the nitrate solution, the middle ferrous sulphate, and the
lowest sulphuric acid ; the middle layer becomes of a smoky or black
hue if a mitrate is present. Organic matter interferes much with the
reaction.
(3) Nitrates in solution, treated in the cold with a zinc copper couple,
are decomposed first into nitrites, and then into ammonia. The nitrites
may be detected by a solution of metaphenyldiamine, which strikes
a red colour with an infinitesimal quantity. Hence, a solution which
gives no red colour with metaphenyldiamine, when submitted to the
action of a zinc copper couple, and tested from time to time, cannot
contain nitrites; therefore no nitrates were originally present.
(4) Nitrates, on being treated with strong sulphuric acid, and then
a solution of indigo carmine dropped in, decolorise the indigo ; this is
a useful test—not conclusive in itself, but readily applied, and if the
cinchonine method of separation has been resorted to, with few sources
of error.
There is a process of separating nitric acid direct from any organic
tissue, which may sometimes be useful :-Place the substance in a strong,
wide-mouthed flask, closed by a caoutchouc cork, and in the flask put
a small, short test tube, charged with a strong solution of ferrous
* A. Lesser, Atlas der gerichtlichen Medicin, Berlin, 1884, Tafel i, fig. 2,
II6 POISONS: THEIR EFFECTS AND DETECTION. [$ 90, 91.
chloride in hydrochloric acid. The flask is connected to the mercury
pump (see fig. p. 50), and made perfectly vacuous by raising and
lowering the reservoir. When this is effected, the tube is adjusted so
as to deliver any gas evolved into a eudiometer, or other gas-measuring
apparatus. By a suitable movement of the flask, the acid ferrous
chloride is allowed to come in contact with the tissue, a gentle heat
applied to the flask, and gases are evolved. These may be carbon
dioxide, nitrogen, and nitric oxide. On the evolution of gas ceasing,
the carbon dioxide is absorbed by passing up under the mercury a
little caustic potash. When absorption is complete, the gas, consisting
of nitrogen and nitric oxide, may be measured. The nitric oxide may
now be absorbed by a strong solution of sodic metasulphite, and from
the contraction the nitric oxide determined.
It is also obvious that, by treating nitric oxide with oxygen, and
absorbing the nitric peroxide present by an alkaline liquid of known
strength and free from nitrates or ammonia, the resulting solution may
be dealt with by a zinc copper couple, and the ammonia developed by
the action of the couple directly estimated by titration by a decinormal
hydrochloric acid, if large in quantity, or by “messlerising,” if small
in quantity.
IV.-Acetic Acid.
$90. In the ten years ending 1903, 21 deaths (10 males and 11 females) occurred
in England and Wales from drinking, by mistake or design, strong acetic acid.
A few cases only have been recorded in medical literature, although there have
been many experiments on animals.
The symptoms in the human subject consist of pain, vomiting, and convulsions.
In animals it causes colic, paralysis of the extremities, bloody urine, and oedema
of the lungs. The lethal dose for plant-eating animals is about 0:49 gramme per kilo.
There should be no difficulty in recognising acetic acid ; the odour alone is, in
most cases, strong and unmistakable. Traces are detected by distilling, neutralising
the distillate by soda, evaporating to dryness, and treating the residue as follows:—
A portion warmed with alcohol and sulphuric acid gives a smell of acetic ether.
Another portion is heated in a small tube of hard glass with arsenious acid ; if
acetic acid is present, or an acetate, a smell of kakodyl is produced.
W.—Ammonia.
§ 91. Ammonia, (NHS), is met with either as a vapour or gas, or as
a solution of the pure gas in water.
Properties. – Pure ammonia gas is colourless, with a strong,
irritating, pungent odour, forming white fumes of ammonic chloride,
if exposed to hydric chloride vapour, and turning moist red litmus-paper
§ 92.] AMMONîA. i 17
strongly blue. By intense cold, or by a pressure of 6% atmospheres
at the ordinary temperature, the gas is readily liquefied ; the liquid
ammonia boils at 38° ; its observed specific gravity is 731 ; it freezes
at – 57'1". Ammonia is readily absorbed by water; at 0° water will
take up 1000 times its own volume, and at ordinary temperatures
about 600 times its volume. Alcohol also absorbs about 10 per cent.
Ammonia is a strong base, and forms a number of salts. Ammonia is
one of the constant products of the putrefaction of nitrogenous sub-
stances; it exists in the atmosphere in small proportions, and in every-
thing that contains water. Indeed, water is the only compound equal
to it in its universality of diffusion. The minute quantities of ammonia
thus diffused throughout nature are probably never in the free state,
but combinations of ammonia with hydric nitrate, carbon dioxide, etc.
§ 92. Uses.”—A solution of ammonia in water has many applications
in the arts and industries; it is used in medicine, and is an indispensable
laboratory reagent.
The officinal caustic preparations of ammonia are—ammoniae liquor
fortior (strong solution of ammonia), which should contain 32°5 per
cent. of ammonia, and have a specific gravity of 891.
Liquor ammoniae (solution of ammonia), specific gravity ‘959, and
containing 10 per cent. of ammonia. There is also a limiment of
ammonia, composed of olive oil, 3 parts, and ammonia, 1 part.
Spiritus Ammonia, Foetidus (foetid spirit of ammonia).-A solution
of asafoetida in rectified spirit and ammonia solution; 100 parts by
measure, contain 10 of strong solution of ammonia.
Strong solution of ammonia is an important ingredient in the “lini-
mentum camphorae composita’’ (compound limiment of camphor), the
composition of which is as follows:—camphor, 2-5 parts; oil of lavender,
'125; strong solution of ammonia, 5:0; and rectified spirit, 15 parts.
Its content of strong solution of ammonia is then about 22.6 per cent.
(equivalent to 7-3 of NHS).f .
The carbonate of ammonia is also caustic ; it is considered to be a
compound of acid carbonate of ammonium, NH, HCOs, with carbamate
of ammonium, NH, NH,CO3. It is in the form of colourless, crystalline
masses; the odour is powerfully ammoniacal ; it is strongly alkaline, and
the taste is acrid. It completely volatilises with heat, is soluble in
water, and somewhat soluble in spirit.
The officinal preparation is the “spiritus ammonice aromaticus,” or
* Sir B. W. Richardson has shown that ammonia possesses powerful antiseptic
properties.—Brit. Med. Jowrmal, 1862.
t There is a common limiment for horses used in stables, and popularly known
As “white oil.” It contains 1 part of ammonia, and 4 parts of olive or rape oil; not
unfrequently turpentine is added. Another veterinary liniment, called “egg oil,”
contains ammonia, oil of origanum, turpentine, and the yelks of eggs,
I I 8 Poisons: THEIR EFFECTS AND DETECTION. [$ 93–95.
aromatic spirit of ammonia. It is made by distilling in a particular way
ammonic carbonate, 4 ozs. ; strong solution of ammonia, 8 ozs. ; rectified
spirit, 120 ozs. ; water, 60 ozs. ; volatile oil of nutmeg, 4% drms. ; and oil
of lemon, 6% drms. Aromatic spirit of ammonia is a solution in a weak
spirit of neutral carbonate, flavoured with oil of lemon and nutmeg ; the
specific gravity should be 0.896.
Smelling salts (sal volatile) are composed of carbonate of ammonia.
$93. Statistics.-Falck has found throughout literature notices of
thirty cases of poisoning by ammonia, or some of its preparations. In
two of these it was used as a poison for the purpose of murder, and in
eight with suicidal intent; the remainder were all accidental. The two
criminal cases were those of children, who both died. Six out of eight
of the suicidal and twelve of the twenty accidental cases also terminated
fatally.
Ammonia was the cause of 123 deaths (60 male, 63 female) by
accident, and of 93 (39 male, 54 female) by suicide, making a total of
186 during the ten years ending 1903 in England and Wales.
§ 94. Poisoning by Ammonia Vapour.--Strong ammoniacal vapour
is fatal to both animal and vegetable life. There are, however, but few
instances of poisoning by ammonia vapour; these few cases have been,
without exception, the result of accident. Two cases of death are re-
corded, due to an attempt to rouse epileptics from stupor, by an
injudicious use of strong ammonia applied to the nostrils. In another
case, when hydrocyamic acid had been taken, there was the same result.
An instance is also on record of poisomous effects from the breaking of a
bottle of ammonia, and the sudden evolution in this way of an enormous
volume of the caustic gas. Lastly, a man employed in the manufacture
of ice, by means of the liquefaction of ammonia (Carré's process), breathed
the vapour, and had a narrow escape for his life.
§ 95. Symptoms.—The symptoms observed in the last case may well
serve as a type of what may be expected to occur after breathing
ammonia vapour. The man remained from five to ten minutes in the
stream of gas; he then experienced a feeling of anxiety, and a sense of
constriction in the epigastrium, burning in the throat, and giddiness. He
vomited. The pulse was small and frequent, the face pale, the mouth
and throat strongly reddened with increased secretion. Auscultation
and percussion of the chest elicited nothing abnormal, although during
the course of four days he had from time to time symptoms of suffocation,
which were relieved by emetics. He recovered by the eighth day.*
In experiments on animals, very similar symptoms are produced.
There is increased secretion of the eyes, nose, and mouth, with redness.
The cry of cats becomes remarkably hoarse, and they generally vomit.
* Schmidt's Jahrbuch, 1872, i. S. 30.
§ 96–98.] - - AMMONIA. I IQ
Great difficulty in breathing and tetanic convulsions are present. When
the animal is confined in a small closed chamber, death takes place in
about a quarter of an hour.
On Section, the bronchial tubes, to the finest ramifications, are found
to be filled with a tenacious mucus, and the air-passages, from the glottis
throughout, reddened. The lungs are emphysematous, but have not
always any special colour; the heart contains but little coagulated
blood; the blood has a dark red colour.
§ 96. The chronic effects of the gas, as shown in workmen engaged in
manufactures in which the fumes of ammonia are frequent, appear to be
an inflammation of the eyes and an affection of the skin. The latter is
thought to be due to the ammonia uniting to form a soap with the oil
of the lubricating skin glands. Some observers have also noticed deaf-
ness, and a peculiar colour of the skin of the nose and forehead, among
those who work in guano manufactories. Its usual action on the body
appears to be a diminution of the healthy oxidation changes, and a
general lowering of bodily strength, with evident anaemia.
§ 97. Ammonia in Solution.—Action on Plants.-Solutions of
strong ammonia, or solutions of the carbonate, act injuriously on vege-
table life, while the neutral salts of ammonia are, on the contrary,
excellent manures. A 30 per cent. Solution of ammonic carbonate kills
most plants within an hour, and it is indifferent whether the whole plant
is watered with this solution, or whether it is applied only to the leaves.
If, after this watering of the plant with ammonic carbonate water, the
injurious salt is washed out as far as possible by distilled water, or by a
weakly acidulated fluid, then the plant may recover, after having shed
more or less of its leaves. These facts sufficiently explain the injurious
effects noticed when urine is applied direct to plants, for urine in a very
short time becomes essentially a solution of ammonic carbonate.
$98. Action on Human Beings and Animal Life.—The violence
of the action of caustic solutions of ammonia almost entirely depends on
the state of concentration.
The local action of the strong solution appears to be mainly the
extraction of water and the Saponifying of fat, making a soluble soap.
On delicate tissues it has, therefore, a destructive action; but S. Samuel +
has shown that ammonia, when applied to the unbroken epidermis, does
not have the same intense action as potash or soda, nor does it coagulate
albumen. Blood, whether exposed to ammonia gas, or mixed with solu-
tion of ammonia, becomes immediately dark red; then, later, through
destruction of the blood corpuscles, very dark, even black; lastly, a dirty
brown-red. The oxygen is expelled, the haemoglobin destroyed, and the
blood corpuscles dissolved. - -
* Virchow's Archiv f. path. Amat., Bd. li. Hft. 1 u, 2, S, 41, etc., 1870.
I2O POISONS : THEIR EFFECTS AND DETECTION. [$ 98.
The albumen of the blood is changed to alkali-albuminate, and the
blood itself will not coagulate. A more or less fluid condition of the
blood has always been noticed in the bodies of those poisoned by
ammonia.
Blood exposed to ammonia, when viewed by the spectroscope, shows
the spectra of alkaline haematin, a weak absorption band, in the neigh-
bourhood of D; but if the blood has been acted on for some time by
ammonia, then all absorption bands vanish. These spectra, however, are
not peculiar to ammonia, the action of caustic potash or soda being
similar. The muscles are excited by ammonia, the functions of the
nerves are destroyed. -
When a solution of strong ammonia is swallowed, there are two main
effects—(1) the action of the ammonia itself on the tissues it comes into
contact with, and (2) the effects of the vapour on the air-passages.
There are, therefore, immediate irritation, redness, and swelling of the
tongue and pharynx, a burning pain reaching from the mouth to the
stomach, with vomiting, and, it may be, nervous symptoms. The saliva
is notably increased. In a case reported by Fonssagrives,” no less than
3 litres were expelled in the twenty-four hours. Often the glands
under the jaw and the lymphatics of the neck are swollen.
Doses of from 5 to 30 grammes of the strong solution of ammonia
may kill as quickly as prussic acid. In a case recorded by Christison,f
death occurred in four minutes from a large dose, doubtless partly by
suffocation. As sudden a result is also recorded by Plenk: a man,
bitten by a rabid dog, took a mouthful of spirits of ammonia, and died
in four minutes.
If death does not occur rapidly, there may be other symptoms—
dependent not upon its merely local action, but upon its more remote
effects. These mainly consist in an excitation of the brain and spinal
cord, and, later, convulsive movements deepening into loss of conscious-
ness. It has been noticed that, with great relaxation of the muscular
system, the patients complain of every movement causing pain. With
these general symptoms added to the local injury, death may follow
many days after the swallowing of the fatal dose.
Death may also occur simply from the local injury done to the
throat and larynx, and the patient may linger some time. Thus, in a
case quoted by Taylor, f in which none of the poison appears actually to
have been swallowed, the man died nineteen days after taking the
poison from inflammation of the throat and larynx. As with the strong
acids, so with ammonia and the alkalies generally, death may also be
* L'Union Médicale, 1857, No. 13, p. 49, No. 22, p. 90.
+ Christison, 167.
4. Principles of Jurisprudence, i. p. 235.
§ 99, IOO.] AMMONIA. f 2 I
caused many weeks and even months afterwards from the effects of con-
traction of the gullet, or from the impaired nutrition consequent upon the
destruction, more or less, of portions of the stomach or intestinal canal.
$99. Post-mortem Appearances. – In recent cases there is an
intense redness of the intestinal canal, from the mouth to the stomach,
and even beyond, with here and there destruction of the mucous mem-
brane, and even perforation. A wax preparation in the museum of
University College (No. 2378) shows the effects on the stomach produced
by swallowing strong ammonia; it is ashen-gray in colour, and most of
the mucous membrane is, as it were, dissolved away; the cardiac end is
much congested.
The contents of the stomach are usually coloured with blood; the
bronchial tubes and glottis are almost constantly found inflamed—even a
croup-like (or diphtheritic) condition has been seen. GEdema of the glottis
should also be looked for : in one case this alone seems to have accounted
for death. The blood is of a clear red colour, and fluid. A smell of
ammonia may be present.
If a sufficient time has elapsed for secondary effects to take place, then
there may be other appearances. Thus, in the case of a girl who, falling
into a fainting fit, was treated with a draught of undiluted spirits of
ammonia and lived four weeks afterwards, the stomach (preserved in
St. George's Hospital museum, 43 b, ser. ix.) is seem to be much dilated
and covered with cicatrices, and the pylorus is so contracted as hardly to
admit a small bougie. It has also been noticed that there is generally a
fatty degeneration of both the kidneys and liver.
It need scarcely be observed that in such cases no free ammonia
will be found, and the question of the cause of death must necessarily
be wholly medical and pathological.
§ 100. Separation of Ammonia.-Ammonia is separated in all cases
by distillation, and if the organic or other liquid is already alkaline,
it is at once placed in a retort and distilled. If neutral or acid, a little
burnt magnesia may be added until the reaction is alkaline. It is gener-
ally laid down that the contents of the stomach in a putrid condition
cannot be examined for ammonia, because ammonia is already present as
a product of decomposition; but even under these circumstances it is
possible to give an opinion whether ammonia in excess is present. For
if, after carefully mixing the whole contents of the stomach, and then
drying a portion and reckoning from that weight the total nitrogen
(considering, for this purpose, the contents to consist wholly of albumen,
which yields about 16 per cent. of nitrogen)—under these conditions,
the contents of the stomach yield more than 16 per cent. of nitrogen as
ammonia reckoned on the dry substance, it is tolerably certain that
ammonia not derived from the food or the tissues is present.
Í 22 POISONS: THEIR EFFECTS AND DETECTION. [š IoI-103.
If, also, there is a sufficient evolution of ammonia to cause white
fumes, when a rod moistened with hydrochloric acid is brought near to
the liquid, an effect never noticed with a normal decomposition, the
presence of extrinsic ammonia is probable.
An alkaline-reacting distillate, which gives a brown colour with the
“Nessler” reagent, and which, when carefully neutralised with sul-
phuric acid, on evaporation to dryness by the careful heat of a water-
bath, leaves a crystalline mass volatilisable by heat, and giving a copious
precipitate with an alcoholic solution of platinic chloride, but is hardly
at all soluble in absolute alcohol, can be no other substance than
ammonia.
§ 101. Estimation.—Ammonia is most quickly estimated by distil-
ling, receiving the distillate in decinormal acid, and then titrating back.
It may also be estimated as the double chloride of ammonium and plati-
mum (NH,Cl), PtCl4. The distillate is exactly neutralised by HCl,
evaporated to near dryness, and an alcoholic solution of platinic chloride
added in sufficient quantity to be always in slight excess, as shown by
the yellow colour of the supernatant fluid. The precipitate is collected,
washed with a little alcohol, dried, and weighed on a tared filter; 100
parts of the salt are equal to 7-6 of NH3.
WI. —Caustic Potash and Soda.
§ 102. There is so little difference in the local effects produced by
potash and soda respectively, that it will be convenient to treat them
together.
Potash (potassa caustica).-Hydrate of potassium (KHO), com-
bining weight 56, specific gravity 2-1.
Properties.—Pure hydrate of potassium is a compact, white solid,
usually met with in the form of sticks. When heated to a temperature
a little under redness, it melts to a nearly colourless liquid ; in this state
it is intensely corrosive. It rapidly absorbs moisture from the air, and
moist potash also absorbs with great avidity carbon dioxide; it is power-
fully alkaline, changing red litmus to blue. It is soluble in half its
weight of cold water, great heat being evolved during solution; it forms
two definite hydrates—one, KHO + H2O ; the other, KHO + 2 H2O. It
is sparingly soluble in ether, but is dissolved by alcohol, wood-spirit,
fusel oil, and glycerin. -
§ 103. Pharmaceutical Preparations.—Potassium hydrate, as well
as the solution of potash, is officinal in all pharmacopoeias. The liquor
potassa, or solution of potash, of the British Pharmacopoeia, is a strongly
alkaline, caustic liquid, of 1:058 specific gravity, and containing 5'84
§ 104–108.] CAUSTIC POTASH AND SODA. I 23
per cent. by weight of KHO. It should, theoretically, not effervesce
when treated with an acid, but its affinity for CO2 is so great that all
solutions of potash, which have been in any way exposed to air, contain
a little carbonate. Caustic sticks of potash and lime used to be officinal
in the British Pharmacopoeia. Filho's caustic is still in commerce, and
is made by melting together two parts of potassium hydrate and one
part of lime in an iron ladle or vessel; the melted mass is now moulded
by pouring it into leaden moulds. Vienna paste is composed of equal
weights of potash and lime made into a paste with rectified spirit or
glycerin.
§ 104. Carbonate of Potash (K2CO3 + 1}H2O), when pure, is in the
form of small white crystalline grains, alkaline in taste and reaction,
and rapidly deliquescing when exposed to moist air ; it gives all the
chemical reactions of potassium oxide, and carbon dioxide. Carbonate
of potash, under the name of salt of tartar, or potashes, is sold at oil
shops for cleansing purposes. It is supplied either in a fairly pure state,
or as a darkish moist mass containing many impurities.
§ 105. Bicarbonate of Potash (KHCO3) is in the form of large
transparent rhombic prisms, and is not deliquescent. The effervescing
solution of potash (liquor potassae effervescens) consists of 30 grains of
KHCOs in a pint of water (3:45 grns. per litre), and as much CO2 as
the water will take up under a pressure of seven atmospheres.
§ 106. Caustic Soda—Sodium Hydrate (NaHO).-This substance is
a white solid, very similar in appearance to potassium hydrate ; it
absorbs moisture from the air, and afterwards carbon dioxide, becom-
ing solid again, for the carbonate is not deliquescent. In this respect,
then, there is a great difference between potash and soda, for the former
is deliquescent both as hydrate and carbonate ; a stick of potash in a
semi-liquid state, by exposure to the air, continues liquid, although
saturated with carbon dioxide. Pure sodium hydrate has a specific
gravity of 2.0; it dissolves in water with evolution of heat, and the
solution gives all the reactions of sodium hydrate, and absorbs carbon
dioxide as readily as the corresponding solution of potash. The liquor
soda of the B.P. should contain 4:1 per cent. of NaHO.
§ 107. Sodae Carbonas–Carbonate of Soda—(Na,CO,10H,0). The
pure carbonate of soda for medicinal use is in colourless and transparent
rhombic octahedrons; when exposed to air, the crystals effloresce and
crumble. The soda carbonas easiccata, or dried carbonate of soda, is
simply the ordinary carbonate, deprived of its water of crystallisation,
which amounts to 62.93 per cent.
§ 108. Bicarbonate of Soda (NaHCO3) occurs in the form of
minute crystals, or, more commonly, as a white powder. The liquor
soda effervescens of the B.P. is a solution of the bicarbonate, 30 grains
I 24 Poisons: THEIR EFFECTS AND DETECTION. [$ 109–11 I.
of the salt in 20 ozs, of water (3:45 grms. per litre), the water being
charged with as much carbonic acid as it will hold under a pressure of
seven atmospheres. The bicarbonate of soda lozenges (trochisc? Soda,
bicarbonatis) contain in each lozenge 5 grains (327 mgrms.) of the
bicarbonate. The carbonate of soda sold for household purposes is of
two kinds—the one, “seconds,” of a dirty white colour and somewhat
impure; the other, “best,” is a white mass of much greater purity.
Javelle water (Eau de Javelle) is a solution of hypochlorite of soda ; its
action is poisonous, more from the caustic alkali than from the chlorine,
and may, therefore, be here included.
§ 109. Statistics.-Poisoning by the fixed alkalies is not so frequent
as poisoning by ammonia. Falck has collected, from medical literature,
27 cases, 2 of which were the criminal administering of Eau de Javelle,
and 5 were suicidal; 22, or 81.5 per cent, died—in l of the cases after
twenty-four hours; in the others, life was prolonged for days, weeks, or
months—in 1 case for twenty-seven months. In the ten years ending
1903, in England and Wales there were 23 deaths from poisoning by
the fixed alkalies, 12 males and 11 females, all due to accident, not a
single case of suicide or murder.
§ 110. Effects on Animal and Vegetable Life.—The fixed alkalies
destroy all vegetable life, if applied in strong solution or in substance,
by dehydrating and dissolving the tissues. The effects on animal
tissues are, in part, due also to the affinity of the alkalies for water.
They extract water from the tissues with which they come in contact,
and also attack the albuminous constituents, forming alkali-albuminate,
which swells on the addition of water, and, in a large quantity, even
dissolves. Cartilaginous and horny tissues are also acted upon, and
strong alkalies will dissolve hair, silk, etc. The action of the alkali is
by no means restricted to the part first touched, but has a remarkable
faculty of spreading in all directions.
§ 111. Local effects.-The effects of strong alkali applied to the
epidermis are similar to, but not identical with, those produced by
strong acids. S. Samuel * has studied this experimentally on the ear
of the rabbit ; a drop of a strong Solution of caustic alkali, placed on the
ear of a white rabbit, caused stasis in the arteries and veins, with first a
greenish, then a black colour of the blood; the epidermis was bleached,
the hair loosened, and there quickly followed a greenish coloration on
the back of the ear, opposite to the place of application. Around the
burned spot appeared a circle of anastomosing vessels, a blister rose, and
a slough separated in a few days. &
The whole thickness of the ear was coloured yellowish-green, and
later the spot became of a rusty brown.
* Virchow's Archiv f. path. Amat., Bd li., 1870.
§ 1 I2, I I 3.] CAUSTIC POTASH AND SODA. I 25
§ 112. Symptoms.-The symptoms observed when a person has
swallowed a dangerous dose of caustic (fixed) alkali are very similar to
those noticed with ammonia, with the important exception that there is
no respiratory trouble, unless the liquid has come into contact with the
glottis; nor has there been hitherto remarked the rapid death which
has taken place with a few ammonia poisonings, the shortest time
hitherto recorded being three hours, as related by Taylor in a case
in which a boy had swallowed 3 ozs. of a strong solution of carbonate of
potash.
There is instant pain extending from the mouth to the stomach, and
a persistent and unpleasant taste; if the individual is not a determined
suicide, and the poison (as is mostly the case) has been taken accidentally,
the liquid should be immediately ejected as much as possible, and water
or other liquid at hand drunk freely. Shock may at once occur, and the
patient die from collapse; but this, even with frightful destruction of
tissue, appears to be rare. Womiting supervenes; what is ejected is
strongly alkaline, and streaked with blood, and has a soapy, frothy
appearance. There may be diarrhoea, great tenderness of the abdomen,
and quick pulse and fever.
With caustic potash, there may be also noticed its toxic effects (apart
from local action) on the heart; the pulse in that case is slow and
weak, and loss of consciousness and convulsions are not uncommon.
If the collapse and after-inflammation are recovered from, then, as in the
case of the mineral acids, there is all the horrid sequence of symptoms
pointing to contractions and strictures of the gullet or pylorus, and
the subsequent dyspepsia, difficulty of swallowing, and not unfrequently
actual starvation.
§ 113. Post-mortem Appearances.—In cases of recent poisoning,
spots on the cheeks, lips, clothing, etc., giving evidence of the contact
of the alkali, should be looked for ; but this evidence in the case of
persons who have lived a few days may be wanting. The mucous
membrane of the mouth, throat, gullet, and stomach is generally more
or less white—here and there denuded, and will be found in various
stages of inflammation and erosion, according to the amount taken, and
the concentration of the alkali. Where there is erosion, the base of the
eroded parts is not brown-yellow, but, as a rule, pale red. The gullet
is most affected at its lower part, and it is this part which is mostly
subject to stricture. Thus Böhm * found that in 18 cases of contraction
of the gullet, collected by him, 10 of the 18 showed the contraction at
the lower third.
The changes which the stomach may present if the patient has lived
some time are well illustrated by a preparation in St. George's museum
* Centralblatt für die Med. Wiss., 1874.
I 26 BOISONS : THEIR EFFECTS AND DETECTION. [š II.4.
(43 a. 264, ser, ix.). It is the stomach of a woman aged 44, who had
swallowed a concentrated solution of carbonate of potash. She vomited
immediately after taking it, and lived about two months, during the
latter part of which she had to be nourished by injections. She died
mainly from starvation. The gullet in its lower part is seen to be much
contracted, its lining membrane destroyed, and the muscular coats ex-
posed. The coats of the stomach are thickened, but what chiefly arrests
the attention is a dense cicatrix at the pylorus, with an aperture so
small as only to admit a probe.
The colour of the stomach is generally bright red, but in that of a child,
preserved in Guy's Hospital museum (No. 1798%), the mucous membrane
is obliterated, the rugae destroyed, and a dark brown stain is a noticeable
feature. The stomach is not, however, necessarily affected. In a pre-
paration in the same museum (No. 1798%) the mucous membrane of the
stomach of a child who swallowed soap-lees is seen to be almost healthy,
but the gullet is much discoloured. The action on the blood is to
change it into a gelatinous mass; the blood corpuscles are destroyed,
and the whole colour becomes of a dirty blackish-red; the spectroscopic
appearances are identical with those already described (see p. 60).
The question as to the effects of chronic poisoning by the alkalies
or their carbonates may arise. Little or nothing is, however, known
of the action of considerable quantities of alkalies taken daily. In
a case related by Dr. Tunstall,” a man for eighteen years had taken
daily 2 ozs. of bicarbonate of soda for the purpose of relieving
indigestion. He died suddenly, and the stomach was found ex-
tensively diseased ; but since the man, before taking the alkali, had
complained of pain, etc., it is hardly well, from this one case, to draw
any conclusion.
It is important to observe that the contents of the stomach may be
acid, although the death has been produced by caustic alkali. A child
aged 4 drank from a cup some 14 per cent. Soda lye. He vomited
frequently, and died in fifteen hours. The stomach contained 80 c.c. of
Sour-smelling turbid fluid, the reaction of which was acid. There were
haemorrhagic patches in the stomach, and signs of catarrhal inflamma-
tion; there was also a similarly inflamed condition of the duodenum.t
§ 114. Chemical Analysis.-The tests for potassium or sodium are
too well known to need more than enumeration. The intense yellow
flame produced when a sodium salt is submitted to a Bunsen flame, and
the bright sodium-line at D when viewed by the spectroscope, is a delicate
test ; while potassium gives a dull red band in the red, and a faint but
very distinct line in the violet. Potassium salts are precipitated by tar-
* Med. Times, Nov. 30, 1850, p. 564.
† Lesser, Atlas d. gericht. Med., Tafel ii.
§ 115, 116.] sodium, POTASSIUM, AND AMMONIUM SALTs. 127
taric acid, while sodium salts do not yield this precipitate ; potassium
salts also give a precipitate with platinic chloride insoluble in strong
alcohol, while the compound salt with sodium is rapidly dissolved by
alcohol or water. This fact is utilised in the separation and estimation
of the two alkalies.
§ 115. Estimation of the Fixed Alkalies.—To detect a fixed
alkali in the contents of the stomach, a convenient process is to proceed
by dialysis, and after twenty-four hours, to concentrate the outer liquid
by boiling, and then, if it is not too much coloured, to titrate directly
with a decinormal sulphuric acid. After exact neutralisation, the liquid
is evaporated to dryness, carbonised, the alkaline salts lixiviated out with
water, the sulphuric acid exactly precipitated by baric chloride, and them,
after separation of the sulphate, the liquid treated with milk of lime.
The filtrate is treated with a current of CO2 gas, boiled, and any pre:
cipitate filtered off; the final filtrate will contain only alkalies. The
liquid may now be evaporated to dryness with either hydrochloric or
sulphuric acids, and the total alkalies weighed as sulphates or chlorides.
Should it be desirable to know exactly the proportion of potassium to
sodium, it is best to convert the alkalies into chlorides—dry gently,
ignite, and weigh; then dissolve in the least possible quantity of water,
and precipitate by platinic chloride, which should be added so as to be a
little in excess, but not much. The liquid thus treated is evaporated
nearly to dryness, and then extracted with alcohol of 80 per cent., which
dissolves out any of the double chloride of platinum and sodium. Finally,
the precipitate is collected on a tared filter and weighed, after drying at
100°. In this way the analyst both distinguishes between the salts of
sodium and potassium, and estimates the relative quantities of each. It
is hardly necessary to observe that, if the double chloride is wholly
soluble in water or alcohol, sodium alone is present. This, however, will
never occur in operating on organic tissues and fluids, for both alkalies
are invariably present. A correction must be made when complex organic
fluids are in this way treated for alkalies which may be maturally in the
fluid. Here the analyst will be guided by his preliminary titration,
which gives the total free alkalinity. In cases where the alkali has been
neutralised by acids, of course no free alkali will be found, but the corre
sponding salt.
VII.-Neutral Sodium, Potassium, and Ammonium Salts.
§ 116. The neutral salts of the alkalies are poisonous, if administered in sufficient
doses, and the poisonous effect of the sulphate, chloride, bromide, iodide, tartrate,
and citrate appears to depend on the specific action of the alkali metal, rather than
on the acid, or halogen in combination. According to the researches of Dr. Ringer
I 28 POISONS: THEIR EFFECTS AND DETECTION. [S 117–122.
and Dr. Harrington Saintsbury,” with regard to the relative toxicity of the three, as
shown by their effect on the heart of a frog—first, the potassium salts were found to
exert the most poisonous action, next come the ammonium, and, lastly, the sodium
salts. The highest estimate would be that sodium salts are only one-tenth as
poisonous as those of ammonium or potassium ; the lowest, that the sodium salts
are one-fifth : although the experiments mainly throw light upon the action of the
alkalies on one organ only, yet the indications obtained probably hold good for the
organism as a whole, and are pretty well borne out by clinical experience.
There appear to be four cases on record of poisoning by the above neutral salts;
none of them belong to recent times, but lie between the years 1837–1856. Hence,
the main knowledge which we possess of the poisonous action of the potassium salts
is derived from experiments on animals.
§ 117. Sodium Salts.-Common salt in such enormous quantity as half a pound
to a pound has destroyed human life, but these cases are so exceptional that the
poisonous action of sodium salts is of scientific rather than practical interest.
§ 118. Potassium Salts.-Leaving for future consideration the mitrate and the
chlorate of potassium, potassic sulphate and tartrate are substances which have
destroyed human life.
Potassic Sulphate (K2SO4) is in the form of colourless rhombic crystals, of bitter
saline taste. It is soluble in ten parts of water.
Hydropotassic Tartrate (KHCH,06), when pure, is in the form of rhombic
crystals, tasting feebly acid. It is soluble in 210 parts of water at 17°.
§ 119. Action on the Frog's Heart.—Both excitability and contractility are
affected to a powerful degree. There is a remarkable slowing of the pulsations,
irregularity, and, lastly, cessation of pulsation altogether.
§ 120. Action on Warm-blooded Animals. -If a sufficient quantity of a
solution of a potassic Salt is injected into the blood-vessels of an animal, there is
almost immediate death from arrest of the heart’s action. Smaller doses, sub-
cutaneously applied, produce slowing of the pulse, dyspnoea, and convulsions, ending
in death. Small doses produce a transitory diminution of the force of arterial
pressure, which quickly passes, and the blood-pressure rises. There is at first, for
a few seconds, increase in the number of pulsations, but later a remarkable slowing
of the pulse. The rise in the blood-pressure occurs even after section of the spinal
cord. Somewhat larger doses cause rapid lowering of the blood-pressure, and apparent
cessation of the heart's action ; but if the thorax be then opened, the heart is seen
to be contracting regularly, making some 120–160 rhythmic movements in the
minute. If the respiration be now artificially maintained, and suitable pressure
made on the walls of the chest, so as to empty the heart of blood, the blood-pressure
quickly rises, and matural respiration may follow. An animal which lay thirty-six
minutes apparently dead was in this way brought to life again (Böhm). The action
of the salts of potassium on the blood is the same as that of sodium salts. The blood
is coloured a brighter red, and the form of the corpuscles changed; they become
shrivelled through loss of water. Voluntary muscle loses quickly its contractility
when a solution of potash is injected into its vessels. Nerves also, when treated
with a 1 per cent. solution of potassic chloride, become inexcitable.
§ 121. Elimination.—The potassium salts appear to leave the body through the
kidneys, but are excreted much more slowly than the corresponding sodium salts.
Thus, after injection of 4 grms. of potassic chloride—in the first sixteen hours
‘748 grm. of KCl was excreted in the urine, and in the following twenty-four hours
2’677 grims.
§ 122. Nitrate of Potash (KNO3).-Pure potassic nitrate crystallises in large
anhydrous hexagonal prisms with dihedral summits; it does not absorb water, and
* Lancet, June 24, 1882,
§ 123–125.] SODIUM, POTASSIUM, AND AMMONIUM SALTs. I 29
does not deliquesce. Its fusing point is about 340°; when melted it forms a trans-
parent liquid, and loses a little of its oxygen, but this is for the most part retained
by the liquid given off when the salt solidifies. At a red-heat it evolves oxygen,
and is reduced first to nitrite ; if the heat is continued, potassic oxide remains.
The specific gravity of the fused salt is 2°06. It is not very soluble in cold water,
100 parts dissolving only 26 at 15'6°; but boiling water dissolves it freely, 100 parts
dissolving 240 of the salt.
A solution of nitrate of potash, when treated with a zinc couple (see “Foods,”
p. 525), is decomposed, the nitrate being first reduced to nitrite, as shown by its
striking a red colour with metaphenylene-diamine, and then the nitrite farther
decomposing, and ammonia appearing in the liquid. If the solution is alkalised,
and treated with aluminium foil, hydrogen is evolved, and the same effect produced.
As with all nitrates, potassic nitrate, on being heated in a test tube with a little
water, some copper filings, and sulphuric acid, evolves red fumes of nitric peroxide.
§ 123. Statistics.-Potassic nitrate, under the popular name of “mitre,” is a
very common domestic remedy, and is also largely used as a medicine for cattle.
There appear to be at least twenty cases of potassic nitrate poisoning on record: of
these, eight were caused by the salts having been accidentally mistaken for magnesic
sulphate, sodic sulphate, or other purgative salt ; two cases were due to a similar
mistake for common salt. In one instance, the nitrate was used in strong solution
as an enema, but most of the cases were due to the taking of too large an internal
dose.
§ 124. Uses in the Arts, etc.—Both sodic and potassic nitrates are called
“mitre’ by the public indiscriminately. Sodic nitrate is imported in large quantities
from the raimless districts of Peru as a manure. Potassic nitrate is much used in
the manufacture of gunpowder, in the preservation of animal substances, in the
manufacture of gun-cotton, of sulphuric and nitric acids, etc. The maximum
medicinal dose of potassium nitrate is usually stated to be 30 grains (19 grm.).
§ 125. Action of Nitrates of Sodium and Potassium.—Both of these salts are
poisonous. Potassic nitrate has been taken with fatal result by man; the poisonous
nature of sodic nitrate is established by experiments on animals. The action of the
nitrates of the alkalies is separated from that of the other neutral salts of potassium,
etc., because in this case the toxic action of the combined nitric acid plays no insig-
nificant part. Large doses, 3–5 grms. (46'3–77 2 grains), of potassic nitrate cause
considerable uneasiness in the stomach and bowels; the digestion is disturbed ;
there may be vomiting and diarrhoea, and there is generally present a desire to
urinate frequently. Still larger doses, 15–30 grms. (231'5–463 grains), rapidly
produce all the symptoms of acute gastro-enteritis—great pain, frequent vomiting
(the ejected matters being often bloody), with irregularity and slowing of the pulse ;
weakness, cold sweats, painful cramps in single muscles (especially in the calves of
the legs); and, later, convulsions, aphonia, quick collapse, and death.
In the case of a pregnant woman, a handful of “nitre” taken in mistake for
Glauber's salts produced abortion after half an hour. The woman recovered. Sodic
nitrate subcutaneously applied to frogs kills them, in doses of -026 grim. (4 grain),
in about two hours ; there are fibrillar twitchings of single groups of muscles and
narcosis. The heart dies last, but after ceasing to beat may, by a stimulus, be made
again to contract. Rabbits, poisoned similarly by sodic nitrate, exhibit also narcotic
symptoms; they lose consciousness, lie upon their side, and respond only to the
sharpest stimuli. The breathing, as well as the heart, is “slowed,” and death
follows after a few spasmodic inspirations.
Sodic nitrite was found by Barth to be a more powerful poison, less than 6
mgrms. ("I grain) being sufficient to kill a rabbit of 455.5 grms. (7028 grains) weight,
when subcutaneously injected. The symptoms, were very similar to those produced
by the nitrate.
9
I 3O POISONS: THEIR EFFECTS AND DETECTION. [S 126–130.
§ 126. The post-mortem appearances from potassic nitrate are as follows:–An
inflamed condition of the stomach, with the mucous membrane dark in colour, and
readily tearing ; the contents of the stomach are often mixed with blood. In a case
related by Orfila, there was even a small perforation by a large dose of potassic
nitrate, and a remarkable preservation of the body was noted.
It is believed that the action of the nitrates is to be partly explained by a reduc-
tion to nitrites, circulating in the blood as such. To detect nitrites in the blood, the
best method is to place the blood in a dialyser, the outer liquid being alcohol. The
alcoholic solution may be evaporated to dryness, extracted with water, and then
tested by metaphenylene-diamine. -
§ 127. Potassic Chlorate (KClO3).--Potassic chlorate is in the form of colour-
less, tabular crystals with four or six sides. About 6 parts of the salt are dissolved
by 100 of water at 15°, the solubility increasing with the temperature, so that at 100°
nearly 60 parts dissolve; if strong sulphuric acid be dropped on the crystals, peroxide
of chlorine is evolved ; when rubbed with sulphur in a mortar, potassic chlorate
detonates. When the salt is heated strongly, it first melts, and then decomposes,
yielding oxygen gas, and is transformed into the perchlorate. If the heat is con-
tinued, this also is decomposed, and the final result is potassic chloride.
§ 128. Uses.—Potassic chlorate is largely used as an oxidiser in calico printing,
and in dyeing, especially in the preparation of aniline black. A considerable
quantity is consumed in the manufacture of lucifer matches and fireworks; it is also
a convenient source of oxygen. Detonators for exploding dynamite are mixtures of
fulminate of mercury and potassic chlorate. It is employed as a medicine both as an
application to inflamed mucous membranes, and for internal administration ; about
2000 tons of the salt for these various purposes are manufactured yearly in the United
Kingdom.
§ 129. Poisonous properties.—The facility with which potassic chlorate parts
with its oxygen by the aid of heat, led to its very extensive employment in medicines.
No drug, indeed, has been given more recklessly, or on a less scientific basis. Wher-
ever there were sloughing wounds, low fevers, and malignant sore throats, especially
those of a diphtheritic character, the practitioner administered potassic chlorate in
colossal doses. If the patient died, it was ascribed to the malignity of the disease—if
he recovered, to the oxygen of the salt; and it is possible, from the light which of
recent years has been thrown on the action of potassic chlorate, that its too reckless
use has led to many unrecorded accidents.
§ 130. Experiments on Animals.-F. Marchand” has studied the effects of
potassic chlorate on animals, and on blood. If either potassic chlorate or sodic chlorate
is mixed with fresh blood, it shows after a little while peculiar changes; the clear
red colour at first produced passes, within a few hours, into a dark red-brown, which
gradually becomes pure brown. This change is produced by a 1 per cent. Solution
in from fifteen to sixteen hours; and a 4 per cent. Solution at 15° destroys every trace
of oxyhaemoglobin within four hours. Soon the blood takes a syrupy consistence
and, with a 2–4 per cent, solution of the salt, passes into a jelly-like mass. The
jelly has much permanence, and resists putrefactive changes for a long time.
Various bloods show various resistances; similarly the effect of potassic chlorate
is unequal in different animals; it takes large doses to kill rabbits; cats are less
resisting. Rabbits are killed by subcutaneous doses of from 5-6 grms. ; cats from
1–1% grim. Dogs require larger doses than cats, but less than rabbits. The resistance
of human beings is about the same as that of dogs.
Marchand fed a dog of 17 kilos. in weight with 5 grms, of potassic chlorate for a
week. As there were no apparent symptoms, the dose was doubled for two days;
and as there was still no visible effect, lastly, 50 grms. of sodic chlorate were given in
* Virchow's Archiv. f. path. Amat., Bd. lxxvii. Hft. 3, S. 455, 1879.
§ 131, 132.] SODIUM, POTASSIUM, AND AMMONIUM SALTs. I3 I
5 doses. In the following night the dog died. The blood was found after death to
be of a sepia-brown colour, and remained unaltered when exposed to the air. The
organs were generally of an unnatural brown colour; the spleen was enormously
enlarged; the kidneys were swollen, and of a dark chocolate-brown—on section,
almost black-brown, the colour being nearly equal, both in the substance and in the
capsule. A microscopical examination of the kidney showed the canaliculi to be
filled with brownish cylinders consisting of altered blood. A spectroscopic examina-
tion of the blood showed weak haemoglobin bands, and a narrow band in the red.
With farther dilution, the haemoglobin bands vanished, but the band in the red
remained. The diluted blood, when exposed to the light, still remained of a
coffee-brown colour; and on shaking, a white-brown froth was produced on the
surface.
A second experiment, in which a hound of from 7–8 kilos. in weight was given
three 5 grn. doses of potassic chlorate in sixteen hours, and killed by bleeding seven
to eight hours after the last dose, showed very similar appearances. The kidneys
were intensely congested, and the peculiar brown colour was noticeable.
§ 131. Effects on Man.—In literature there are more than forty cases recorded,
in which poisonous symptoms were directly ascribed to the action of chlorate of
potassium ; twenty-nine of these terminated fatally. At Morecambe a little boy took
about 60 grains of potassic chlorate and died in six hours (Lancet, Aug. 22, 1903).
A quadruple instance of poisoning, recorded by Brouardel and L’Hote,” illustrates
many of the points relative to the time at which the symptoms may be expected to
commence, and the general aspect of potassic chlorate poisoning. The supérieure
of a religious institution was in the habit of giving, for charitable purposes, a potion
containing 15 grims. (3-8 drms.) of potassic chlorate, dissolved in 360 c.c. (about
12% ozs.) of a vegetable infusion.
This potion was administered to four children—viz., David, aged 24; Cousin,
aged 3% ; Salmont, 2% ; and Guérin, 2%. David took the whole in two and a half
hours; the symptoms commenced after the potion was finished, and the child died
five and a half hours after taking the first dose; there were vomiting and diarrhoea.
Cousin took the medicine in seven hours ; the symptoms also commenced after the
last spoonful, and the death took place eight and a half hours from the first spoonful;
the symptoms were mainly those of great depression ; the lips were blue, the pulse
feeble, there was no vomiting, no diarrhoea. Salmont took the medicine in nine
hours, and died in twelve ; there was some diarrhoea, the stools were of a green
colour. Guérin took the whole in two hours; the symptoms commenced in four
hours; the lips were very pale, the gums blue ; death took place in four days.
There was an autopsy in the case of David only. The stomach showed a large
ecchymosis on its mucous membrane, as if it had been burnt by an acid ; the spleen
was gorged with blood, and its tissue friable ; the kidneys do not seem to have been
thoroughly examined, but are said to have been tumefied. Potassic chlorate was
discovered by dialysis. In the cases of the children just detailed, the symptoms
appear to be a mixture of the depressing action of the potassium, and irritant action
of the chlorate.
§ 132. In adults, the main symptoms are those of nephritis, and the fatal dose
for an adult is somewhere about an ounce (28-3 grims.), but half this quantity would
probably be dangerous, especially if given to a person who had congestion or disease
of the kidneys.
Dr. Jacobi + gives the following cases.
Dr. Fountain, in 1858, experimenting on himself, took 29.2 grims. (87 drums.) of
potassic chlorate ; he died on the seventh day from nephritis. A young lady
* Annales d’Hygiène publique, 1881, p. 232.
i Amer. Med. Times, 1860.
I 32 POISONS: THEIR EFFECTS AND DETECTION. [$ 133–135.
swallowed 30 grms. (8°5 drms.), when using it as a gargle; she died in a few days
from nephritis. A man, 30 years of age, died in four days after having taken 48
grms. (12-3 drms.) of sodic chlorate in six hours. The shortest time in which
the salt appears to have been fatal is a case related by Dr. Manouvriez, in which a
woman took 45 grims., and died in five hours. The smallest dose which has proved
fatal is one in which an infant 3 years old was killed by 3 grms. (46.3 grains).
Jacobi considers that the maximum dose to be given in divided doses during
the twenty-four hours, to infants under 3, should be from 1–1.5 grim. (15'4–23°l
grains); to children from 3 years old, up to 2 grims. (30-8 grains); and adults from
6–8 grims. (92.6–123°4 grains).
§ 133. Elimination.—Potassic chlorate is quickly absorbed by mucous mem-
branes, and by the inflamed skin, and rapidly separated from the body by the action
of the kidneys. Wöhler, as early as 1824, recognised that it in great part passed
out of the body unchanged ; and, lately, Isambert, in conjunction with Hirne,”
making quantitative estimations, recovered from the urine no less than 95 per cent.
of the ingested salts. Otto Hehner has also made several auto-experiments, and
taking 2% drms., found that it could be detected in the urine an hour and a half
afterwards. At that time 1723 per cent. of the salt had been excreted, and, by the
end of eleven hours, 93.8 per cent. was recovered. It is them difficult to believe that
the salt gives any oxygen to tºo tissues, for though it is true that in all the investi-
gations a small percentage remains to be accounted for, and also that Binz,t making
experiments by mixing solutions of potassic chlorate with moist organic substances,
such as pus, yeast, fibrin, etc., has declared that, at a blood heat, the chlorate is
rapidly reduced, and is no longer recognisable as chlorate—yet it may be affirmed
that potassic chlorate is recovered from the urine as completely as anything which is
ever excreted by the body, and that deductions drawn from the changes undergone
by the salt in solutions of fibrin, etc., have only an indirect bearing on the question.
§ 134. The essential action of potassic chlorate seems to be that it causes a
peculiar change in the blood, acting on the colouring matter and corpuscles; the
latter lose their property as oxygen carriers ; the haemoglobin is in part destroyed ;
the corpuscles dissolved. The decomposed and altered blood corpuscles are crowded
into the kidneys, spleen, etc.; they block up the uriniferous camaliculi, and thus the
organs present the curious colouring seen after death, and the kidneys become
inflamed.
Detection and Estimation of Potassic Chlorate.
§ 135. Organic ſluids are best submitted to dialysis ; the dialysed fluid should
them be concentrated and qualitative tests applied. One of the best tests for the
presence of a chlorate is, without doubt, that recommended by Fresenius. The fluid
to be tested is acidulated with a few drops of sulphuric acid ; sulphate of indigo
added sufficient to colour the solution blue, and finally a few drops of sulphurous
acid. In presence of potassic or sodic chlorate, the blue colour immediately vanishes.
This method is capable of detecting 1 part in 128,000 ; provided the solution is not
originally coloured, and but little organic matter is present.
The urine can be examined direct, but if it contain albumen, the blue colour may
disappear and yet chlorate be present ; if too much sulphurous acid be also added,
the test may give erroneous results. These are but trivial objections, however, for
if the analyst obtains a response to the test, he will naturally confirm or disprove it
by the following process:–
* Gaz, Méd. de Paris, 1875, Nro, 17, 35, 41, 43.
+ Berlin klin. Wochemschr., xi. 10, S. 119, 1874.
§ 136.] DETECTION OF ALKALI SALTS. I33
The liquid under examination, organic or otherwise, is divided into two equal
parts. In the one, all the chlorine present is precipitated as chloride by silver
nitrate in the usual way, and the chloride of silver collected and weighed. In the
other, the liquid is evaporated to dryness and well charred by a dull red heat, the
ash dissolved in weak nitric acid, and the chlorides estimated as in the first case. If
chlorates were present, there will be a difference between the two estimations, pro-
portionate to the amount of chlorates which have been converted into chlorides by
the carbonisation, and the first silver chloride subtracted from the second will give
an argentic chloride which is to be referred to chlorate. In this way also the amount
present may be quantitatively estimated, 100 parts of silver chloride equalling 85'4
of potassic chlorate.
Toxicological Detection of Alkali Salts.
(See also ante, p. 127.)
§ 136. Sodium, in combination, especially with tº 'orine, and also with sulphuric,
carbonic, and phosphoric acids, is found in the plasma of the blood, in the urinary
secretion, in the pancreatic juice, in human bile, and in serous transudations, etc.
Potassium, in combination, is especially found in the red blood corpuscles, in the
muscles, in the nervous tissues, and in milk. Ammonia, in combination with acids,
is naturally found in the stomach, in the contents of the intestine ; it is also a
natural constituent of the blood in small traces, and in a corpse is copiously evolved
from putrefactive changes.
It hence follows, that mere qualitative tests for these elements in the tissues or
fluids of the body are of not the slightest use, for they are always present during the
life of the healthiest individual, and can be found after death in persons dying from
any malady whatever. To establish the fact of a person having taken an unusual
dose of any of the alkali salts, by simply chemical evidence, it must be proved that
the alkalies are present in unusual quantities or in an abnormal state of combination.
In cases of rapid death, caused by sodic or potassic salts, they will be found in
such quantity in the contents of the stomach, or in matters vomited, that there will
probably be no difficulty in coming to a direct conclusion ; but if some time has
elapsed, the analyst may not find a sufficient ground for giving a decided judgment,
the excretion of the alkali salts being very rapid.
In most cases, it will be well to proceed as follows:—The contents of the stomach
are, if necessary, diluted with distilled water, and divided into three parts, one of
which is submitted to dialysis, and then the dialysed liquid evaporated to a small
bulk and examined qualitatively, in order to ascertain whether a large amount of
the alkaline Salts is present, and in what form. In this way, the presence or absence
of nitrate of potassium or sodium may be proved, or the iodide, bromide, sulphate,
and chlorate detected.
To find, in this way, mitrate of potassium, a coarse test is preferable to the finer
tests dependent upon conversion of the nitrate into nitrites or into ammonia, for
these tests are so delicate that nitrates may be detected in traces; whereas, in this
examination, to find traces is of no value. Hence, the old-fashioned test of treating
the concentrated liquid in a test tube with copper filings and then with sulphuric
acid, and looking for the red fumes, is best, and will act very well, even should, as
is commonly the case, some organic matters have passed through the dialyser.
Chlorates are indicated if the liquid is divided into two parts and tested in the
manner recommended in the previous section. If present in any quantity, chlorates
or nitrates may be indicated by the brilliant combustion of the organic matter when
I 34 POISONS : THEIR EFFECTS AND DETECTION. [S 136.
heated to redness, as also by the action of strong sulphuric acid on the solid sub-
stances—in the one case, yellow vapours of peroxide of chlorine being evolved—in the
other, the red fumes already mentioned of nitric peroxide.
With regard to a substance such as the hydro-potassic tartrate, its insolubility in
wafer renders it not easy of detection by dialysis; but its very insolubility will aid
the analyst, for the contents of the stomach may be treated with water, and thus all
soluble salts of the alkalies extracted. On now microscopically examining the
insoluble residue, crystals of bitartrate, if present, will be readily seen. They may
be picked up on a clean platinum wire and heated to redness in a Bunsen flame, and
spectroscopically examined. After heating, the melted mass will have an alkaline
reaction, and give a precipitate with platinic chloride. All other organic salts of
potassium are soluble, and a white crystal giving such reaction must be hydro-
potassic tartrate.
Ammonium Salts.—If the body is fresh, and yet the salts of ammonium present
in large amount, it is safe to conclude that they have an external origin ; but there
might be some considerable difficulty in criminal poisoning by a neutral salt of
ammonium, and search for it in a highly putrid corpse. Probably, in such an excep-
tional case, there would be other evidence. With regard to the quantitative separa-
tion and estimation of the fixed alkalies in the ash of organic substances, the reader
is referred to the processes given in “Foods,” p. 96 et seq., and in the present work,
p. 27.
PART W. — MORE OR LESS WOLATILE POISONOUS SUB-
STANCES CAPABLE OF BEING SEPARATED BY DISTIL-
LATION FROM NEUTRAL OR ACID LIQUIDS.
HYDROCARBONS–CAMPHOR ALCOHOL AMYL NITRITE–
ETHER—CHLOROFORM AND OTHER ANAESTHETICS.–
CHLORAL–CARBON DISULPHIDE CARBOLIC ACID—
NITRO-BENZENE–PRUSSIC ACID—PHOSPHORUS.
I.—Hydrocarbons.
1. PETROLEUM.
§ 137. Petroleum is a general term for a mixture of hydrocarbons of the paraffin
series, which are found naturally in certain parts of the world, and are in com-
merce under liquid and solid forms of various density. Crude petroleum is not im-
ported into England, the original substance having previously undergone more or
less rectification. The lighter and more volatile portions are known under the name
of cymogene, rhigolene, gasolene, and naphtha.
§ 138. Cymogene has a specific gravity of 590, and boils at 0°. It has been
employed in refrigerating machines. It appears to consist chiefly of butane
(C4H10).
§ 139. Rhigolene is now used in medicine in the form of spray to produce local
anaesthesia. It boils at 18°, and has a density of 650.
§ 140. Gasolene has a density of '680–688; it has received technical applica-
tions in the “naphthalising” of air and gas.
§ 141. Benzoline (mineral naphtha, petroleum naphtha, petroleum spirit,
petroleum ether, petrol) is a mixture of the lighter series of hydrocarbons; the
greater part consists of heptane, and there is also a considerable quantity of pentane
(C5H12) present. The specific gravity varies from 69 to '74. It is very inflammable,
and is used in motor cars, sponge lamps, and also as a solvent for gutta-percha,
naphthalene, paraffin, wax, and many other bodies. The ordinary petrol that is
used in cars has a gravity of '680–708 at 15° C. and a boiling-point of 85°C. It is
much employed by the practical chemist.
The similarity of the terms benzoline and benzene has caused benzoline to be often
confused with benzol or benzene, the leading constituent of coal-tar naphtha (C6Hs).
Mr. Allen" gives in the following table a summary of the chief points of distinction,
* Commercial Organic Analysis, vol. ii. p. 31.
I3S
I 36 POISONS: THEIR EFFECTS AND DETECTION. [$ 142, 143.
both between petroleum naphtha, shale naphtha, and coal-tar naphtha. The table
is founded upon the examination of particular samples, and commercial samples may
present a few minor deviations.
TABLE OF THE WARIETIES OF NAPHTHA.
Petroleum Naphtha.
Shale Naphtha.
Coal-tar Naphtha.
Contains at least 75 per
cent. of heptane, C. His,
and other hydrocarbons of
the marsh gas or paraffin
series; the remainder ap-
parently olefins, CnH2n,
with Histºl traces of
benzene and its homo-
logues.
Specific gravity at 15°,
"600.
Distils between 65° and
Dissolves coal-tar pitch
but slightly ; liquid, but
little coloured even after
prolonged contact.
On shaking three mea-
sures of the sample with
one measure of fused crys-
Contains at least 60 to
70 per cent. of heptylene,
C, H14, and other hydro-
carbons of the olefin
series ; the remainder
paraffins. No trace of
benzene or its homologues.
Specific gravity at 15°,
‘718.
Distils between 65° and
100°.
Behaves similarly to
petroleum naphtha with
regard to the solution of
pitch.
When treated with
fused carbolic acid crys-
tals, the liquids mix per-
t
Consists almost wholly
of benzene, C6H6, and
other homologous hydro-
carbons, with a small per-
centage of light hydro-
carbons in some samples.
Specific gravity '876.
Distils between 80° and
120°.
Readily dissolves pitch,
forming a deep brown
solution.
The liquids form a
homogeneous mixture
when treated with fused
tals of absolute carbolic
acid, no solution. Liquids
not miscible.
fectly. carbolic acid crystals.
Combines slowly with
30–40 per cent. of its
weight of bromine.
Combines with upwards
of 90 per cent. of its
weight of bromime.
Combines with 10 per
cent. of its weight of
bromine in the cold.
§ 142. Paraffin Oil (or kerosine mineral oil, photogen, etc.) is the chief product
resulting from the distillation of American petroleum—the usual specific gravity is
about 802—it is a mixture of hydrocarbons of the paraffin series. It should be free
from the more volatile constituents, and hence should not take fire when a flame is
applied near the surface of the cold liquid.
§ 143. Effects of Petroleum.—Since we have here to deal with a commercial
substance of such different degrees of purity, and various samples of which are com-
posed of such various proportions of different hydrocarbons, its action can only be
stated in very general terms. Eulenberg “ has experimented with the lighter pro-
ducts obtained from the distillation of Canadian petroleum. This contained sulphur
products, and was extremely poisonous, the vapour killing a rabbit in a short time,
with previous insensibility and convulsions. The autopsy showed a thin extravasa-
tion of blood on the surface of each of the bulbi, much coagulated blood in the heart,
congested lungs, and a bloody mucus covering the tracheal mucous membrane. An
* Gewerbe-Hygiene.
§ 144, 145.] HYDROCARBONS. I 37
experiment made on a cat with the lighter petroleum (which had no excess of
sulphur) in the state of vapour, showed that it was an anaesthetic, the anaesthesia
being accompanied by convulsions, which towards the end were tetanic and violent.
The evaporation of 1.5 grm, in a close chamber killed the animal in three hours.
The lungs were found congested, but little else was remarkable. Much petroleum
vapour is breathed in certain factories, especially those in which petroleum is
refined.” From this cause there have been rather frequent toxic symptoms among
the workmen. Eulenberg t describes the symptoms as follows:–A person, after
breathing an overdose of the vapour, becomes very pale, the lips are livid, the
respiration slow, the heart's action weak and scarcely to be felt. If he does not
immediately go into the open air away from the poisonous vapour, these symptoms
may pass on to insensibility, convulsions, and death. It often occasions a condition
of the voluntary muscles similar to that induced by drunkenness, and on recovery
the patient is troubled by singing in the ears and noises in the head. The smell
and taste of the poison may remain for a long time.
§ 144. Poisoning by taking light petroleum into the stomach is not common. In
a case recorded by Taylor, a woman, for the purpose of suicide, swallowed a pint
of petroleum. There followed a slight pain in the stomach, and a little febrile dis-
turbance, and a powerful smell of petroleum remained about the body for six days;
but she completely recovered. In August 1870 a sea-captain drank a quantity of
paraffin, that is, lighting petroleum, and died in a few hours in an unconscious state.
A child, 2 years old, was brought to King's College Hospital within ten minutes
after taking a teaspoonful of paraffin. It was semi-comatose and pale, with con-
tracted pupils; there was no vomiting or purging. Emetics of sulphate of zinc were
administered, and the child recovered in twenty-four hours. In another case treated
at the same hospital, a child had swallowed an unknown quantity of paraffin. It
fell into a comatose state, which simulated tubercular meningitis, and lasted for
nearly three weeks. § In a case recorded by Mr. Robert Smith, a child, 4 years of
age, had swallowed an unknown quantity of paraffin. A few minutes afterwards,
the symptoms commenced ; they were those of suffocation, with a constant cough ;
there was no expectoration ; the tongue, gums, and cheeks were blanched and
swollen where the fluid touched them ; recovery followed. A woman, aged 32,
who had taken a quarter of a pint of paraffin, was found unconscious and very cold ;
the stomach-pump was used, and she recovered." Hence it is tolerably certain, from
the above instances, that should a case of petroleum poisoning occur, the expert will
not have to deal with infinitesimal quantities; but while the odour of the oil will
probably be distinctly perceptible, there will be also a sufficient amount obtained
either from matters vomited, or the contents of the stomach, etc., so that no diffi-
culty will be experienced in identifying it.
§ 145. In order to separate petroleum from any liquid, the substances under
examination must be carefully distilled in the manner recommended under “Ether.”
The lighter petroleums will distil by the aid of a water-bath; but the heavier require
a stronger heat ; redistillation of the distillate may be necessary. The odour of the
liquid, its inflammable character, and its other properties, will be sufficient for
identification.
* The vapour most likely to rise at the ordinary temperature, and mix with the
atmosphere, is that of the lighter series, from cymogene to benzoline.
f Op. cit. 3: Poisoms, p. 656.
Š Brit. Med. Jowrm., Sept. 16, 1876, p. 365.
| Brit. Med. Journ., Oct. 14, 1876.
"I Pharm. Journ., Feb. 12, 1875; also for other cases see Brit. Med. Journ.,
Nov. 4, 1876; and Köhler's Physiol. Therap., p. 437.
138 POISONS: THEIR EFFECTS AND DETECTION. [$ 146–149.
2. COAL-TAR-NAPHTHA—BENZENE.
§ 146. Coal-tar-naphtha, in its crude state, is an extremely complex liquid, of a
most disagreeable smell. Much benzene (C6H6) is present with higher homologues of
the benzene series. Toluene (C7Hs), naphthalene (C10Hs), hydrocarbons of the
paraffin series, especially hexane (C6H14), and hydrocarbons of the olefin series, especi-
ally pentylene, hexylene, and heptylene (C5H10,C8H19 and C.H14). Besides these,
there are nitrogenised bases, such as aniline, picoline, and pyridine ; phenols, especi-
ally carbolic acid ; ammonia, ammonium sulphide, carbon disulphide, and probably
other sulphur compounds; acetylene and aceto-nitrile. By distillation and fractional
distillation are produced what are technically known “once rum,” naphtha, 90 per
cent. benzol, 50 and 90 per cent. benzol, * 30 per cent. benzol, solvent naphtha, and
residue known as “last runnings.”
§ 147. Taylor + records a case in which a boy, aged 12, swallowed about 3 ozs. of
naphtha, the kind usually sold for burning in lamps, and died with symptoms of
narcotic poisoning. The child, after taking it, ran about in wild delirium ; he then
sank into a state of collapse, breathing stertorously, and the skin became cold and
clammy. On vomiting being excited, he rejected about two tablespoonfuls of the
naphtha, and recovered somewhat, but again fell into collapse with great muscular
relaxation. The breathing was difficult; there were no convulsions; the eyes were
fixed and glassy, the pupils contracted ; there was frothing at the mouth. In spite
of every effort to save him, he died in less than three hours after taking the poison.
The body, examined three days after death, smelt strongly of naphtha, but the post-
mortem appearances were in no way peculiar, save that the stomach contained a pint
of semi-fluid matter, from which a fluid, having the characteristics of impure benzene,
was separated.
§ 148. The effects of the vapour of benzene have been studied by Eulenberg in
experiments on cats and rabbits, and there are also available observations on men :
who have been accidentally exposed to its influence. From these sources of informa-
tion, it is evident that the vapour of benzene has a distinctly narcotic effect, while
influencing also in a marked degree the spinal cord. There are, as symptoms, noises
in the head, convulsive trembling and twitchings of the muscles, with difficulty of
breathing.
DETECTION AND SEPARATION OF BENZENE.
§ 149. Benzene is separated from liquids by distillation, and may be recognised
by its odour, and by the properties described at p. 136. The best process of identifica-
tion, perhaps, is to purify and convert it into nitro-benzene, and then into aniline, in
the following manner:—
1. Purification.—The liquid is agitated with a solution of caustic soda ; this
dissolves out of the benzene any bodies of an acid character, such as phenol, etc. The
purified liquid should again be distilled, collecting that portion of the distillate which
passes over between 80° and 120° ; directly the thermometer attains nearly the 120°,
the distillation should be stopped. The distillate, which contains all the benzene
present, is next shaken with concentrated sulphuric acid in the cold ; this will
dissolve out all the hydrocarbons of the ethylene and acetylene series. On removing
the layer of benzene from the acid, it must be again shaken up with dilute soda, so
as to remove any trace of acid. The benzene is, by this rather complicated series of
* Or 50/90 benzol, this indicates that 50 per cent. distils over below 100°; and
40, making in all 90, below 120°.
+ Op. cit., p. 657.
† Dr. Stone, Med. Gaz., vol. xii. p. 1077, 1848.
§ 15O, I 5 I.] HYDROCARBONS. I 39
operations, obtained in a very fair state of purity, and may be converted into nitro-
benzene, as follows:–
2. Conversion into Nitro-Benzene.—The oily liquid is placed in a flask, and
treated with four times its volume of fuming nitric acid. The flask must be furnished
with an upright condenser; a vigorous action mostly takes place without the
application of heat, but if this does not occur, the flask may be warmed for a few
minutes.
After the conversion is over, the liquid, while still warm, must be transferred
into a burette furnished with a glass tap, or to a separating funnel, and all, except
the top layer, run into cold water ; if benzene was originally present, either oily
drops of nitro-benzene will fall, or if the benzene was only in small quantity, a fine
precipitate will gradually settle down to the bottom of the vessel, and a distinct
bitter-almond smell be observed ; but if there be no benzene in the original liquid,
and, consequently, no nitro-benzene formed, no such appearance will be observed.
3. Conversion into Aniline.—The nitro-benzene may itself be identified by
collecting it on a wet filter, dissolving it off the filter by alcohol, acidifying the
alcoholic solution by hydrochloric acid, and then boiling it for some time with
metallic zinc. In this way aniline is formed by reduction. On neutralising and
diluting the liquid, and cautiously adding a little clear solution of bleaching-powder,
a blue or purple colour passing to brown is in a little time produced.
3. TERPENES–ESSENTIAL OILS–OIL OF TURPENTINE.
§ 150. The terpenes are hydrocarbons of the general formula CnH2n-4. The
natural terpenes are divided into three classes:—
1. The true terpenes, formula (C10H16)—a large number of essential oils, such
as those of turpentine, orange peel, nutmeg, caraway, anise, thyme, etc., are mainly
composed of terpenes.
2. The cedrenes, formula (C15H23)—the essential oil of cloves, rosewood, cubebs,
calamus, cascarilla, and patchouli belong to this class.
3. The colophene hydrocarbons, formula (C20H82), represented by colophony.
Of all these, oil of turpentine alone has any toxicological significance ; it is, how-
ever, true that all the essential oils, if taken in considerable doses, are poisonous,
and cause, for the most part, vascular excitement and complex nervous phenomena,
but their action has not been very completely studied. They may all be separated
by distillation, but a more convenient process for recovering an essential oil from a
liquid is to shake it up with petroleum ether, separating the petroleum and evapo-
rating spontaneously ; by this means the oil is left in a fair state of purity.
4. OIL OF TURPENTINE–Sl?IRIT OF TURPENTINE–"TURPs.”
§ 151. Various species of pine yield a crude turpentine, holding in solution more
or less resin. The turpentine may be obtained from this exudation by distillation,
and when the first portion of the distillate is treated with alkali, and then redistilled,
the final product is known under the name of “rectified oil of turpentine,” and is
sometimes called “campliene.” It mainly consists of terebentheme. Terebentheme
obtained from French turpentine differs in some respects from that obtained from
English or American turpentime. They are both mobile, colourless liquids, having
the well-known odour of turpentine and highly refractive; but the French tere-
benthene turns a ray of polarised light to the left – 40'3" for the sodium ray, and
the English to the right +21:5°; the latter terebentheme is known scientifically as
austra-terebentheme. This action on polarised light is retained in the various
compounds and polymers of the two turpentine oils.
I4O POISONS: THEIR EFFECTS AND DETECTION. [$ 152.
The specific gravity of turpentine oil is ‘864; its boiling-point, when consisting of
pure terebentheme, 156°, but impurities may raise it up to 160°; it is combustible
and burns with a smoky flame. Oil of turpentine is very soluble in ether, petroleum
ether, carbon disulphide, chloroform, benzene, fixed and essential oils, and by the
use of these solvents it is conveniently separated from the contents of the stomach.
It is insoluble in water, glycerin, and dilute alkaline and acid solutions, and very
soluble in absolute alcohol, from which it may be precipitated by the addition of
Water.
It is polymerised by the action of strong sulphuric acid, the polymer, of course,
boiling at a higher temperature than the original oil. With water it forms a crys-
talline hydrate (C10H26O2, H2O). On passing nitrosyl chloride gas into the oil, either
pure or diluted with chloroform or alcohol, the mixture being cooled by ice, a white
crystalline body is deposited, of the formula C10H16 (NOCl). By treating this com-
pound with alcoholic potash, the substitution product (C10H16NO) is obtained. By
treating turpentine with an equal bulk of warm water, and shaking it in a large
bottle with air, camphoric acid and peroxide of hydrogen are formed. When
turpentine oil is left in contact with concentrated hydrochloric acid, there is formed
terebentheme dihydrochloride (CoH162HCl), which forms rhombic plates, insoluble
in water, and decomposable by boiling alcoholic potash, with formation of terpinol,
(CoPH17)30. The dihydrochloride gives a colour-reaction with ferric chloride. This
is an excellent test—not, it is true, confined to oil of turpentime, but common to the
dihydrochlorides of all the terpenes. A few drops of the oil are stirred in a porcelain
capsule with a drop of hydrochloric acid, and one of ferric chloride solution ; on
gently heating, there is produced first a rose colour, then a violet-red, and lastly
a blue.
§ 152. Effects of the Administration of Turpentine.—L. W. Liersch * exposed
animals to the vapour of turpentine, and found that a cat and a rabbit died within
half an hour. There was observed uneasiness, reeling, want of power in the limbs
(more especially in the hinder extremities), convulsions partial, or general, difficulty
of respiration ; and the heart’s action was quickened. Death took place, in part,
from asphyxia, and in part was attributable to a direct action on the nervous centres.
The autopsy showed congestion of the lungs, ecchymoses of the kidney, and much
blood in the liver and spleen. Small doses of turpentine-vapour cause (according to
Sir B. W. Richardson) f giddiness, deficient appetite, and anaemia. From half an
ounce to an ounce is frequently prescribed in the country as a remedy for tapeworm ;
in smaller quantities it is found to be a useful medicine in a great variety of ailments.
The larger doses produce a kind of intoxication with giddiness, followed often by
purging and strangury; not unfrequently blood and albumen (or both) is found in the
urine. When in medical practice the senior author has given the oil, and seen it given
by others, in large doses for tapeworm to adults, in perhaps 40 cases, but in no one
instance were the symptoms severe ; the slight intoxication subsided quickly, and in a
few hours the patients recovered completely. Nevertheless it has been known to destroy
the lives of children, and cause most serious symptoms in adults. Two fatal cases
are mentioned by Taylor ; one was that of a child who died fifteen hours after taking
half an ounce of the oil ; in another an infant, 5 months old, died rapidly from a
teaspoonful. The symptoms in these fatai cases were profound coma and slight
convulsions; the pupils were contracted, and there was slow and irregular breathing.
Turpentine is eliminated in a changed form by the kidneys, and imparts an odour of
violet to the urine ; but the nature of the odoriferous principle has not yet been
investigated.
* Clarus in Schmidt’s Jahrbücher, Bd. cxvii., i., 1863; and Vierteljahrsschr, für
ger. Med., xxii., Oct. 1862.
| Brit, and For, Med.-Chir. Review, April 1863.
§ I53–155.] CAMPHOR. I4 I
II.—Camphor.
§ 153. A great many essential oils deposit, after exposure to air, camphors pro.
duced by oxidation of their terpenes. Ordinary camphor is imported in the rough
state from China and Japan, and is prepared by distilling with water the wood of
Cinnamomum camphora; it is resublimed in England. The formula of camphor is
C10H16O ; it has a density of '986 to '996; melts at 175°, and boils at 205°. It is
readily sublimed, especially in a vacuum, and is indeed so volatile at all tempera.
tures, that a lump of camphor exposed to the air wastes away. It is slightly
soluble in water (about 1 part in 1000), but this is enough to impart a distinct
taste to the water ; it is insoluble in chloroform, ether, acetone, acetic acid, carbon
disulphide, and oils. It has a fragrant odour and a burning taste. A 10 per cent.
solution in alcohol turns a ray of polarised light to the right +42°8°. By distillation
with zinc chloride, cymene and other products are produced. By prolonged treat.
ment with nitric acid, camphor is oxidised to camphoric acid (CoH16O.). Camphor
unites with bromine to form a crystalline, unstable dibromide, which splits up on
distillation into hydrobromic acid and monobrom-camphor (CoHigErO). The latter
is used in medicine ; it crystallises in prisms fusible at 76°, and is readily soluble in
alcohol.
§ 154. Pharmaceutical Preparations.—The preparations officinal in the British
Pharmacopoeia are camphor water—water Saturated with camphor, containing about
1 part per 1000.
Camphor Liniment.—A solution of camphor in olive oil, strength 25 per cent.
Compound Camphor Liniment.—Composed of camphor, oil of lavender, strong
solution of ammonia and alcohol ; strength in camphor about 11 per cent.
Spirit of Camphor.—A solution of camphor in spirit; strength, 10 per cent.
Camphor is also a constituent of the compound tincture of camphor; but in this
case it may be considered only a flavouring agent. There is a homoeopathic solution
of camphor in spirit (Rubini’s Essence of Camphor). The solution is made by satu-
rating alcohol with camphor; it is, therefore, very strong—about half the bulk con-
sisting of camphor. Camphor is used in veterinary medicine, both externally and
internally. i
§ 155. Symptoms.-Camphor acts emergetically on the brain and nervous system,
especially if it is given in strong alcoholic solution, and thus placed under conditions
favouring absorption. Some years ago, Dr. G. Johnson” published a series of cases
arising from the injudicious use of “homoeopathic solution of camphor,” from 7 to
40 drops of Rubini's homoeopathic camphor taken for colds, sore throat, etc., having
produced coma, foaming at the mouth, convulsions, and partial paralysis. All the
patients recovered, but their condition was for a little time alarming.
The cases of fatal poisoning by camphor are very rare. A woman, aged 46, preg-
nant four months, took 12 grims. (about 184 grains) in a glass of brandy for the
purpose of procuring abortion. In a very short time the symptoms commenced ;
she had intolerable headache, the face was flushed, and there was a sensation of
burning in the stomach. In eight hours after taking the dose she had strangury
and vomiting, and the pain in the epigastrium was intense. These symptoms con-
tinued with more or less severity until the third day, when she became much worse.
Her face was pale and livid, the eyes hollow, the skin cold and insensible, pulse
weak and thready, breathing laboured. There were violent cramps in the stomach
and retention of urine for twenty-four hours, and then coma. The patient lingered
on yet another three days, aborted, and died. †
* Brit. Med. Journ., Feb. 27, 1878, p. 272; see also ibid., Feb. 1875.
f Journ. de Chim. Méd., May 1860.
I42 POISONS: THEIR EFFECTS AND DETECTION. [$ 156-159.
Dr. Schaaf’ has recorded three cases of poisoning—one of which was fatal. A
woman gave about half a teaspoonful of a camphor solution to each of her three
children, the ages being respectively 5 and 3 years, and 15 months. The symptoms
noted were pallor of the face, a burning pain in the throat, thirst, vomiting, purging,
convulsions, and afterwards coma. The youngest child died in seven hours ; the
others recovered. The smallest dose known to have produced violent symptoms in
an adult person is 13 grim. (20 grains); the largest dose known to have been re-
covered from is 10°4 grms, (160 grains), t
§ 156. Post-mortem. Appearances.—The bodies of animals or persons dying from
poisoning by camphor, smell strongly of the substance. The mucous membrane of
the stomach has been found inflamed, but there seem to be no characteristic lesions.
§ 157. Separation of Camphor from the Contents of the Stomach. —The identi-
fication of camphor would probably in no case present any difficulty. It may be
readily dissolved out from organic fluids by chloroform. If dissolved in fixed oils,
enough for the purposes of identification may be obtained by simple distillation. It
is precipitated from its alcoholic solution by the addition of water.
III.-Alcohols.
1. ETHYLIC AICOHOL.
§ 158. The chemical properties of ordinary alcohol are fully de-
scribed, with the appropriate tests, in “Foods,” pp. 379–398, and the
reader is also referred to the same volume for the composition and
strength of the various alcoholic drinks.
Statistics.-If we were to include in one list the deaths indirectly
due to chronic, as well as acute poisoning by alcohol, it would stand
first of all poisons in order of frequency, but the taking of doses so large
as to cause death in a few hours is rare. The deaths from alcohol are
included by the English Registrar-General under two heads, viz., those
returned as dying from delirium tremens, and those certified as due
directly to intemperance.
From 1875 to 1903 the deaths registered as due to intemperance
have varied from a minimum of 1269 up to 3638, the maximum occur-
ring in 1900. The curve on the opposite page clearly shows the alcoholic
death-rate per million living during the period. Alcoholic deaths, with
a few intermissions, increased from 1879 to 1900, and since that year
have declined.
During the ten years ending 1903, 82 deaths (56 males and 26
females) were ascribed, under the head of “accident or negligence,”
directly to alcohol. -
§ 159. Criminal or Accidental Alcoholic Poisoning.—Suicide by
alcohol, in the common acceptation of the term, is rare, and murder
* Journ. de Chim. Méd., 1850, p. 507.
+ Taylor on Poisons, 3rd ed., 661.
§ I 59.] ETHYLIC ALCOHOL. I43
still rarer, though not unknown. In the ten years ending 1903, only
DEATHS PER MILLION LIVING FROM ALCOHOL FROM 1875–1903
5 deaths from alcohol (3 males and 2 females) are recorded as suicidal.
Perhaps the most common cause of fatal acute poisoning by alcohol is

I44 POISONS: THEIR EFFECTS AND DETECTION. [S 160, 161.
either a foolish wager, by which a man bets that he can drink so many
glasses of spirits without bad effect ; or else the drugging of a person
already drunk by his companions in a sportive spirit.
§ 160. Fatal Dose.--It is difficult to say what would be likely to
prove a lethal dose of alcohol, for a great deal depends, without doubt,
on the dilution of the spirit, since the mere local action of strong
alcohol on the mucous membranes of the stomach, etc., is severe (one
may almost say corrosive), and would aid the more remote effects. In
Maschka's case,” a boy of 9 years and a girl of 5 died from about
2% ounces of spirit of 67 per cent, strength, or 48.2 c.c. (1.7 oz.) of
absolute alcohol.
In a case related by Taylor, a child, 7 years old, died from some
quantity of brandy, probably about 113.4 c.c. (4 ozs.), which would be
equal to at least 56'7 c.c. (2 ozs.) of absolute alcohol. From other cases
in which the quantity of absolute alcohol can be, with some approxi-
mation to the truth, valued, it is evident that, for any child below 10
or 12, quantities of from 28-3 to 56.6 c.c. (1–2 ozs.) of absolute
alcohol contained in brandy, gin, etc., would be a highly dangerous and
probably fatal dose ; while the toxic dose for adults is somewhere
between 718–141:7 c.c. (2.5–5 ozs.).
§ 161. Symptoms.—In the cases of rapid poisoning by a large dose
of alcohol, which alone concern us, the preliminary, and too familiar
excitement of the drunkard, may be hardly observable ; but the second
stage, that of depression, rapidly sets in ; the unhappy victim sinks
down to the ground helpless, the face pale, the eyes injected and
staring, the pupils dilated, acting sluggishly to light, and the skin re-
markably cold. Fräntzel f found, in a case in which the patient survived,
* Recorded by Maschka (Gutachten der Prager Facultät, iv. 239; see also
Maschka's Handbuch der gericht. Medicin, Band ii. p. 384). The following is a
brief summary :-Franz. Z., 9 years old, and Caroline Z., 5 years old, were poisoned
by their stepfather with spirit of 67 per cent, strength taken in small quantities
by each—at first by persuasion, and the remainder administered by force. About
one-eighth of a pint is said to have been given to each child. Both vomited some-
what, then lying down, stertorous breathing at once came on, and they quickly
died. The autopsy, three days after death, showed dilatation of the pupils ; rigor
mortis present in the boy, not in the girl; and the membranes of the brain filled
with dark fluid blood. The smell of alcohol was perceptible on opening the chest :
the mucous membrane of the bronchial tubes and gullet was normal, both lungs
occlematous, the fine tubes gorged with a bloody frothy fluid, and the mucous mem-
brane of the whole intestinal canal was reddened. The stomach was not, unfortu-
mately, examined, being reserved for chemical analysis. The heart was healthy; the
pericardium contained some straw-coloured fluid. Chemical analysis gave an entirely
negative result, which must have been from insufficient material having been sub-
mitted to the analyst, for it is hard to see how the vapours of alcohol could have been
detected by the smell, and yet have evaded chemical processes.
+ Temperaturerniedrigung durch Alcoholintoxication, Charité Annalen, i. 371.
§ 162.] ETHYLIC ALCOHOL. I45
a temperature of only 24.6° in the rectum, and in that of another
person who died, a temperature of 23.8°. The mucous membranes are
of a peculiar dusky blue; the pulse, which at first is quick, soon becomes
slow and small ; the respiration is also slowed, intermittent, and
stertorous; there is complete loss of consciousness and motion ; the
breath smells strongly of the alcoholic drink, and if the coma continues
there may be vomiting and involuntary passing of excreta. Death
ultimately occurs through paralysis of the respiratory centres. Con-
vulsions in adults are rare, in children frequent. Death has more than
once been immediately caused, not by the poison, but by accidents de-
pendent upon loss of consciousness. Thus food has been sucked into the
air-tubes, or the person has fallen, so that the face was buried in water,
ordure, or mud; here suffocation has been induced by mechanical causes.
A remarkable course not known with any other narcotic is that in
which the symptoms remit, the person wakes up, as it were, moves about
and does one or more rational acts, and then suddenly dies. In this
case also, the death is not directly due to alcohol, but indirectly—the
alcohol having developed Oedema, pneumonia, or other affection of the
lungs, which causes the sudden termination when the first effect of the
poison has gone off. The time that may elapse from the commence-
ment of coma till death varies from a few minutes to days; death has
occurred after a quarter of an hour, half an hour, and an hour. It
has also been prolonged to three, four, and six days, during the whole
of which the coma has continued. The average period may, however,
be put at from six to ten hours.
§ 162. Post-mortem Appearances.—Cadaveric rigidity lasts toler.
ably long. Casper has seen it still existing nine days after death, and
Seidel” seven days (in February). Putrefaction is retarded in those
cases in which a very large dose has been taken, but this is not a very
noticeable or constant characteristic. The pupils are mostly dilated.
The smell of alcohol should be sought for ; sometimes it is only
present in cases where but a short time has elapsed between the taking
of the poison and death ; putrefaction may also conceal it, but under
favourable circumstances, especially if the weather is cold, the alcoholic
smell may remain a long time. Alcohol may cause the most intense
redness and congestion of the stomach. The most inflamed stomach I
(A. W. B.) ever saw, short of inflammation by the corrosive poisons, was
that of a sailor, who died suddenly after a twenty-four hours' drinking
bout ; all the organs of the body were fairly healthy, the man had suffered
from no disease ; analysis could detect no poison but alcohol; and the
history of the case, moreover, proved clearly that it was a pure case of
alcoholic poisoning.
* Seidel, Maschka's Handbuch, Bd. ii. p. 380.
IO
I46 POISONS : THEIR EFFECTS AND DETECTION. [$ 163.
In a case related by Taylor, in which a child drank 4 ozs. of brandy
and died, the mucous membrane of the stomach presented patches of
intense redness, and in several places was thickened and softened, some
portions being actually detached and hanging loose, and there were
evident signs of extravasations of blood. The effect may not be con-
fined to the stomach, but extend to the duodenum and even to the
whole intestimal canal. The blood is generally dark and fluid, and
usually the contents of the skull are markedly hyperamic, the pia very
full of blood, the sinuses and plexus gorged ; occasionally, the brain
substance shows signs of unusual congestion ; serum is often found in
the ventricles. The great veins of the neck, the lungs, and the right
side of the heart are very often found full of blood, and the left side
empty. CEdema of the lungs also occurs with tolerable frequency.
The great veins of the abdomen are also filled with blood, and if the
coma has been prolonged, the bladder will be distended with urine. A
rare phenomenon has also been noticed—namely, the occurrence of
blebs on the extremities, etc., just as if the part affected had been burnt
or scalded. Lastly, with the changes directly due to the fatal dose may
be included all those degenerations met with in the chronic drinker,
provided the case had a history of previous intemperance.
§ 163. Excretion of Alcohol. — Alcohol, in the diluted form, is
quickly absorbed by the blood-vessels of the stomach, etc., and circulates
in the blood; but what becomes of it afterwards is by no means settled.
There can be little doubt that the lungs are the main channels
through which it is eliminated; with persons given up to habits of
intemperance, the breath has constantly a very peculiar ethereal odour,
probably dependent upon some highly volatile oxidised product of
alcohol.
Alcohol is eliminated in small proportion only by the kidneys.
Thudichum, in an experiment * by which 4000 grns, of absolute
alcohol were consumed by thirty-three men, could only find in the
collected urine 10 grns. of alcohol. The numerous experiments by
Dupré also establish the same truth, that but a fraction of the total
alcohol absorbed is excreted by the kidneys. According to Lallemand,
Perrin, and Duroy, the content of the brain in alcohol is more than
that of the other organs. One of us (A. W. B.) has found also that
the brain after death has a wonderful attraction for alcohol, and yields
it up at a water-heat very slowly and with difficulty. In one experiment,
in which a finely divided portion of brain, which had been soaking in
alcohol for many weeks, was submitted to a steam-heat of 100°, twenty-
four hours' consecutive heating failed to expel every trace of spirit.
* See Thudichum’s Pathology of the Urine, London, 1877, in which both his
own and Dr. Dupré's experiments are summarised.
§ 164.] ETHYLIC ALCOHOL. I47
It is probable that true alcoholates of the chemical constituents of
the brain are formed. In the case of vegetable colloidal bodies, such,
for example, as the pulp of cherries, a similar attraction has been
observed, the fruit condensing, as it were, the alcohol in its own tissues,
and the outer liquid being of less alcoholic strength than that which
can be expressed from the steeped cherries. Alcohol is also excreted
by the sweat, and minute fractions have been found in the faces.
§ 164. Toxicological Detection of Alcohol (see “Foods,” pp.
382–384).-The living cells of the body produce minute quantities of
alcohol, as also some of the bacteria normally inhabiting the small
intestine produce small quantities of alcohol, and it is often found in
traces in putrefying fluids. Hence, mere qualitative proofs of the
presence of alcohol are insufficient on which to base an opinion as to
whether alcohol had been taken during life or not, and it will be
necessary to estimate the quantity accurately by some of the processes
detailed in “Foods,” p. 385 et seq. In those cases in which alcohol
is found in quantity in the stomach, there can, of course, be no diffi-
culty; in others, the whole of the alcohol may have been absorbed, and
chemical evidence, unless extremely definite, must be supplemented
by other facts.
Alcohols may in many instances be identified by converting them
into the dinitro-benzoate esters. - -
The following directions for ethyl alcohol are given by Mulliken “
for the preparation of ethyl 3: 5 dinitro-benzoate, and are applicable to
the series generally, with a few obvious modifications, provided the
alcohol is pure and contains no more than 10 per cent. water,
Heat together gently over a small flame 0:15 grm. 3: 5 dinitro-
benzoic acid and 0.29 grim. phosphorus pentachloride. When signs of
chemical action appear, the heat is removed for a few seconds. The
heat is then reapplied, and the liquefied mixture boiled for exactly one
minute. The product is poured out on to a watch-glass and allowed
to solidify. The liquid phosphorus oxychloride, with which the mass
is impregnated, is got rid of by rubbing the latter between two pieces
of porous tile. The powder is placed in a dry test tube, and four drops
of alcohol are allowed to fall on it (with propyl or butyl alcohols six drops
are added instead of four, because the alcohol must be in excess), the tube
is at once stoppered, and the lower part immersed in water at 75°–85°.
The tube is shaken gently and warmed in this way for ten minutes.
When the mixture is cold, any hard lumps of ester which may have
formed are crushed with a stirring rod, and in the case of ethyl dinitro
benzoate boiled gently with 15 c.c. of methyl alcohol until all is
dissolved.
* A Method for the Identification of Pure Organic Compounds, New York, 1904,
I48 Poisons: THEIR EFFECTS AND DETECTION. [$ 165–168.
(With most other esters, instead of methyl alcohol as a solvent,
ethyl alcohol is used.)
If the solution is not clear it must be filtered hot. The final
crystals are recrystallised from boiling methyl alcohol, washed with the
Same solvent, spread out on a porous tube to dry, and the melting-
point determined.
Methyl 3: 5 dinitro-benzoate melts at . sº e ... 107.5°
Ethyl y 3 » . . . & 92°, 93°
Iso-butyl 2 3 3 y & 83°–83 °5°
Propyl } } - 3 3 º e e * 73°
Butyl * 5 3 3 º g º & 64°
2. AMYLIC ALCOHOL.
§ 165. Amylic Alcohol—Formula, C5Hu HO. —There is more than one amylic
alcohol, according to theory ; eight isomers are possible, and seven are known. The
amylic alcohols differ in certain physical properties, primary amylic alcohol boiling
at 137°, and iso-amyl alcohol at 131.6°. The latter has a specific gravity of 8148,
and is the variety produced by fermentation and present in fusel oil.
§ 166. The experiments of Eulenberg “ on rabbits, Crosst on pigeons, Rabuteau:
on frogs, and Furst on rabbits, with those of Sir B. W. Richardson Š on various
animals, have shown it to be a powerful poison, more especially if breathed in a
state of vapour.
Richardson, as the result of his investigations, considers that amyl alcohol
when breathed sets up quite a peculiar class of symptoms which last for many hours,
and are of such a character that it might be thought impossible for the animal to
recover, although they have not been known to prove fatal. There is muscular
paralysis with paroxysms of tremulous convulsions; the spasms are excited by
touching the animal, breathing upon it, or otherwise subjecting it to trifling
excitation.
§ 167. Hitherto, neither the impure fusel oil, nor the purer chemical preparation,
has had any toxicological importance. Should it be necessary at any time to recover
small quantities from organic liquids, the easiest way is to shake the liquid up with
chloroform, which readily dissolves amylic alcohol, and on evaporation leaves it in a
state pure enough to be identified. Amyl alcohol is identified by the following
tests:—(1) its physical properties; (2) if warmed with twice its volume of strong
sulphuric acid, a rose or red colour is produced ; (3) heated with an acetate and
strong sulphuric acid, amyl acetate, which has the odour of the jargonelle pear, is
formed ; (4) heated with sulphuric acid and potassic dichromate, valeric aldehyde is
first produced, and then Valeric acid is formed ; the latter has a most peculiar and
strong odour.
§ 168. Amyl Nitrite, Iso-amyl Ester Nitrite (C6H11NO2). —Boiling-point 97° to
99°, specific gravity '877. Amyl nitrite is a limpid, and, generally, slightly yellow
* Gewerbe Hygiene, 1876, p. 440.
+ De l'Alcohol Amylique et Methyl sur l'Organisme (Thèse), Strasburg, 1863.
: “Ueber die Wirkung des Aethyl, Butyl u. Amyl Alcohols,” L'Union, Nos.
90, 91, 1870. Schmidt’s Jahrb., Bd. cxlix. p. 263.
§ Trans. Brit. Association, 1864, 1865, and 1866. Also, Brit. and Foreign
Med. Chºir. Rev., Jan. 7, 1867, p. 247.
§ 169, 170.] ETHER. I 49
liquid; it has a peculial and characteristic odour. On heating with alcoholic potash,
the products are nitrite of potash and amylic alcohol; the amylic alcohol may be
distilled off and identified. The presence of a nitrite in the alkaline solution is readily
shown by the colour produced, by adding a few drops of a solution of meta-phenylene-
diamine.
Sir B. W. Richardson and others have investigated the action of amyl nitrite, as
well as that of the acetate and iodide ; they all act in a similar manner, the nitrite
being most potent. After absorption, the effects of amyl nitrite are especially seen
on the heart and circulation : the heart acts violently, there is first dilatation of the
capillaries, then this is followed by diminished action of the heart and contraction
of the capillaries.
According to Richardson, it suspends the animation of frogs. No other sub-
stance known will thus suspend a frog's animation for so long a time without killing
it. Under favourable circumstances, the animal will remain apparently dead for
many days, and yet recover. Warm-blooded animals may be thrown by amyl
nitrite into a cataleptic condition. It is not an anaesthetic, and by its use conscious-
ness is not destroyed, unless a condition approaching death be first produced. When
this occurs there is rarely recovery, the animal passes into actual death.
Post-mortem. Appearances.—If administered quickly, the lungs and all the other
organs are found blanched and free from blood, the right side of the heart gorged
with blood, the left empty, the brain being free from congestion. If administered
slowly, the brain is found congested, and there is blood both on the left and right
sides of the heart.
IV. —Ether.
§ 169. Ether, Ethylic Ether, Ethyl Oxide, (C.H.),0.—Ethylic ether
is a highly mobile liquid of peculiar penetrating odour and sweetish,
pungent taste. It is perfectly colourless, and evaporates so rapidly,
that when applied in the form of spray to the skin, the latter becomes
frozen, and is thus deprived of sensibility.
Pure ether has a density of 713, its boiling-point is 35°, but com-
mercial samples, which often contain water (1 part of water is soluble in
35 of ether), may have a higher gravity, and also a higher boiling-point.
The readiest way to know whether an ether is anhydrous or not, is to
shake it up with a little carbon disulphide. If it is hydrous, the
mixture is milky. Methylated ether is largely used in commerce ; its
disagreeable odour is due to contamination by methylated compounds;
otherwise the ether made from methylated spirit is ethylic ether, for
methylic ether is a gas which escapes during the process. Hence the
term “methylated ” ether is misleading, for it contains no methylic
ether, but is essentially a somewhat impure ethylic ether.
§ 170. Ether as a Poison.—Ether has but little toxicological im-
portance. There are a few cases of death from its use as an anaesthetic,
and a few cases of suicide. Ether is used by some people as a stimulant,
but ether drinkers are uncommon. It causes an intoxication very
similar to that of alcohol, but of brief duration. In a case of chronic
I 50 POISONS: THEIR EFFECTS AND DETECTION. [$ 171–173.
ether-taking recorded by Martin,” in which a woman took daily doses
of ether for the purpose of allaying a gastric trouble, the patient suffered
from shivering or trembling of the hands and feet, muscular weakness,
cramp in the calves of the legs, pain in the breast and back, inter-
mittent headaches, palpitation, singing in the ears, vomitings, and
wakefulness; the ether being discontinued, the patient recovered. In
one of Orfila's experiments, half an ounce of ether was administered to a
dog. The animal died insensible in three hours. The mucous membrane
of the stomach was found highly inflamed, the inflammation extending
somewhat into the duodenum ; the rest of the canal was healthy. The
lungs were gorged with fluid blood.
§ 171. Fatal Dose.—The fatal dose of ether, when taken as a liquid,
is not known. 4 grms. (1:28 drums.) cause toxic symptoms, but the effect
soon passes. Buchanan has seen a brandy-drinker consume 25 grns.
(7 drms.) and yet survive. It is probable that most adults would be
killed by a fluid ounce (28.4 c.c.).
§ 172. Ether as an Anaesthetic.—Ether is now much used as an
anaesthetic, and generally in conjunction with chloroform. Anaesthesia
by ether is said to compare favourably with that produced by chloroform.
In 92,000 cases of operations performed under ether, the proportion
dying from the effects of the anaesthetic was only 3 per 10,000 (Morgan),
while chloroform gives a higher number (see p. 156). The mortality in
America, again, from a mixture of chloroform and ether in 11,000 cases
is reckoned at 1.7 per 10,000; but this proportion is rather above some
of the calculations relative to the mortality from pure chloroform, so that
the question can hardly be considered settled. The symptoms of ether
narcosis are very similar to those produced by chloroform. The chief
point of difference appears to be its action on the heart. Ether, when
first breathed, stimulates the heart's action, and the after-depression that
follows never reaches so high a grade as with chloroform, Ether is said
to kill by paralysing the respiration, and in cases which end fatally
the breathing is seen to stop suddenly : convulsions have not been
noticed. The post-mortem appearances, as in the case of chloroform,
are not characteristic.
§ 173. Separation of Ether from Organic Fluids, etc.—Despite the
low boiling-point of ether, it is by no means easy to separate it from
organic substances so as to recover the whole of the ether present. The
best way is to place the matters in a flask connected with an ordinary
Liebig's condenser, the tube of the latter at its farther end fitting closely
into the doubly perforated cork of a flask. Into the second perforation
is adapted an upright tube about 2 feet long, which may be of small
diameter, and must be surrounded by a freezing mixture of ice and salt.
* Comptes Remulus, 1868.
§ 174.] CHLOROFORM. I 5 I
The upper end of this tube is closed by a thistle-head funnel with
syphon, and in the bend of the syphon a little mercury serves as a valve.
Heat is now applied to the flask by means of a water-bath, and continued
for several hours; the liquid which has distilled over is then treated
with dry calcic chloride and redistilled exactly in the same way. To
this distillate again a similar process may be used, substituting dry
potassic carbonate for the calcic chloride. It is only by operating on
these principles that the expert can recover in an approximate state of
anhydrous purity such a volatile liquid. Having thus obtained it pure,
it may be identified (1) by its smell, (2) by its boiling-point, (3) by its
inflammability, and (4) by its reducing chromic acid. The latter test
may be applied to the vapour. An asbestos fibre is soaked in a mixture
of strong sulphuric acid and potassic dichromate, and then placed in the
tube connected with the flask—the ethereal (or alcoholic) vapour passing
over the fibre immediately reduces the chromic acid to chromic oxide,
with the production of a green colour.
W.—Chloroform.
CHLOROFORM, TRICHLOROMETHANE OR METHYL CHLORIDE
(CHCl2).
§ 174. Chloroform appears to have been discovered independently by
Soubeyran and Liebig, about 1830. It was first employed in medicine
by Simpson, of Edinburgh, as an anaesthetic. Pure chloroform has a
density of 1:491 at 17°, and boils at 60°8'; but commercial samples have
gravities of from 1:47 to 1491. It is a colourless liquid, strongly
refracting light ; it cannot be ignited by itself, but, when mixed with
alcohol, burns with a smoky flame edged with green. Its odour is
heavy, but rather pleasant ; the taste is sweet and burning.
Chloroform sinks in water, and is only slightly soluble in that fluid
(44 in 100 c.c.); it is perfectly neutral in reaction, and very volatile.
When rubbed on the skin, it should completely evaporate, leaving no
odour. Pure absolute chloroform gives an opaline mixture if mixed
with from 1 to 5 volumes of alcohol, but with any quantity above
5 volumes the mixture is clear ; it mixes in all proportions with ether.
Chloroform coagulates albumen, and is an excellent solvent for most
organic bases—camphor, caoutchouc, amber, opal, and all common resins.
It dissolves phosphorus and sulphur slightly—more freely iodine and
bromine. It floats on hydric sulphate, which only attacks it at a boiling
heat.
Chloroform is sometimes impure from faulty manufacture or decom-
I 52 POISONS: THEIR EFFECTS AND DETECTION. [$ 174.
position. The impurities to be sought are alcohol, methylated chloro-
form,” dichloride of ethylene (CH,Cl), chloride of ethyl (C.H,Cl),
aldehyde, chlorine, hydrochloric, hypochlorous, and traces of sulphuric
acid : there have also been found chlorinated oils. One of the best tests
for contamination by alcohol, wood spirit, or ether, is that known as
Roussin's; dinitrosulphide of iron f is added to chloroform. If it contain
any of these impurities, it acquires a dark colour; but if pure, remains
bright and colourless. ©
The presence of alcohol or ether, or both, may also be discovered by
the bichromate test, which is best applied as follows:—A few milli-
grammes of potassic bichromate are placed at the bottom of a test tube
with four or five drops of sulphuric acid, which liberates the chromic
acid; next, a very little water is added to dissolve the chromic acid;
and lastly, the chloroform. The whole is now shaken, and allowed to
separate. If the chloroform is pure, the mass is hardly tinged a greenish-
yellow, and no layer separates. If, however, there is anything like 5
per cent. of alcohol or ether present, the deep green of chromium
chloride appears, and there is a distinct layer at the bottom of the
tube.
Another way to detect alcohol in chloroform, and also to make an
approximate estimation of its quality, is to place 20 c.c. of chloroform
in a burette, and then add 80 c.c. of water. On shaking violently, pure
chloroform will sink to the bottom in clear globules, and the measurement
will be as nearly as possible the original quantity; but if anything like
a percentage of alcohol be present, the chloroform is seen to be diminished
in quantity, and its surface is opalescent, the diminution being caused
by the water dissolving out the alcohol. The addition of a few drops
of potash solution destroys the meniscus, and allows of a close reading
of the volume. The supernatant water may be utilised for the detection
of other impurities, and tested for sulphuric acid by baric chloride, for
free chlorine and hypochlorous acid by starch and potassic iodide, and
for hydrochloric acid by silver nitrate.f Fuchsine, proposed by Städeler,
is also a delicate reagent for the presence of alcohol in chloroform, the
sample becoming red in the presence of alcohol, and the tint being
proportionate to the quantity present. The most delicate test for
* Methylated chloroform is that which is prepared from methylated spirit. It
is liable to more impurities than that made from pure alcohol, but, of course, its
composition is the same, and it is now manufactured from this source almost
chemically pure.
+ Made by slowly adding ferric sulphate to a boiling solution of ammonic sulphide
and potassic nitrite, as long as the precipitate continues to redissolve, and then
filtering the solution.
+ Neither an alcoholic nor an aqueous solution of silver nitrate causes the slightest
change in pure chloroform.
§ 175—177.] CHLOROFORM. - I 53
alcohol is, however, the iodoform test fully described in “Foods,” p. 383.”
Dichloride of ethylene is detected by shaking up the chloroform with
dry potassic carbonate, and then adding metallic potassium. This does
not act on pure chloroform, but only in presence of ethylene dichloride,
when the gaseous chlor-ethylene (C, H,Cl) is evolved. Ethyl-chloride is
detected by distilling the chloroform and collecting the first portions of
the distillate ; it will have a distinct odour of ethyl-chloride should it
be present. Methyl compounds and empyreumatic oils are roughly
detected by allowing the chloroform to evaporate on a cloth. If present,
the cloth, when the chloroform has evaporated, will have a peculiar,
disagreeable odour. Aldehyde is recognised by its reducing action on
argentic nitrate; the mineral acids by the reddening of litmus-paper,
and the appropriate tests. Hypochlorous acid first reddens, and then
bleaches, litmus-paper.
Dr. Dott (Pharm. Journ., 1894, p. 629) gives the following tests:—
Specific gravity, 1490 to 1:495. On allowing 3 fluid drm. to evaporate
from a clean surface, no foreign odour is perceptible at any stage of the
evaporation. When 1 fluid drm. is agitated with an equal volume of
solution of silver nitrate, no precipitate or turbidity is produced after
standing for five minutes. On shaking up the chloroform with half its
volume of distilled water, the water should not redden litmus-paper.
When shaken with an equal volume of sulphuric acid, little or no colour
should be imparted to the acid. -
§ 175. The ordinary method of manufacturing chloroform is by
distilling alcohol with chlorinated lime; but another mode is now much
in use—viz., the decomposition of chloral hydrate. By distilling it
with a weak alkali, this process yields such a pure chloroform, that, for
medicinal purposes, it should supersede every other.
1. AS A LIQUID.
§ 176. Poisonous Effects of Chloroform—Statistics.—Falck finds
recorded in medical literature 27 cases of poisoning by chloroform
having been swallowed—of these 15 were men, 9 were women, and
3 children. Eighteen of the cases were suicidal, and 10 of the 18
died; the remainder took the liquid by mistake.
§ 177. Local Action of Chloroform.—When applied to the skin or
mucous membranes in such a way that the fluid cannot evaporate—as,
* An attempt has been made by Besnou to estimate the amount of alcohol by
the specific gravity. He found that a chloroform of 1:4945 gravity, mixed with 5
per cent of alcohol, gave a specific gravity of 1:4772; 10 per cent., 14602; 20 per
cent., 1'4262; and 25 per cent., 14090. It would, therefore, seem that every per-
centage of alcohol lowers the gravity by '0034.
I 54 POISONs: THEIR EFFECTS AND DETECTION. [$ 178, 179.
for example, by means of a cloth steeped in chloroform laid on the bare
skin, and covered over with some impervious material—there is a
burning sensation, which soon ceases, and leaves the part anaesthetised,
while the skin, at the same time, is reddened, and sometimes even
blistered.
§ 178. Chloroform added to blood, or passed through it in the state
of vapour, causes it to assume a peculiar brownish colour owing to
destruction of the red corpuscles and solution of the haemoglobin in
the plasma. The change does not require the presence of atmospheric
air, but takes place equally in an atmosphere of hydrogen. It has been
shown by Schmiedeberg that the chloroform enters in some way into a
state of combination with the blood corpuscles, for the entire quantity
cannot be recovered by distillation; whereas the plasma, similarly
treated, yields the entire quantity which has in the first place been
added. Schmiedeberg also asserts that the oxygen is in firmer com-
bination with the chloroformised blood than usual, as shown by its slow
extraction by stamnous oxide. Muscle, exposed to chloroform liquid by
arterial injection, quickly loses excitability and becomes rigid. Nerves
are first stimulated, and then their function for the time is annihilated;
but on evaporation of the chloroform, the function is restored.
§ 179. General Effects of the Liquid.—However poisonous in a
state of vapour, chloroform cannot be considered an extremely active
poison when taken into the stomach as a liquid, for enormous quantities,
relatively, have been drunk without fatal effect. Thus, there is the case
recorded by Taylor, in which a man, who had swallowed 113-4 grms.
(4 ozs.), walked a considerable distance after taking the dose. He
subsequently fell into a state of coma, with dilated pupils, stertorous
breathing, and imperceptible pulse. These symptoms were followed by
convulsions, but the patient recovered in five days.
In a case related by Burkart,” a woman desired to kill herself with
chloroform, and procured for that purpose 50 grms. (a little less than
one ounce and a half); she drank some of it, but the burning taste and
the sense of heat in the mouth, throat, and stomach, prevented her from
taking the whole at once. After a few moments, the pain passing off,
she essayed to drink the remainder, and did swallow the greater portion
of it, but was again prevented by the suffering it caused, Finally, she
poured what remained on a cloth, and placing it over her face, soon
sank into a deep marcosis. She was found lying on the bed very pale,
with blue lips, and foaming a little at the mouth ; the head was rigidly
bent backwards, the extremities were lax ; the eyes were turned upwards
and inwards, the pupils dilated and inactive ; the face and extremities
were cold, the body somewhat warmer ; there was no pulse at the wrist,
* Vierteljahrsschr, für ger. Med., 1876.
§ 180, 181.] CHLOROFORM. I 55
the carotids beat feebly ; the breathing was deep and rattling, and after
five or six inspirations ceased. By the aid of artificial respiration, etc.,
she recovered in an hour.
A still larger dose has been recovered from in the case of a young
man, aged 23,” who had swallowed no less than 75 grms. (2-6 ozs.)
of chloroform, but yet, in a few hours, awoke from the stupor. He
complained of a burning pain in the stomach ; on the following day he
suffered from vomiting, and on the third day symptoms of jaundice
appeared—a feature which has been several times noticed as an effect
of chloroform.
On the other hand, even small doses have been known to destroy
life. In a case related by Taylor, a boy, aged 4, swallowed 3-5 grms.
(1 drm.) of chloroform and died in three hours, notwithstanding that
every effort was used for his recovery.
§ 180. The smallest dose that has proved fatal to an adult is 15 grns.
(a little over 4 drms.).
From twenty-two cases in which the quantity taken had been ascer-
tained with some degree of accuracy, Falck draws the following con-
clusions:—In eight of the cases the dose was between 4 and 30 grms.,
and one death resulted from 15 grms. As for the other fourteen
persons, the doses varied from 35 to 380 grns, and eight of these
patients died—two after 40, two after 45, one after 60, 90, 120, and
180 grms, respectively. Hence, under conditions favouring the action
of the poison, 15 grms. (4:3 drms.) may be fatal to an adult, while doses
of 40 grns. (11:3 drms.) and upwards will almost certainly kill.
§ 181. Symptoms.--The symptoms can be well gathered from the
cases quoted. They commence shortly after the taking of the poison;
and, indeed, the local action of the liquid immediately causes first a
burning sensation, followed by numbness.
Often after a few minutes, precisely as when the vapour is adminis-
tered, a peculiar, excited condition supervenes, accompanied, it may be,
by delirium. The next stage is marcosis, and the patient lies with pale
face and livid lips, etc., as described at p. 154; the end of the scene is
often preceded by convulsions. Sometimes, however, consciousness
returns, and the irritation of the mucous membranes of the gastro-
intestinal canal is shown by bloody vomiting and bloody stools, with
considerable pain and general suffering. In this way, a person may
linger several days after the ingestion of the poison. In a case observed
by Pomeroy, the fatal malady was prolonged for eight days. Among
those who recover, a common sequela, as before mentioned, is jaundice.
A third form of symptoms has been occasionally observed, viz. –
The person awakes from the coma, the breathing and pulse become
* Brit, Med. Journ., 1879.
W
I 56 POISONS: THEIR EFFECTS AND DETECTION. [$ 182, 183.
again matural, and all danger seems to have passed, when suddenly,
after a longer or shorter time, without warning, a state of general
depression and collapse supervenes, and death occurs.
§ 182. Post-mortem Appearances.—The post-mortem appearances
from a fatal dose of liquid chloroform mainly resolve themselves into
redness of the mucous membrane of the stomach, though occasionally,
as in Pomeroy's case, there may be an ulceration. In a case recorded
by Hoffman,” a woman, aged 30, drank 35 to 40 grms, of chloroform
and died within the hour. Almost the whole of the chloroform taken
was found in the stomach, as a heavy fluid, coloured green, through the
bile. The epithelium of the pharynx, epiglottis, and gullet was of a
dirty colour, partly detached, whitened, softened, and easily stripped off.
The mucous membrane of the stomach was much altered in colour and
consistence, and, with the duodenum, was covered with a tenacious grey
slime. There was no ecchymosis.
2. THE WAPOUR OF CHLOROFORM.
§ 183. Statistics.—Accidents occur far more frequently in the use
of chloroform vapour for anaesthetic purposes than in the use of the
liquid. *
Most of the cases of death through chloroform vapour are those
caused accidentally in surgical and medical practice. A smaller
number are suicidal, while for criminal purposes its use is extremely
infrequent.
The percentage of deaths caused by chloroform administered during
operations is unaccountably different in different years, times, and places.
The diversity of opinion on the subject is partly (though not entirely)
explicable, by the degrees of purity in the anaesthetic administered, the
different modes of administration, the varying lengths of time of the
anaesthesia, and the varying severity of the operations.
During the Crimean war, according to Baudens and Quesnoy,
30,000 operations were done under chloroform, but only one death
occurred attributable to the anaesthetic. Sansom i puts the average
mortality at 75 per 10,000, Nussbaum at 1:3, Richardson at 28, :
Morgan Š at 3:4. In the American war of secession, in 11,000
operations, there were 7 deaths—that is, 6.3 per 10,000, the highest
number on a large scale which appears to be on record. In the ten
years ending 1903, 830 deaths are attributed to chloroform in Eng-
land and Wales—viz., 520 males, 292 females, from use as a general
* Lehrbuch der ger. Medicin, 2te Aufl.
† Chloroform : its Action, etc., London, 1865.
† Med. Times and Gazette, 1870. § Med. Soc. of Virginia, 1872.
*
§ 184, 185.] CHLOROFORM. I 57
anaesthetic; 17 (9 males, 8 females) from suicide; and a solitary case of
murder.
§ 184. Suicidal and Criminal Poisoning by Chloroform.—Suicidal
poisoning by chloroform will generally be indicated by the surrounding
circumstances; and in no case hitherto reported has there been any
difficulty or obscurity as to whether the narcosis was self-induced or
not. An interesting case is related by Schauenstein,” in which a
physician resolved to commit suicide by chloroform, a commencing
amaurosis having preyed upon his mind, and his choice having been
determined by witnessing an accidental death by this agent. He
accordingly plugged his nostrils, fitted on to the face an appropriate
mask, and fastened it by strips of adhesive plaster. In such an
instance, there could be no doubt of the suicidal intent, and the
question of accident would be entirely out of the question.
A dentist in Potsdam, f in a state of great mental depression from
embarrassed circumstances, killed his wife, himself, and two children by
chloroform. Such crimes are fortunately very rare.
There is a vulgar idea that it is possible, by holding a cloth saturated
with chloroform to the mouth of a sleeping person (or one, indeed, per-
fectly awake), to produce sudden insensibility; but such an occurrence
is against all experimental and clinical evidence. It is true that a
nervous person might, under such circumstances, faint and become
insensible by mere nervous shock; but a true sudden narcosis is
impossible.
Dolbeau has made some interesting experiments in order to ascer-
tain whether, under any circumstances, a sleeping person might be
anaesthetised. The main result appears to answer the question in the
affirmative, at least with certain persons; but even with these, it can
only be done by using the greatest skill and care, first allowing the
sleeper to breathe very dilute chloroform vapour, and then gradually
exhibiting stronger doses, and taking the cloth or inhaler away on the
slightest symptom of approaching wakefulness. In 75 per cent. of the
cases, however, the individuals awoke almost immediately on being
exposed to the vapour. This cautious and scientific narcosis, then, is
not likely to be used by the criminal class, or, if used, to be successful.
§ 185. Physiological Effects.-Chloroform is a protoplasmic poison.
According to Jumelle, plants can even be narcotised, ceasing to
assimilate and no longer being sensitive to the stimulus of light.
Isolated animal cells, like leucocytes, lose through chloroform vapour
their power of spontaneous movement, and many bacteria cease to
multiply if in contact with chloroform water. According to Binx,
* Maschka, Handbuch der gerichtlich. Medicin, p. 787, Tübingen, 1882.
t Casper, Handbuch der ger. Med.
I 58 POISONS : THEIR EFFECTS AND DETECTION, [S 186.
chloroform narcosis in man is to be explained through its producing a
weak coagulation of the cerebral ganglion cells. As already mentioned,
chloroform has an affinity for the red blood corpuscles. Chloroform
stimulates the peripheral ends of the nerves of sensation, so that it
causes irritation of the skin or mucous membranes when locally applied.
Flourens considers that chloroform first affects the cerebrum, then the
cerebellum, and finally the spinal cord; the action is at first stimulating,
afterwards paralysing. Most anaesthetics diminish equally the ex-
citability of the grey and the white nervous substance of the brain,
and this is the case with chloroform, ether, and morphine; but
apparently this is not the case with chloral hydrate, which only
diminishes the conductivity of the cortical substance of the brain, and
leaves the grey substance intact. Corresponding to the cerebral para-
lysis, the blood-pressure sinks, and the heart beats slower and weaker.”
The Hyderabad Commission made 735 researches on dogs and monkeys,
and found that in fatal narcosis, so far as these animals are concerned,
the respiration ceased before the heart, and this may be considered the
normal mode of death; but it is probably going too far to say that it is
the exclusive form of death in man, for there have been published cases
in which the heart failed first.
§ 186. Symptoms. There is but little outward difference between
man and animals in regard to the symptoms caused by breathing
chloroform ; in the former we have the advantage that the sensations
preceding narcosis can be described by the individual.
The action of chloroform is usually divided into three more or less
distinct stages. In the first there is a “drunken' condition, changes
in the sense of smell and taste, and it may be hallucinations of vision
and hearing; there are also often curious creeping sensations about the
skin, and sometimes excessive muscular action, causing violent struggles.
Epileptiform convulsions are seen occasionally, and delirium is almost
always present. The face during this stage is generally flushed,
covered with perspiration, and the pupils contracted. The first stage
may last from one minute to several, and passes into the second stage,
or that of depression. Spontaneous movements cease, sensibility to all
external stimuli vanishes, the patient falls into a deep sleep, the con-
sciousness is entirely lost, and reflex movements are more and more
annihilated. The temperature is less than normal, the respirations are
slow, and the pulse is full and slow. The pupils in this stage are
usually dilated, all the muscles are relaxed, and the limbs can be bent
about in any direction. If now the inhalation of chloroform is inter-
mitted, the patient wakes within a period which is usually from twenty
to forty minutes, but may be several hours, after the last inhalation.
* Kobert's Lehrbuch der Intoxicationem.
§ 187, 188.] , , CHLOROFORM. I 59
The third stage is that of paralysis; the pulse becomes irregular, the
respirations superficial, there is a cyanotic colouring of the lips and skin,
while the pupils become widely dilated. Death follows quickly through
paralysis of the respiratory centre, the respirations first ceasing, then
the pulse; in a few cases, the heart ceases first to beat.
According to Sansom's facts,” in 100 cases of death by chloroform
44-6 per cent. occurred before the full narcosis had been attained, that
is in the first stage, 34-7 during the second stage, and 20.6 shortly after.
So, also, Kappeler has recorded that in 101 cases of death from chloro-
form, 47.7 per cent. occurred before the full effect, and 52:2 during the
full effect. This confirms the dictum of Billroth, that in all stages of
anaesthesia by chloroform, death may occur. The quantity of chloroform,
which, when inhaled in a given time, will produce death, is unknown ;
for all depends upon the greater or less admixture of air, and probably
on other conditions. It has been laid down, that the inhalation of
chloroform should be so managed as to ensure that the air breathed shall
never contain more than 3.9 per cent. of chloroform. Fifteen drops have
caused death ; but Taylor, on the other hand, records a case of tetanus,
treated at Guy's Hospital, in which no less a quantity than 700 grms.
(22.5 ozs.) was inhaled in twenty-four hours. Frequent breathing of
chloroform in no way renders the individual safe from fatal accident.
A lady f having repeatedly taken chloroform, was anaesthetised by the
same agent merely for the purpose of having a tooth extracted. About
6 grims. (1-5 drm.) were poured on a cloth, and after nine to ten inspira-
tions, dangerous symptoms began—rattling breathing and convulsive
movements—and, despite all remedies, she died.
§ 187. Chronic chloroform poisoning is not unknown. It leads to
various ailments, and seems to have been in one or two instances the
cause of insanity.
Buchner records the case of an opium-eater, who afterwards took to
chloroform ; he suffered from periodic mania. In a remarkable case
related by Meric, the patient, who had also first been a morphine-eater,
took 350 grims, of chloroform in five days by inhalation; as often as he
woke he would chloroform himself again to sleep. In this case, there
was also mental disturbance, and instances in which chloroform produced
marked mental aberration are recorded by Böhm ; and by Wiglas
§ 188. Post-mortem Appearances.—The lesions found on section
are neither peculiar to, nor characteristic of, chloroform poisoning. It
has been noted that bubbles of gas are, from time to time, to be
observed after death in the blood of those poisoned by chloroform, but
it is doubtful whether the bubbles are not merely those to be found in
* Op. cit. t Edim. Med. Jowrm., 1855.
# Ziemssen’s Handbuch, Bd. xv. § Med. Tinnes, 1855.
I6O POISONS : THEIR EFFECTS AND DETECTION. [$ 189.
any other corpse—in 189 cases, only eighteen times were these gas-
bubbles observed,” so that, even if they are characteristic, the chances
in a given case that they will not be seen are greater than the reverse.
The smell of chloroform may be present, but has been noticed very
seldom.
§ 189. The detection and estimation of chloroform from organic
substances is not difficult, its low boiling-point causing it to distil readily.
Accordingly (whatever may be the ultimate modifications, as suggested
by different experimenters), the first step is to bring the substances,
unless fluid, into a pulp with water, and submit this pulp to distillation
by the heat of a water-bath. If the liquid operated upon possesses no
particular odour, the chloroform may in this way be recognised in the
distillate, which, if necessary, may be redistilled in the same manner,
so as to concentrate the volatile matters in a small compass.
There are four chief tests for the identification of chloroform :-
(1) The final distillate is tested with a little aniline, and an alcoholic
solution of soda or potash lye ; either immediately, or upon gently
warming the liquid, there is a peculiar and penetrating odour of phenyl-
carbylamine, C.H.NC; it is produced by the following reaction:—
CHCl2 + 3 KOH + Cº. H.NH,--CBI,NC +3KCl +3H,0.
Chloral, trichloracetic acid, bromoform and iodoform also give the same
reaction; on the other hand, ethylidene chloride does not yield under
these circumstances any carbylamine (isonitrile).
(2) Chloroform reduces Fehling's alkaline copper solution, when
applied to a distillate, thus excluding a host of more fixed bodies which
have the same reaction; it is a very excellent test, and may be made
quantitative. The reaction is as follows:—
CHCl, + 5.KHO + 2CuO = Cu,0+ K2CO, +3KCl +3H,0;
thus, every 100 parts of cuprous oxide equals 83-75 of chloroform.
(3) The fluid to be tested (which, if acid, should be neutralised) is
distilled in a slow current of hydrogen, and the vapour conducted
through a short bit of red-hot combustion tube containing platinum
gauze. Under these circumstances, the chloroform is decomposed and
hydrochloric acid formed ; hence, the issuing vapour has an acid re-
action to test paper, and if led into a solution of silver nitrate, gives the
usual precipitate of argentic chloride. Every 100 parts of silver chloride
equal 27-758 of chloroform.
(4) The fluid is mixed with a little thymol and potash; if chloro-
form be present, a reddish-violet colour is developed, becoming more
distinct on the application of heat.f
* Schauenstein (op. cit.).
+ S. Vidali in Deutsch-Amerikan. Apoth. -Zeitung, vol. iij., Aug. 15, 1882.
§ 190, 191.] CHLORAL. I6 I
§ 190. For the quantitative estimation of chloroform the method
recommended by Schmiedeberg” is, however, the best. A combustion
tube of 24 to 26 cm. long, and 10 to 12 mm. in diameter, open at both
ends, is furnished at the one end with a plug of asbestos, while the
middle part, to within 5–6 cm. of the other end, is filled with pieces of
caustic lime, from the size of a lentil to that of half a pea. The lime
must be pure, and is made by heating a carbonate which has been pre-
cipitated from calcic nitrate. The other end of the tube is closed by a
cork, carrying a silver tube, 16–18 cm. long, and 4 mm. thick. The
end containing the asbestos plug is fitted by a cork to a glass tube.
The combustion tube thus prepared is placed in the ordinary combustion
furnace ; the flask containing the chloroform is adapted, and the dis-
tillation slowly proceeded with. It is best to add a tube, bent at right
angles and going to the bottom of the flask, to draw air continuously
through the apparatus. During the whole process, the tube containing
the lime is kept at a red heat. The chloroform is decomposed, and the
chlorine combines with the lime. The resulting calcic chloride, mixed
with much unchanged lime, is, at the end of the operation, cooled, dis-
solved in dilute nitric acid, and precipitated with silver nitrate. Any
silver chloride is collected and weighed and calculated into chloroform.f
WI.—Chloral.
§ 191. Chloral Hydrate (C.HCl2O, H2O) is made by mixing equivalent
quantities of anhydrous chloral f and water. The purest chloral is in
the form of small, granular, sugar-like crystals. When less pure, the
crystals are larger. These melt into a clear fluid at from 48° to 49°,
and the melted mass solidifies again at 48.9°. Chloral boils at 97-5°;
it is not very soluble in cold chloroform, requiring four times its weight.
The only substance with which chloral hydrate may well be confused is
chloral alcoholate (C, H,Cl2O3), but chloral alcoholate melts at a lower
temperature (45°), and boils at a higher (113-5°); it is easily soluble
* Ueber die quantitative Bestimmung des Chloroforms im Blute. Inaug. Dissert.,
Dorpat, 1866.
t S. Vidali has made the ingenious suggestion of developing hydrogen in the
usual way, by means of zinc and sulphuric acid, in the liquid supposed to contain
chloroform, to ignite the hydrogen, as in Marsh's test, when it issues from the tube,
and them to hold in the flame a clean copper wire. Since any chloroform is burnt up
in the hydrogen flame to hydrochloric acid, the chloride of copper immediately
volatilises and colours the flame green.
# Anhydrous chloral (C2HCl2O) is an oily liquid, of specific gravity 1-502 at 18° ;
it boils at 97.7°. It is obtained by the prolonged action of chlorine on absolute
alcohol.
II
I62 POISONS: THEIR EFFECTS AND DETECTION. [Š 192, 193.
in cold chloroform, and inflames readily, whereas chloral scarcely
burns.
Chloral hydrate completely volatilises, and can be distilled in a
vacuum without change. If, however, boiled in air, it undergoes slow
decomposition, the first portions of the distillate being overhydrated, the
last underhydrated; the boiling-point, therefore, undergoes a continuous
rise. The amount of hydration of a commercial sample is of practical
importance; if too much water is present, the chloral deliquesces, espe-
cially in warm weather; if too little, it may become acid, and in part
insoluble from the formation of meta-chloral (C6H3Cl2O3). Chloral
hydrate, by the action of the volatile or fixed alkalies, is decomposed, an
alkaline formate and chloroform resulting thus—
C.HCl,0, H,0+ NaHO->NaCHO,--H,0+CHCl,
Trichlor-acetic acid is decomposed in a similar manner.
Statistics.-Chloral caused, during the ten years ending 1903, in
England and Wales, 96 deaths—viz., 82 (66 males, 16 females) acci-
dentally, and 14 (12 males, 2 females) from suicide.
§ 192. Detection.—It is, of course, obvious that after splitting up
chloral into chloroform, the latter can be detected by distillation and
applying the tests given at p. 160 and seq. Chloral hydrate is soluble
in one and a half times its weight of water; the solution should be
perfectly neutral to litmus. It is also soluble in ether, in alcohol, and
in carbon disulphide. It may be extracted from its solution by shaking
out with ether. There should be no cloudiness when a solution is tested
with silver nitrate in the cold; if, however, to a boiling solution nitrate
of silver and a little ammonia are added, there is a mirror of reduced
silver.
§ 193. The assay of chloral hydrate in solutions is best effected by
distilling the solution with slaked lime; the distillate is received in
water contained in a graduated tube kept at a low temperature. The
chloroform sinks to the bottom, and is directly read off; the number of
c.c. multiplied by 2-064 equals the weight of the chloral hydrate
present,
Another method, accurate but only applicable to the fairly pure sub-
stance, is to dissolve 1 to 2 grims. in water, remove any free acid by
baric carbonate, and then treat the liquid thus purified by a known
volume of standard soda. The Soda is now titrated back, using litmus
as an indicator; each c.c. of normal alkali neutralised by the sample
corresponds to 0-1655 grn. of chloral hydrate. Small quantities of
chloral hydrate may be conveniently recovered from complex liquids by
shaking them up with ether, and removing the ethereal layer. A con-
venient tube for this purpose suitable for either liquids which like ether
*
§ 194] CHLORAL, I63
float to the top, or like chloroform sink to the bottom, is represented in
the accompanying illustration. A is a mercury reservoir connected with
a graduated tube T.; a two-way stopcock S permits liquids to be drawn
in through the thistle-head funnel or expelled by the side tube; when
chloroform is used it can be removed through a lower two-way stopcock
g, by the tube d. The ether may be allowed to evaporate spontaneously;
but there is in this way much loss of chloral. The best method of
estimating minute quanti-
ties is to alkalise the liquid,
and slowly distil the vapour A
through a red-hot combus-
tion tube charged with pure
lime, as in the process de-
scribed at p. 161. A dilute
solution of chloral may also
be treated with a zinc-
copper couple ; the nascent
hydrogen breaks the mole-
cule up, and the resulting
chloride may be titrated,
as in water analyses, by
silver nitrate and potassic
chromate.
§ 194. Effects of
Chloral Hydrate on Ani-
mals. – Experiments on
animals have taught us all
that is known of the physio-
logical action of chloral.
It has been shown that the
drug influences very con-
siderably the circulation,
at first exciting the heart's
action, and then paralysing the automatic centre. The heart, as in
animals poisoned by atropine, stops in diastole, and the blood-pressure
sinks in proportion to the progressive paralysis of the cardiac centre.
At the same time, the respiration is slowed and finally ceases, while
the heart continues to beat. The body temperature of the warm-
blooded animals is very remarkably depressed, according to Falck, even
to 7.6°. Vomiting has been rather frequently observed with dogs and
cats, even when the drug has been taken into the system by subcutaneous
injection.
The secretion of milk, according to Röhrig, is also diminished. Reflex


I64 POISONs: THEIR EFFECTS AND DETECTION. [Š 195, 196.
actions through small doses are intensified; through large, much
diminished. 025–05 grnm, (-4-7 grain), injected subcutaneously into
frogs, causes a slowing of the respiration, a diminution of reflex excita-
bility, and lastly, its complete cessation; this condition lasts several
hours; at length the animal returns to its normal state. If the dose is
raised to 1 grm. (1.5 grain) after the cessation of reflex movements, the
heart is paralysed—a paralysis not due to any central action of the
vagus, but to a direct action on the cardiac ganglia. Rabbits of the
ordinary weight of 2 kilos. are fully narcotised by the subcutaneous
injection of 1 grn. ; the sleep is very profound, and lasts several hours;
the animal wakes up spontaneously, and is apparently none the worse.
If 2 grims. are administered, the narcotic effects, rapidly developed, are
much prolonged. There is a remarkable diminution of temperature, and
the animal dies, the respiration ceasing without convulsion or other sign.
Moderate-sized dogs require 6 grns, for a full narcosis, and the symptoms
are similar ; they also wake after many hours, in apparent good health.*
§ 195. Liebreich considered that the action of chloral was due to
its being broken up by the alkali of the blood, and the system being thus
brought into a state precisely similar to its condition when anaesthetised
by chloroform vapour. This view has, however, been proved to be
erroneous. Chloral hydrate can, it is true, be decomposed in some degree
by the blood at 40”; but the action must be prolonged for several hours.
A 1 per cent. solution of alkali does not decompose chloral at a blood-heat
in the time within which chloral acts in the body ; and since narcotic
effects are commonly observed when, in the fatty group, hydrogen has
been displaced by chlorine, it is more probable that chloral hydrate is
absorbed and circulates in the blood as such, and is not broken up into
chloroform and an alkaline formate.
§ 196. Effects of Chloral Hydrate on Man.-Since the year 1869,
in which chloral was first introduced to medicine, it has been the cause
of a number of accidental and other cases of poisoning. In mearly all
the cases the poison was taken by the mouth, but in one instance the
patient died in three hours, after having injected into the rectum 5-86
grims, of chloral hydrate. There is also on record a case in which, for
the purpose of producing surgical anaesthesia, 6 grns, of chloral were
injected into the veins; the man died in as many minutes.f
* C. Ph. Falck has divided the symptoms into—(1) preliminary hypnotic ; (2) an
adynamic state; and (3) a comatose condition.
+ This dangerous practice was introduced by M. Ore. In a case of traumatic
tetanus, in which M. Ore injected into the veins 9 grms, of chloral in 10 grms, of
water, there was profound insensibility, lasting eleven hours, during which time a
painful operation on the thumb was performed. The next day 10 grms, were in-
jected, when the insensibility lasted eight hours; and 9 grns, were injected on each
of the two following days. . The man recovered. In another case, Ore anaesthetised
§ 197.] CHLORAL. 165
§ 197. Fatal Dose.—It is impossible to state with any exactness the
precise quantity of chloral which may cause death. Children bear it
better, in proportion, than adults, while old persons (especially those
with weak hearts, and those inclined to apoplexy) are likely to be strongly
affected by very small doses. A dose of 19 grm. (3 grains) has been
fatal to a child a year old in ten hours. On the other hand, according
to Bouchut's observations on 10,000 children, he considers that the full
therapeutic effect of chloral can be obtained safely with them in the
following ratio —
Children of 1 to 3 years, dose 1 to 1.5 grm. (15°4 to 23°1 grains)
3 y 3, 5 , , , , 2, 3 , , (30-8 , , 46.3 , , )
3 y 5, 7 , , , , 3, 4 », (46'3. , 61-7 , , )
—these quantities being dissolved in 100 c.c. of water.
These doses are certainly too high, and it would be dangerous to take
them as a guide, since death has occurred in a child, aged 5, from a dose
of 3 grms. (46.3 grains). Medical men in England consider 20 grains a
very full dose for a child of 4 years old, and 50 for an adult, while a
case is recorded in which a dose of 19 grm. (30 grains) proved fatal in
thirty-five hours to a young lady aged 20. On the other hand, we find
a case * in which, to a patient suffering from epileptic mania, a dose of
31.1 grims. (1:1 oz.) of chloral hydrate was administered ; she sank into a
deep sleep in five minutes. Subcutaneous injections of strychnine were
applied, and after sleeping for forty-eight hours, there was recovery. On
the third day a vivid Scarlatinal rash appeared, followed by desquamation.
The examples quoted—the fatal dose of 19 grim., and recovery from 31
grms.-are the two extremes for adults. From other cases, it appears
tolerably plain that most people would recover, especially with appropriate
treatment, from a single dose under 8 grns., but anything above that
quantity taken at one time would be very dangerous, and doses of 10
grms, and above, almost always fatal. If, however, 8 grims, were taken in
divided doses during the twenty-four hours, it could (according to Sir
B. W. Richardson) be done with safety. The time from the taking of the
poison till death varies considerably, and is in part dependent on the dose.
In seven cases of lethal poisoning, three persons who took the small
doses of 1:25, 2:5, and 1.95 grims, respectively, lived from eight to ten
hours; two, taking 4 and 5 grims, respectively, died very shortly after
the administration of the chloral. In a sixth case, related by Brown, in
immediately a patient by plunging the subcutaneous needle of his syringe into the
radial vein, and injected 10 grms. of chloral hydrate with 30 of water. The patient
became insensible before the whole quantity was injected with “une immobilité rap-
pellant celle du cadavre.” On finishing the operation, the patient was roused imme-
diately by the application of an electric current, one pole on the left side of the neck,
the other on the epigastrium. Journ. de Pharm. et de Chimie, t. 19, p. 314.
* Chicago Medical Review, 1882.
I66 POISONs: THEIR EFFECTS AND DETECTION. [Š 198, 199.
which 3-12 grms. had been taken, the patient lived an hour; and in
another, after a dose of 5 grums., recorded by Jolly, death took place
within a quarter of an hour.
§ 198. Symptoms.-With moderate doses there are practically no
symptoms, save a drowsiness coming on imperceptibly, and followed by
heavy sleep. With doses up to 2 grnms. (30-8 grains), the hypnotic state
is perfectly under the command of the will, and if the person chooses to
walk about or engage in any occupation, he can ward off sleep; but with
those doses which lead to danger, the narcosis is completely uncontrol-
lable, the appearance of the sleeper is often strikingly like that of a
drunken person. There is great diminution of temperature commencing
in from five to twenty minutes after taking the dose—occasionally sleep
is preceded by a delirious state. During the deep slumber the face is
much flushed, and in a few cases the sleep passes directly into death
without any marked change. In others, symptoms of collapse appear,
and the patient sinks through exhaustion.
With some persons doses, which, in themselves, are insufficient to
cause death, yet have a peculiar effect on the mental faculties. A case
of great medico-legal interest is described by the patient himself, Dr.
Manjot.” He took in three doses, hourly, 12 grms. of chloral hydrate.
After the first dose the pain, for which he had recourse to chloral,
vanished ; but Manjot, although he had all the appearance of being per-
fectly conscious, yet had not the slightest knowledge of what he was
doing or speaking. He took the other two doses, and sank into a deep
sleep which lasted twelve hours. He then awoke and answered ques-
tions with difficulty, but could not move ; he lay for the next twelve
hours in a half slumber, and the following night slept soundly—to wake
up recovered. -
§ 199. The treatment of acute chloral poisoning which has been most
successful is that by strychnine injections, and the application of
warmth to counteract the loss of temperature which is so constant a
phenomenon. As an illustration of the treatment by Strychnine, an
interesting case recorded by Levinstein i may be quoted.
A man, 35 years old, took at one dose, for the purpose of suicide,
24 grns. of chloral hydrate. In half an hour afterwards he was
found in a deep sleep, with flushed face, swollen veins, and a pulse 160
in the minute. After a further half hour, the congestion of the head
was still more striking; the temperature was 39.5°; the pulse hard and
bounding 92; the breathing laboured, at times intermittent.
Artificial respiration was at once commenced, but, in spite of this, in
about another half-hour the face became deadly pale, the temperature
sank to 32.9°. The pupils contracted and the pulse was scarcely to be
* Gaz, des Hop., 1875. f Vierteljahrsschº'. f. ger. Med., Bd. xx., 1874.
§ 200.] CHLORAL. 167
felt ; 3 mgrims. ('04 grain) of strychnine were now injected subcutane-
ously; this caused tetanic convulsions in the upper part of the body
and trismus. The heart's action again became somewhat stronger, the
temperature rose to 33'3", and the pupils dilated; but soon followed,
again, depression of the heart's action, and the respiration could only be
kept going by faradisation. Two mgrms. ('03 grain) of strychnine
were once more injected, and the heart's action improved. During the
succeeding six hours the respiration had to be assisted by faradisation.
The temperature gradually rose to 36.5°; ten hours after taking the
dose the patient lay in a deep sleep, breathing spontaneously and
reacting to external stimuli with a temperature of 38.5°. Eighteen
hours from the commencement, the respiration again became irregular,
and the galvanic current was anew applied. The last application
aroused the sleeper, he took some milk and again slept ; after twenty-
seven hours he could be awakened by calling, etc., but had not full con-
sciousness; he again took some milk and sank to sleep. It was not
until thirty-two hours had elapsed from the ingestion of the poison that
he awoke spontaneously; there were no after-effects.
§ 200. Chronic Poisoning by Chloral Hydrate.—An enormous mum-
ber of people habitually take chloral hydrate. The history of the habit
is usually that some physician has given them a chloral prescription for
neuralgia, for loss of sleep, or other cause, and finding that they can
conjure sleep, oblivion, and loss (it may be) of suffering whenever they
choose, they go on repeating it from day to day until it becomes a
necessity of their existence. A dangerous facility to chloral-drinking is
the existence of patent medicines, advertised as sleep-producers, and
containing chloral as the active ingredient. A lady, aged 35, died in
1876, at Exeter, from an overdose of “Hunter's solution of chloral, or
sedative draught and sleep producer.” Its strength was stated at the
inquest to be 25 grains to the drachm (41.6 per cent.).”
The evil results of this chloral-drinking are especially to be looked
for in the mental faculties, and the alienists have had since 1869 a new
insanity-producing factor. In the asylums may usually be found
several cases of melancholia and mania referred rightly (or wrongly) to
chloral-drinking. Symptoms other than cerebral are chilliness of the
body, inclination to fainting, clonic convulsions, and a want of co-ordina-
tion of the muscles of the lower extremities. In a case recorded by
Husband,i a lady, after twelve days’ treatment by chloral hydrate, in
doses of from 1 to 2 grims. (15.4 to 30°S grains), suffered from a scar-
latina-like rash, which was followed by desquamation. Among the
insane, it has also been noticed that its use has been followed by nettle-
rash and petechiae (Reimer and others).
* Eaceter and Plymouth Gazette, Jan. 12, 1876. | Lancet, 1871.
I68 POISONS: THEIR EFFECTS AND DETECTION. [$ 201, 202.
§ 201. Excretion of Chloral.—Chloral hydrate is separated in the
urine partly as urochloral acid (C,EI, Cl,0). Butylchloral is separated
as urobutylchloral acid (Clo HigCl,O.). Urochloral acid is crystalline,
soluble in water, in alcohol, and in ether, reduces copper from Fehling's
Solution, and rotates a ray of polarised light to the left. Urochloral
acid, on boiling with either dilute sulphuric or hydrochloric acid, splits
up into trichlorethyl alcohol and glycuronic acid—
CŞHuCl2O, + H2O -> C, HgCl2O + CoEIloC).
Trichloralcohol is an oily fluid (boiling-point 150°–152"); it yields by
Oxidation trichloracetic acid. -
Urobutylchloral acid gives, on treatment with mineral acids, trichlor-
butyl alcohol and glycuronic acid.
To separate urochloral acid from the urine the following process has
been found successful:— * -
The urine is evaporated to a syrup at the heat of the water-bath,
and then strongly acidulated with sulphuric acid and repeatedly shaken
out in a separating tube with a mixture of 3 vols, of ether and 1 vol. of
alcohol. The ether-alcohol is separated and distilled off, the acid resi-
due is neutralised with KHO, or potassic carbonate, and evaporated;
the dry mass is then taken up with 90 per cent. alcohol, the filtrate
precipitated with ether, and the precipitate washed with ether and
absolute alcohol.
Next the precipitate is boiled with absolute alcohol and filtered hot.
On cooling, the potassium salt of urochloral acid separates out in tufts
of silky needles. The crystals are dried over sulphuric acid and again
washed several times with absolute alcohol and ether to remove
impurities. .
To obtain the free acid, the potassium salt is dissolved in a little
water and acidulated with hydrochloric acid; the liquid is then shaken
out in a separating tube, with a mixture of 8 vols. of ether and 1 of
alcohol. The ether-alcohol is distilled off, the residue treated with
moist silver oxide until no farther separation of silver chloride occurs,
the silver chloride is separated by filtration, the soluble silver salt decom-
posed by SH2, and the filtrate carefully evaporated to a syrup; after a
few hours, the acid crystallises in stars of needles.
Urobutylchloral acid can be obtained in quite a similar way.”
§ 202. Separation of Chloral from Organic Matters.--It will be
most convenient to place the organic fluid or pulped-up solid, mixed
with water, in a retort, to acidify with tartaric acid, and to distil. -
Chloral hydrate distils over from a liquid acidified with tartaric
* W. Mering u. Musculus, Ber., viii. 662; v. Mering, ibid., xv. 1019; E. Kulz,
Ber., xv. 1538. ,
§ 202.] CHLORAL. -- 169
acid ; to obtain the whole of the chloral requires distillation in a
vacuum almost to dryness.
The distillation will, unless there is also some partly decomposed
chloral, not smell of chloroform, and yet give chloroform reactions.
To identify it, to the distillate should be added a little burnt
magnesia, and the distillate thus treated boiled for half an hour in a
flask connected with an inverted condenser; in this way the chloral
hydrate is changed into chloroform * and magnesium formate—
2CC1,OH(OH)2 + MgO – 2CHCl2 + (HCOO),Mg+ H2O.
The fluid may now be tested for formic acid : it will give a black pre-
cipitate with solution of silver nitrate— .
(HCOO),Mg+4AgNO3=4Ag+ Mg(NO3)2 + 2CO2 + 2HNO3,
It will give a white precipitate of calomel when treated with mercuric
chloride solution—
(HCOO),Mg+4HgCl, -2Hg2Cl2 + MgCl, + 2 HCl + 2CO3.
Chloral (or chloroform), when boiled with resorcinol and the liquid
made strongly alkaline with NaHO, gives a red colour, which disappears
on acidifying and is restored by alkalies. If, on the other hand, there
is an excess of resorcinol and only a very small quantity of NaHO used,
the product shows a yellowish-green fluorescence; ºr of a milligramme
of chloral hydrate gives this reaction distinctly when boiled with 50
mgrms. of resorcinol and 5 drops of a normal solution of sodium
hydrate.f
Dr. Frank Ogston ; has recommended sulphide of ammonium to be
added to any liquid as a test for chloral. The contents of the stomach
are filtered or submitted to dialysis, and the test applied direct. If
chloral is present, there is first an orange-yellow colour; on standing,
the fluid becomes more and more brown, then troubled, an amorphous
precipitate falls to the bottom, and a peculiar odour is developed.
With 10 mgrms. of chloral in 1 c.c. of water, there is an evident pre-
cipitate, and the odour can readily be perceived ; with 1 mgrm. dissolved
in 1 c.c. of water, there is an orange-yellow colour, and also the odour,
but no precipitate ; with 1 mgrim. in 1 c.c. of water, there is a weak,
pale, straw-yellow colour, which can scarcely be called characteristic.
The only substance giving in neutral solutions the same reactions is
* Kippenberger (Arch. Pharm., ccxxxviii., 1900) states that when chloroform is
distilled with an alkali some of it is decomposed, giving carbon monoxide and a
chloride. The carbon monoxide may be estimated by means of palladium chloride.
One part of metallic palladium = 1 12-6 parts of chloroform.
+ C. Schwarz, Pharm. Zeit., xxxiii. 419.
+ Vierteljahrsschrift f. gericht!. Medicin, 1879, Bd. xxx. Hiſt. 1, S. 268.
I7o PbISONS: THEIR EFFECTS AND DETECTION. [$ 203–207.
antimony; but, on the addition of a few drops of acid, the antimony
falls as an orange-yellow precipitate, while, if chloral alone is present,
there is a light white precipitate of sulphur.
VII.-Minor Anaesthetics and Narcotics.
§ 203. When chlorine acts upon marsh-gas, the hydrogen can be displaced atom
by atom ; and from the original methane (CHA) can be successively obtained chloro-
methane or methyl chloride (CH3Cl), dichloromethane, or methene dichloride,
methylene dichloride (CH2Cl2), trichloromethane, or chloroform (CHCl3), already
described, and carbon tetrachloride (CCl3). All these are, more or less, capable of
producing anaesthesia ; but none of them, save chloroform, are of any toxicological
importance.
Metheme dichloride, recommended by Sir B. W. Richardson as an anaesthetic, has
come somewhat into use. It is a colourless, very volatile liquid, of specific gravity
1'360, and boiling at 41°. It burns with a smoky flame, and dissolves iodine with a
brown colour.
§ 204. Pentane (C5H12).—There are three isomers of pentane ; that which is
used as an anaesthetic is normal pentane, CH3 – CH2 – CH2 – CH2 – CH3 ; its boiling -
point is 37-38.” It is one of the constituents of petroleum ether.
Under the name of “Pental" it is used in certain hospitals extensively, for
instance, at the Kaiser Friederich's Children's Hospital, Berlin.” It is stated to
have no action on the heart. -
One death + has been recorded from its use :-A lad, aged 14, was put under
pental for the purpose of having two molars painlessly extracted. He was only a
minute or two insensible, and 4–5 grims. of pental was the quantity stated to have
been inhaled. The boy spat out after the operation, then suddenly fainted and died.
The post-mortem showed Oedema of the lungs; the right side of the heart was empty.
The organs of the body smelled strongly of pental.
O
§ 205. Aldehyde (Acetaldehyde), C2H4O or CH,-có , a fluid obtained by the
. H
careful oxidation of alcohol (boiling-point, 20°8°), is in large doses toxic ; in smaller,
it acts as a narcotic.
Metaldehyde (C2H4O2)2, obtained by treating acetaldehyde at a low temperature
with hydrochloric acid. It occurs in the form of prisms, which sublime at about
112° ; it is also poisonous.
§ 206. Paraldehyde (C6H12O3) is a colourless fluid, boiling at 124°; specific gravity
'998 at 15°. By the action of cold it may be obtained in crystals, the melting-
point of which is 10.5°. It is soluble in eight parts of water at 13°; in warm water
it is less soluble ; hence, on Warming a solution, it becomes turbid. Paraldehyde is
said to paralyse the anterior cornua of spinal cord. In two recorded cases + of
poisoning there was unconsciousness, perspiration, shallow breathing, and inter-
mittent pulse.
Treatment with amyl nitrite and strychnine has proved effective.
§ 207. Somoform.S.—This is a mixture of ethyl chloride, 65 parts; methyl chloride,
* Zeit. f. Kinderheilk., Bd. iii.-iv., 1893. -
| Dr. Bremme, Vierteljahrsschº'. f. gerichtliche Medicin, Bd. v., 1893.
† Lancet, Sept. 23, 1900, 875; and Sept. 6, 1902.
§ Proc. Physiol. Soc., XXV., 1903.
§ 208.] MINOR ANAESTHETICS AND NARCOTICS. 17 I
30 parts; and ethyl bromide, 5 parts. In toxic doses it causes death by tonic
stoppage of diaphragm while the heart still beats strongly.
§ 208. Sulphones—Sulphonal, Trional, Tetronal.—Of these, sulphonal, trional,
and tetronal are in commerce, and much in use as narcotics. The sulphones are
regarded as urethane, in which the hydrogen atoms are replaced by alkyl and
alkyl sulphonic radicles; thus sulphonal is a dimethyl sulphone diethyl ethane,
m. p. 126°,
CH3 SO2-C2H5
N /
C
/ N
CH3 SO2-C2H5
Trional, m.p. 75°, is a monomethyl-ethyl sulphone-di-ethyl ethane,
CH3 SO.C.,H,
N /
/ N
C2H5 SO2C2H5
while tetronal, m.p. 85°, is a diethyl sulphone diethyl ethane.
Bauman and Kast “ have shown that there is a relation between narcotic power
and the number of ethyl groups, dimethyl sulphone-dimethyl ethane being without
action, while the corresponding ethyl (tetronal) compound exercises the strongest
narcotic action ; if a sulphonal methyl group is replaced by phenyl CºHº no narcotic
action is produced, but if both methyl groups are replaced as in diphenyl diethyl
sulphone methame, C6H5C(SO2C3H5)2C6H5, an intense poison is produced, the fatal
dose for cats being 0°5 grm, per kilo.
The ordinary sleeping dose of sulphonal for adults is from 10 to 20 grains
('65 grm. – 13 grim.); single occasional doses of this magnitude do not seem to
appreciably affect the health, but if taken day after day serious changes may be
produced. A woman f aged 53, took for some time 15 grains (1 grnm.) of sulphonal.
At last there was marked mental confusion, difficulty of speech, and a peculiar
sighing dyspnoea. The urine was tinged a deep pink colour, stiffness and paralysis
of both legs soon developed, and death; the pathological changes were fatty degenera-
tion of the heart, liver, and kidneys.
J. C. Whatley, M.R.C.S., f records a case in which a single dose of 20 grains
apparently produced an attack of urticaria. If suitable treatment is at hand large
doses may be recovered from. A single woman, Š aged 27, suffering from melancholia,
took 365 grains (23.9 grim.) with suicidal intent. Twelve hours after taking the
poison she was discovered profoundly comatose; there was no corneal reflex, and the
knee-jerks and the radial reflexes were absent. She was treated by Washing the
stomach out and subcutaneous injections of sº grain of Strychnine and ºn grain of
digitalin. She completely recovered in about eight days.
There are but few cases of poisoning by trional on record. Dr. Warren Coleman ||
describes an interesting case in which a woman aged 35 took, during seventy-two hours,
9 drachms (about 32 grims.) of trional. She was at the time suffering from delirium,
the result of alcoholic excess. She became somnolent, but was easily roused. There
was no disturbance of the circulation or respiration. The speech was thick and the
gait ataxic. There was no hemato-porphyuria. Recovery was ultimately complete.
* H. Hildebrant, Arch. f. eaſper. Path, u. Pharm., Bol. liii.
† Lancet, July 28, 1900.
† Lancet, April 9, 1904.
§ Alfred E. Hind, Lancet, Jan. 28, 1904.
|| Med. News, July 28, 1900.
I72 POISONS: THEIR EFFECTS AND DETECTION. [$ 209–2 II.
The sulphones described above may be shaken out of a feebly alkaline solution
by ether. -
Organic matters are extracted by 90 per cent. hot alcohol ; the liquid is cooled,
filtered and freed from alcohol by distillation; the residual liquid is filtered while hot,
made feebly alkaline by means of KHO, and shaken out in a separating funnel by ether.
The ethereal solution is evaporated to dryness and leaves the sulphone in the form of
white crystals. That it is a sulphone may be proved as follows: fused with sodium-
peroxide, an orange-red mass results. A solution in water gives with sodium nitro-
prusside a purple colour, showing the presence of a polysulphide ; sulphur separates
when the mass is treated with hydrochloric acid, and a solution of chloride of barium
precipitates barium sulphate. A melting-point should be taken ; as before stated,
sulphonal melts at 126°, trional at 75°, and tetronal at 85°, all temperatures so far
apart as to admit of practical application for the purposes of identification.
§ 209. Veronal.—Diethyl-malonyl carbamide, and ethyl-butyryl carbamide,
diethyl-malonyl carbamide, and dipropyl-malonyl carbamide, all have a narcotic
action, the first being as powerful as sulphonal, and the last four times as strong.”
Diethyl-malonyl carbimide or diethyl-barbeturic acid is in commerce under the
name of veronal, and consists of small colourless transparent crystals melting at
190° C. The crystals are soluble in 145 parts of water at 20°, freely soluble in alcohol
and in ether. Boiled with caustic alkali it is converted into diethyl-malonic acid,
which, melting at 120° C., at above 170° forms CO2 and diethyl-acetic acid.
One death (suicidal) from veronal is reported to have taken place in Cornwall in
May 1904.
Dr. G. Fernandez Clarke f records a case in which 34 grammes were taken for
several nights, causing narcosis and erythematosis, the coma alternating with
delirium. -
VIII.-Bisulphide of Carbon.
§ 210. Bisulphide of carbon–carbon disulphide, carbon, Sulphide
(CS3)—is a colourless, volatile fluid, strongly refracting light. Commer-
cial samples have a most repulsive and penetrating odour, but chemi-
cally pure carbon sulphide has a smell which is not disagreeable. The
boiling-point is 47° ; the specific gravity at 0° is 1:293. It is very
inflammable, burning with a blue flame, and evolving sulphur dioxide ;
is little soluble in water, but mixes easily with alcohol or ether.
Bisulphide of carbon, on account of its solvent powers for sulphur,
phosphorus, oils, resins, caoutchouc, gutta-percha, etc., is in great
request in certain industries. It is also utilised for disinfecting purposes,
the liquid being burnt in a lamp.
§ 211. Poisoning by Carbon Bisulphide.—In spite of the cheapness
and numerous applications of this liquid, poisoning is very rare. There
appears to be a case on record of attempted self-destruction by this
agent, in which a man took 2 ozs. (56.7 c.c.) of the liquid, but without
a fatal result. The symptoms in this case were pallor of the face,
wide pupils, frequent and weak pulse, lessened bodily temperature, and
* E. Fischer and von Mering (Chem. Centr., 1903, i.).
t Lancet, Jan. 23, 1904.
§ 2 I 1.] BISULPHIDE of CARBON. I73
spasmodic convulsions. Carbon disulphide was detected in the breath
by leading the expired air through an alcoholic solution of triethyl-
phosphin, with which it struck a red colour. It could also be found in
the urine in the same way. An intense burning in the throat, giddiness,
and headache lasted for several days.
Experiments on animals have been frequent, and it is found to be
fatal to all forms of animal life. There is, indeed, no more convenient
agent for the destruction of various noxious insects, such as moths, the
weevils in biscuits, the common bug, etc., than bisulphide of carbon. It
has also been recommended for use in exterminating mice and rats.”
Different animals show various degrees of sensitiveness to the vapour;
frogs and cats being less affected by it than birds, rabbits, and guinea-
pigs. It is a blood poison; methaemoglobin is formed, and there is
disintegration of the red blood corpuscles. There is complete anaesthesia
of the whole body, and death occurs through paralysis of the respiratory
centre, but artificial respiration fails to restore life.
Chronic Poisoning.—Of some importance is the chronic poisoning
by carbon disulphide, occasionally met with in manufactures necessitat-
ing the daily use of large quantities for dissolving caoutchouc, etc.
When taken thus in the form of vapour daily for some time, it gives
rise to a complex series of symptoms which may be divided into two
principal stages—viz., a stage of excitement and one of depression. In
the first phase, there is more or less permanent headache, with consider-
able indigestion, and its attendant loss of appetite, nausea, etc. The
sensitiveness of the skin is also heightened, and there are curious
sensations of creeping, etc. The mind at the same time in some degree
suffers, the temper becomes irritable, and singing in the ears and noises
in the head have been noticed. In one factory a workman suffered from
an acute mania, which subsided in two days upon removing him from
the noxious vapour (Eulenberg). The sleep is disturbed by dreams, and,
according to Delpech,t there is considerable sexual excitement, but this
statement has in no way been confirmed. Pains in the limbs are a
constant phenomenon, and the French observers have noticed spasmodic
contractions of certain groups of muscles.
The stage of depression begins with a more or less pronounced anaes-
thesia of the skin. This is not confined to the outer skin, but also
affects the mucous membranes; patients complain that they feel as if
the tongue were covered with a cloth. The anaesthesia is very general.
In a case recorded by Bernhardt, I a girl, 22 years old, who had worked
* Cloëz, Compt. Rend., t. lxiii. 85.
f Mémoire sur les Accidents que developpe chez les ouvrières en caoutchouc du sul-
fure de carb. en vapewr, Paris, 1865.
† Ber. klin. Wochenschrift, No. 32, 1866.
I 74 POISONS: THEIR EFFECTS AND DETECTION. [$ 212–216.
six weeks in a caoutchouc factory, suffered from mental weak-
mess and digestive troubles; there were anaesthesia and algesis of the
whole skin. In these advanced cases the mental debility is very pro-
nounced, and there is also weakness of the muscular system. Paralysis
of the lower limbs has been noted, and in one instance a man had his
right hand paralysed for two months. It seems uncertain how long a
person is likely to suffer from the effects of the vapour after he is
removed from its influence. If the first stage of poisoning only is
experienced, then recovery is generally rapid ; but if mental and
muscular weakness and anaesthesia of the skin have been developed, a
year has been known to elapse without any considerable improvement,
and permanent injury to the health may be feared.
§ 212. Post-mortem Appearances.—The pathological appearances
found after sudden death from disulphide of carbon are but little
different to those found after fatal chloroform breathing.
§ 213. Detection and Separation of Carbon Disulphide.—The
extreme volatility of the liquid renders it easy to separate it from
organic liquids by distillation with reduced pressure in a stream of CO2.
Carbon disulphide is best identified by (1) Hofman's test, viz., passing
the vapour into an ethereal solution of triethyl-phosphin, (C.H.),P.
Carbon disulphide forms with triethyl-phosphin a compound which
crystallises in red scales. The crystals melt at 95° C., and have the
following formula—P(C.H.)3CS3. This will detect 0.54 mgrm. Should
the quantity of bisulphide be small, no crystals may be obtained, but
the liquid will become of a red colour. (2) CS, gives, with an alcoholic
solution of potash, a precipitate of potassic Xanthate, CS,C,E,OK.
§ 214. Xanthogenic acid or ethyloxide-sulphocarbonate (CS.C.H.OH) is pre-
pared by decomposing potassic Xanthogenate by diluted hydrochloric or sulphuric
acid. It is a colourless fluid, having an unpleasant odour, and a weakly acid and
rather bitter taste. It burns with a blue colour, and is easily decomposed at 24°,
splitting up into ethylic alcohol and hydric sulphide. It is very poisonous, and
has an anaesthetic action similar to bisulphide of carbon. Its properties are probably
due to CS, being liberated within the body.
§ 215. Potassic Xanthogenate (CS2C3H5OK) and potassic Xanthamylate
(CS.C.H.OK) (the latter being prepared by the substitution of amyl alcohol for ethyl
alcohol), both on the application of a heat below that of the body, develop CS2, and
are poisonous, inducing symptoms very similar to those already detailed. Reid Hunt
states that the fatal dose of pot. Xanthogenate for rodents (mice) lies between 0°4 and
0.5 grim, per kilo. of body weight; in non-fatal doses it is antagonistic to nitrates.
IX. —The Tar Acids-Phenol–Cresol.
§ 216. Carbolic Acid. Syn. Phenol, Phenol Alcohol, Phenylic
Hydrate; Phenic Acid; Coal-Tar Creasote.—The formula for carbolic
acid is C.H.HO. The pure substance appears at the ordinary tempera-
§ 217.] THE TAR ACIDS. I75
ture as a colourless solid, crystallising in long prisms; the fusibility of the
crystals is given variously by different authors: from our own observa-
tion, the pure crystals melt at 40°–41°, any lower melting-point being
due to the presence of cresylic acid or other impurity; the crystals
again become solid about 15°. Melted carbolic acid forms a colourless
limpid fluid, sinking in water. It boils under the ordinary pressure at
182", and distils without decomposition; it is very readily and
completely distilled in a vacuum at about the temperature of 100°.
After the crystals have been exposed to the air, they absorb water,
and a hydrate is formed containing 16.07 per cent. of water. The
hydrate melts at 17°, any greater hydration prevents the crystallisation
of the acid; a carbolic acid, containing about 27 per cent. of water,
and probably corresponding to the formula CH2O,2H,0, is obtained by
gradually adding water to carbolic acid so long as it continues to be
dissolved. Such a hydrate dissolves in 11-1 times its measure of water,
and contains 8:56 per cent. of real carbolic acid. Carbolic acid does
not redden litmus, but produces a greasy stain on paper, disappearing
on exposure to the air; it has a peculiar smell, a burning numbing
taste, and in the fluid state it strongly refracts light. Heated to a high
temperature it takes fire, and burns with a sooty flame.
When an aqueous solution of carbolic acid is shaken up with ether,
benzeme, carbon disulphide, or chloroform, it is fully dissolved by the
solvent, and is thus easily separated from most solutions in which it
exists in the free state. Petroleum ether, on the other hand, only
slightly dissolves it in the cold, more on warming. Carbolic acid mixes
in all proportions with glycerin, glacial or acetic acid, and alcohol. It
coagulates albumen, the precipitate being soluble in an excess of albumen ;
it also dissolves iodine, without changing its properties. It dissolves
many resins, and also sulphur, but, on boiling, sulphuretted hydrogen is
disengaged. Indigo blue is soluble in hot carbolic acid, and may be
obtained in crystals on cooling. Carbolic acid is contained in castoreum,
a secretion derived from the beaver, but it has not yet been detected in
the vegetable kingdom. The source of carbolic acid is at present
coal-tar, from which it is obtained by a process of distillation. There
are, however, a variety of chemical actions in the course of which
carbolic acid is formed.
§ 217. The common disinfecting carbolic acid is a dark reddish
liquid, with a very strong odour; at present there is very little phenol
in it; it is mainly composed of meta- and para-cresol. It is officinal in
Germany, and there must contain at least 50 per cent. of the pure
carbolic acid. The pure crystallised carbolic acid is officinal in our own
and all the Continental pharmacopoeias. In the British Pharmacopoeia,
a solution of carbolic acid in glycerin is officinal; the proportions are 1
176 POISONs: THEIR EFFECTS AND DETECTION. [$ 218, 219.
part of carbolic acid and 4 parts of glycerin, that is, strength by measure =
20 per cent. The Pharmacopoeia Germanica has a liquor matri carbolic?
made with 5 parts carbolic acid, 1 caustic soda, and 4 of water; strength
in carbolic acid = 50 per cent. There is also a strongly alkaline crude
sodic carbolate in use as a preservative of wood. The Privy Council
order of July 26, 1900, declares that liquid preparation of carbolic acid
and its homologue containing more than 3 per cent. of phenols shall,
except in certain cases connected with agriculture and horticulture, be
declared poisons within the meaning of the Pharmacy Act, 1868.
There are various disinfecting fluids containing amounts of carbolic
acid, from 10 per cent. upwards. Many of these are somewhat complex
mixtures, but, as a rule, any poisonous properties they possess are mainly
due to their content of phenol or cresol. A great variety of disinfecting
powders, under various names, are also in commerce, deriving their
activity from carbolic acid. Macdougall's disinfecting powder is made by
adding a certain proportion of impure carbolic acid to a calcic sulphite,
which is prepared by passing sulphur dioxide over ignited limestone.
Calvert's carbolic acid powder is made by adding carbolic acid to
the siliceous residue obtained from the manufacture of aluminic sulphate
from shale. There are also various carbolates which, by heating or de-
composing with sulphuric acid, give off carbolic acid. -
Carbolic acid soaps are also made on a large scale—the acid is free,
and some of the soaps contain as much as 10 per cent. In the inferior
carbolic acid soaps there is little or no carbolic acid, but cresylic takes
its place. Neither the soaps nor the powders have hitherto attained
any toxicological importance, but the alkaline carbolates are very
poisomous.
§ 218. The chief uses of carbolic acid are indicated by the foregoing
enumeration of the principal preparations used in medicine and com-
merce. The bulk of the carbolic acid manufactured is for the purposes
of disinfection. It is also utilised in the preparation of certain colouring
matters or dyes, and during the last few years has had another applica-
tion in the manufacture of salicylic acid. In medicine it is administered
occasionally internally, while the antiseptic movement in surgery,
initiated by Lister, has given it great prominence in surgical operations.
§ 219. Statistics.-The tar acids, i.e. pure carbolic acid and the
impure acids sold under the name of carbolic acid, but consisting (as
stated before) mainly of cresol, are, of all powerful poisons, the most
accessible, and the most recklessly distributed. We find them at the
bedside of the sick, in back-kitchens, in stables, in public and private
closets and urinals, and, indeed, in almost all places where there are
likely to be foul odours or decomposing matters. It is, therefore, no
wonder that poisoning by carbolic acid has, of late years, assumed large
§ 219) THE TAR ACIDS. 177
proportions. The acid has become vulgarised, and quite as popularly
known, as the most common household drugs or chemicals. This
familiarity is the growth of a very few years, since it was not discovered
until 1834, and does not seem to have been used by Lister until about
1863. It was not known to the people generally until much later. At
present it occupies the highest place in fatality of all poisons in England.
During the ten years ending 1903 carbolic acid has killed 1959 people,
either accidentally or suicidally; there are also five cases of murder by
carbolic acid within the same period, bringing the total up to 1964.
Falck has collected, since the year 1868, 87 cases of poisoning from
carbolic acid recorded in medical literature. In one of the cases the
individual died in nine hours from a large dose of carbolate of soda ; in
a second, violent symptoms were induced by breathing for three hours
carbolic acid vapour; in the remaining 85, the poisoning was caused by
the liquid acid. Of these 85 persons, 7 had taken the poison with
suicidal intent, and of the 7, 5 died ; 39 were poisoned through the
medicinal use of carbolic acid, 27 of the 39 by the antiseptic treatment
of wounds by carbolic acid dressings, and of these 8 terminated fatally ;
in 8 cases, symptoms of poisoning followed the rubbing or painting
of the acid on the skin for the cure of scabies, favus, or psoriasis, and
6 of these persons died. In 4 cases, carbolic acid enemata, administered
for the purpose of dislodging ascarides, gave rise to symptoms of
poisoning, and in one instance death followed.
The substitution of carbolic acid for medicine happened as follows:—
Cases.
Taken instead of Tincture of Opium, . I
7 5 } > Infusion of Senna, . 3
* 5 5 5 Mineral Water, 2
$ 2 2 3 other Mixtures, º te 3
,, inwardly instead of applied outwardly, 3
12
Of these 12, 8 died.
Again, 10 persons took carbolic acid in mistake for various alcoholic
drinks, such as schnapps, brandy, rum, or beer, and 9 of the 10 suc-
cumbed ; 17 persons drank carbolic acid simply “by mistake,” and of
these 13 died. Thus, of the whole 85 cases, no less than 51 ended
fatally—nearly 60 per cent.
It must be always borne in mind that, with regard to statistics gener-
ally, the term “carbolic acid '' is not used by coroners, juries, or
medical men in a strictly chemical sense, the term being made to include
disinfecting fluids which are almost wholly composed of the cresols, and
contain scarcely any phenol. In this article, with regard to symptoms
and pathological appearances, it is only occasionally possible to state
I 2
178 POISONS: THEIR EFFECTS AND DETECTION. [$ 220, 221.
whether the pure medicinal crystalline phenol or a mixture of tar-acids
was the cause of poisoning.
§ 220. Fatal Dose.—The minimum fatal dose for cats, dogs, and
rabbits, appears to be less than 5 grm. per kilogramme. Falck has put
the minimum lethal dose for man at 15 grms. (231°5 grains), which
would be about 2 per kilo., basing his estimate on the following reason-
ing. In 33 cases he had a fairly exact record of the amount of acid
taken, and out of the 33, he selects only those cases which are of use
for the decision of the question. Among adults, in 5 cases the dose
was 30 grms., and all the 5 cases terminated by death, in times
varying from five minutes to an hour and a half. By other 5 adults
a dose of 15 grms. was taken ; of the 5, 3 men and a woman died,
in times varying from forty-five minutes to thirty hours, while 1 woman
recovered. Doses of 11.5, 10:8, and 9 grms. were taken by different
men, and recovered from ; on the other hand, a suicide who took one
and a half teaspoonful (about 6 grms.) of the concentrated acid,
died in fifty minutes. Doses of 3 to 3 grms. have caused symptoms of
poisoning, but the patients recovered, while higher doses than 15 grns.
in 12 cases, with only one exception, caused death. Hence, it may be
considered tolerably well established, that 15 grms. (231°5 grains) may
be taken as representing the minimum lethal dose.
The largest dose from which a person appears to have recovered is
probably that given in a case recorded by Davidson, in which 150 grms.
of crude carbolic acid had been taken. It must, however, be remembered
that, as this was the impure acid, only half of it would be really carbolic
acid. The German Pharmacopoeia prescribes as a maximum dose '05
grm. (8 grain) of the crystallised acid, and a daily maximum quantity
given in divided doses of 15 grim. (2-3 grains).
§ 221. Effects on Animals.--Carbolic acid is poisonous to both
animal and vegetable life.
Infusoria.-One part of the acid in 10,000 parts of water rapidly
kills ciliated animalcules—the movements become sluggish, the sarcode
substance darker, and the cilia in a little time cease moving.
Fish.-One part of the acid in 7000 of water kills dace, minnows,
roach, and gold-fish. In this amount of dilution the effect is not ap-
parent immediately; but, at the end of a few hours, the movements
of the fish become sluggish, they frequently rise to the surface to
breathe, and at the end of twenty-four hours are found dead. Quantities
of carbolic acid, such as 1 part in 100,000 of water, appear to affect
the health of fish, and render them more liable to be attacked by the
fungus growth which is so destructive to fish-life in certain years.
Frogs.-If '01 to '02 grm. of carbolic acid be dissolved in a litre
of water in which a frog is placed, there is almost immediately signs of
§ 222.] THE TAR ACIDS, 179
uneasiness in the animal, showing that pain from local contact is
experienced; a sleepy condition follows, with exaltation of reflex
sensibility; convulsions succeed, generally, though not always; then
reflex sensibility is diminished, ultimately vanishes, and death occurs;
the muscles and nerves still respond to the electric current, and the heart
beats, but slowly and weakly, for a little after the respiration has ceased.
§ 222. Warm-blooded Animals—For a rabbit of the average weight
of 2 kilos., 15 grm. is an active dose, and 3 a lethal dose (that is 15
per kilo.). The sleepy condition of the frog is not noticed, and the chief
symptoms are clonic convulsions with dilatation of the pupils, the
convulsions passing into death, without a noticeable paralytic stage.
The symptoms observed in poisoned dogs are almost precisely similar,
the dose, according to body weight, being the same. It has, however,
been noticed that with doses large enough to produce convulsions, a
weak condition has supervened, causing death in several days. There
appears to be no cumulative action, since equal toxic doses can be
given to animals for some time, and the last dose has no greater effect
than the first or intermediate ones. The pathological appearances met
with in animals poisoned by the minimum lethal doses referred to are
not characteristic ; but there is a remarkable retardation of putrefaction.
Meili “ has studied the relative lethal effects on rabbits of phenol
and the cresols. Meta-cresol he found less poisonous than phenol, the
deadly dose being 0-5 grm. per kilo.; phenol, less poisonous than ortho-
and para-cresol; and the latter most poisonous of all.
Karl Tollens,f experimenting on cats, mice, and frogs, gave the follow-
ing results:—
FATAL DOSE IN GRMS. PER KILOGRAMME OF BODY WEIGHT.
Cats. Mice. Frogs.
Phenol, 0 °09 0 °35 0.10
Para-cresol, . 0.08 0 15 () -15
Ortho- , , 0-09 0 °35 0 °20
Meta- , , e - e e s w e e 0-12 0 °45 0 25
Carbolate of soda reckoned in weight of phenol, . - - 0 °35 0 10
Cresolate of soda in terms of cresol—
Para-cresol, 0 15 0-15
Ortho- , , 0 °35 0.20
Meta- , , º 0 °45 0.25
I. Crude cresol, 0 °35 O'20
II. , , , - 0 °25 0.20
III. , , } } * * * * * 0 °20 0.20
I. Liq. Gresol Saponis in terms of cresol, 0 °30 0-15
II. 5 y * } } 2 3 3 y 0 °25 0-15
III. 3 y 3 3 3 * } 3 0-20 0.15 ;
* Dissertation. Berne, 1891.
† Archiv. f. ea:periment. Path. w. Pharm., Bd, lii. S. 239.
I8O POISONS : THEIR EFFECTS AND DETECTION. [$ 223.
§ 223. Symptoms in Man, external application.—A 5 per cent.
solution of carbolic acid, applied to the skin, causes a peculiar numbness,
followed, it may be, by irritation. Young subjects, and those with
sensitive skins, sometimes exhibit a pustular eruption, and concentrated
solutions cause more or less destruction of the skin. Lemaire * describes
the action of carbolic acid on the skin as causing a slight inflammation,
with desquamation of the epithelium, followed by a very permanent
brown stain; but this he alone has observed. Applied to the mucous
membrane, carbolic acid turns the epithelial covering white ; the
epithelium, however, is soon thrown off, and the place rapidly heals;
there is the same numbing, aconite-like feeling before noticed. The
vapour of carbolic acid causes redness of the conjunctivae, and irritation
of the air-passages. If the application is continued, the mucous mem-
brane swells, whitems, and pours out an abundant secretion.
Dr. Whitelock, of Greenock, has related two instances in which
children were treated with carbolic acid lotion (strength 2% per cent.) as
an application to the scalp for ringworm ; in both, symptoms of poisoning
occurred—in the one, the symptoms at once appeared ; in the other,
they were delayed some days. In order to satisfy his mind, the
experiment was repeated twice, and each time gastric and urinary
troubles followed. -
Nussbaum, of Munich, records a case f in which symptoms were
induced by the forcible injection of a solution of carbolic acid into the
cavity of an abscess.
Macphail i gives two cases of poisoning by carbolic acid from
external use. In the one, a large tumour had been removed from a
woman aged 30, and the wound covered with gauze steeped in a solution
of carbolic acid, in glycerin, strength 10 per cent. ; subsequently, there
was high fever, with diminished sulphates in the urine, which smelt
strongly of carbolic acid, and was very dark. On substituting boracic
acid, none of these troubles were observed. The second case was that
of a servant suffering from axillary abscess; the wound was syringed
out with carbolic acid solution, of strength 2% per cent., when effects
were produced similar to those in the first case. It was noted that in
both these cases the pulse was slowed. J. A. Raubenheimer (Lancet,
April 18, 1903) describes the case of a child aged 6, prepared for
operation on genu valgum of both sides, by the nurse, who wrapped the
legs from the ankles to the groin with towels impregnated with carbolic
acid (1: 40); in an hour the patient was sleepy, in two hours unconscious,
* Lemaire, Jul., De l'Acide phenique, Paris, 1864.
+ Leitfaden zur antiseptischer Wundbehandlung, 141. f
: “Carbolic Acid Poisoning (Surgical),” by S. Rutherford Macphail, M.B., Ed.
Med. Jowrmal cccxiv., Aug. 1881, p. 134.
§ 223.] THE TAR ACIDS. I8I
cyanosed, and almost pulseless. In six hours the urine showed carboluria,
which persisted for the next twenty-five hours; the patient, under treat-
ment, recovered. Scattered throughout surgical and medical literature,
there are many other cases recorded, though not all so clear as those
cited. Several cases are also on record in which poisonous symptoms (and
even death) have resulted from the application of carbolic acid lotion as
a remedy for scabies or itch.
A surgeon prescribed for two joiners who suffered from scabies a
lotion, which was intended to contain 30 grims. of carbolic acid in 240
c.c. of water; but the actual contents of the flasks were afterwards from
analysis estimated by Hoppe-Seyler to be 33°26 grms, and the quantity
used by each to be equal to 1337 grns. (206 grains) of carbolic acid.
One of the men died ; the survivor described his own symptoms as
follows:—He and his companion stood in front of the fire, and rubbed
the lotion in ; he rubbed it into his legs, breast, and the front part of
his body; the other parts were mutually rubbed. Whilst rubbing his
right arm, and drying it before the fire, he felt a burning sensation, a
tightness and giddiness, and mentioned his sensations to his companion,
who laughed. This condition lasted from five to seven minutes, but he
did not remember whether his companion complained of anything, nor
did he know what became of him, nor how he himself came to be in bed.
He was found holding on to the joiner's bench, looking with wide staring
eyes, like a drunken man, and was delirious for half an hour. The
following night he slept uneasily and complained of headache and
burning of the skin. The pulse was 68; the appearance of the urine,
appetite, and sense of taste were normal; the bowels confined. He
soon recovered.
The other joiner seems to have died as suddenly as if he had taken
prussic acid. He called to his mother, “Ich habe einen Rausch,” and
died with pale livid face, after taking two deep, short inspirations.
The post-mortem examination showed the sinuses filled with much
fluid blood, and the vessels of the pia mater congested. Frothy, dark,
fluid blood was found in the lungs, which were hyperaemic ; the mucous
tissues of the epiglottis and air-tubes were reddened, and covered with
a frothy slime. Both ventricles—the venæ cavae and the vessels of the
spleen and kidneys—were filled with dark fluid blood. The muscles
were very red; there was no special odour. Hoppe-Seyler recognised
carbolic acid in the blood and different organs of the body.”
In another case, a child died from the outward use of a 2 per cent.
solution of carbolic acid. It is described as follows:—An infant of
7 weeks old suffered from varicella, and one of the pustules became
* R. Köhler, Würtem. Med. Cory. Bl., xlii., No. 6, April 1872 ; H. Abelin,
Schmidt’s Jahrbücher, 1877, Bd. clxxiii. S. 163.
I82 POISONS : THEIR EFFECTS AND DETECTION, [$ 224.
the centre of an erysipelatous inflammation. To this place a 2 per cent.
solution of carbolic acid was applied by means of a compress steeped in
the acid; the following morning the temperature rose from 36'5" (97.7°
F.) to 37° (98.6° F.), and poisonous symptoms appeared. The urine
was coloured dark. There were sweats, vomitings, and contracted
pupils, spasmodic twitchings of the eyelids and eyes, with strabismus,
slow respiration, and, lastly, inability to swallow. Under the influence
of stimulating remedies the condition temporarily improved, but the
child died twenty-three and a half hours after the first application. An
examination showed that the vessels of the brain and the tissue of the
lungs were abnormally full of blood. The liver was softer than natural,
and exhibited a notable yellowishness in the centre of the acini. Some-
what similar appearances were noticed in the kidneys, the microscopic
examination of which showed the tubuli contorti enlarged and filled with
fatty globules. In several places the epithelium was denuded, in other
places swollen, and with the nuclei very visible.
In an American case,” death followed the application of carbolic
acid to a wound. A boy had been bitten by a dog, and to the wound,
at 1 o'clock in the afternoon, a lotion, consisting of nine parts of
carbolic acid and one of glycerin, was applied. At 7 o'clock in the
evening the child was unconscious, and died at 1 o'clock the following
day. -
§ 224. Internal Administration.—Carbolic acid may be taken into
the system, not alone by the mouth, but by the lungs, as in breathing
carbolic acid spray or carbolic acid vapour. It is also absorbed by the
skin when outwardly applied, or in the dressing or the spraying of
wounds with carbolic acid. Lastly, the ordinary poisonous effects have
been produced by absorption from the bowel, when administered as an
enema. When swallowed undiluted, and in a concentrated form, the
symptoms may be those of early collapse, and speedy death. Hence,
the course is very similar to that witnessed in poisoning by the mineral
acids.
If lethal, but not excessive doses of the diluted acid are taken, the
symptoms are—a burning in the mouth and throat, a peculiarly unpleasant
persistent taste, and vomiting. There is faintness with pallor of the
face, which is covered by a clammy sweat, and the patient soon becomes
unconscious, the pulse small and thready, and the pupils sluggish to
light. The respiration is profoundly affected ; there is dyspnoea, and the
breathing becomes shallow. Death occurs from paralysis of the respira-
tory apparatus, and the heart is observed to beat for a little after the
respiration has ceased. All these symptoms may occur from the applica
tion of the acid to the skin or to mucous membranes, and have been
Americant Jowrmal of Pharmacy, vol. li., 4th Ser. ; Vol. ix., p. 57, 1879,
§ 225, 226.] THE TAR ACIDS. 183
noticed when solutions of but moderate strength have been used—e.g.
there are cases in gynaecological practice in which the mucous membrane
(perhaps eroded) of the uterus has been irrigated with carbolic acid
injections. Thus, Küster * relates a case in which, four days after con-
finement, the uterus was washed out with a 2 per cent. solution of
carbolic acid without evil results. Afterwards a 5 per cent. solution was
used, but it at once caused violent symptoms of poisoning—the face
became livid, clonic convulsions came on, and at first loss of conscious-
ness, which after an hour returned. The patient died on the ninth day.
There was intense diphtheria of the uterus and vagina. Several other
similar cases (although not attended with such marked or fatal effects)
are on record.i
§ 225. The symptoms of carbolic acid poisoning admit of considerable
variation from those already described. The condition is occasionally
that of deep coma. The convulsions may be general, or may affect only
certain groups of muscles. Convulsive twitchings of the face alone,
and also muscular twitchings only of the legs, have been noticed. In all
cases, however, a marked change occurs in the urine. Subissi i has
noted the occurrence of abortion, both in the pig and the mare, as a
result of carbolic acid, but this effect has not hitherto been recorded in
the human subject.
It has been experimentally shown by Küster, that previous loss of
blood, or the presence of septic fever, renders animals more sensitive
to carbolic acid. It is also said that children are more sensitive than
adults.
The course of carbolic acid poisoning is very rapid. In 35 cases
collected by Falck, in which the period from the taking of the poison to
the moment of death was accurately noted, the course was as follows:—
12 patients died within the first hour, and in the second hour 3; so that
within two hours 15 died. Between the third and the twelfth hour, 10
died; between the thirteenth and the twenty-fourth hour, 7 died; and
between the twenty-fifth and the sixtieth hour, only 3 died. Therefore,
slightly over 71 per cent, died within twelve hours, and 91.4 per cent.
within the twenty-four hours.
§ 226. Changes in the Urine.—The urine of patients who have
absorbed in any way carbolic acid is dark in colour, and may smell
* Centralblatt f. Gymäkologie, ii. 14, 1873.
+ A practitioner in Calcutta injected into the bowel of a boy, aged 5, an enema of
diluted carbolic acid, which, according to his own statement, was 1 part in 60, and
the whole quantity represented 144 grains of the acid. The child became insensible
a few minutes after the operation, and died within four hours. There was no post-
mortem examination ; the body smelt strongly of carbolic acid.-Lancet, May 19,
1883.
† L’Archivio della Veterinaria Ital.., xi., 1874.
I 84 POISONS: THEIR EFFECTS AND DETECTION. [$ 226.
strongly of the acid. It is now established—chiefly by the experiments
and observations of Baumann *—that carbolic acid, when introduced into
the body, is mainly eliminated in the form of phenyl-sulphuric acid,
CeBigHSO4, or more strictly speaking as potassic phenyl - sulphate,
CeBIs KSO, a substance which is not precipitated by chloride of barium
until it has been decomposed by boiling with a mineral acid. Cresol is
similarly excreted as cresol sulphuric acid, CaFIACHs HSOp ortho-, meta-,
or para-, according to the kind of cresol injected; a portion may also
appear as hydro-tolu-chinone-sulphuric acid. Hence it is that, with doses
of phenol or cresol continually increasing, the amount of sulphates matur-
ally in the urine (as estimated by simply acidifying with hydrochloric
acid, and precipitating in the cold with chloride of barium) continually
decreases, and may at last vanish, for all the sulphuric acid present is
united with the phenol. On the other hand, the precipitate obtained by
prolonged boiling of the strongly acidified urine, after filtering off any
BaSO, thrown down in the cold, is ever increasing.
Thus, a dog voided urine which contained in 100 c.c., 262 grm. of
precipitable sulphuric acid, and '006 of organically-combined sulphuric
acid; his back was now painted with carbolic acid, and the normal
proportions were reversed, the precipitable sulphuric acid became
:004 grim., while the organically-combined was 190 in 100 c.c. In
addition to phenyl-sulphuric acid, it is now sufficiently established i
that hydroquinone (C.H.;) (paradihydroxyl phenol) and pyro-cate-
chim (C.H.;) (orthodihydroxyl phenol) are constant products of a
portion of the phenol. The hydroquinone appears in the urine, in the
first place, as the corresponding ether-sulphuric acid, which is colourless;
but a portion of it is set free, and this free hydroquinone (especially in
alkaline urine) is quickly oxidised to a brownish product, and hence the
peculiar colour of the urine. Out of dark coloured carbolic acid urine the
hydroquinone and its products of decomposition can be obtained by shak-
ing with ether ; on separation of the ether, an extract is obtained,
reducing alkaline silver solution, and developing quinone on warming
with ferric chloride.
To separate pyro-Catechin, 200 c.c. of urine may be evaporated to an
extract, the extract treated with strong alcohol, the alcoholic liquid
evaporated, and the extract then treated with ether. On separation and
evaporation of the ether a yellowish mass is left, from which the pyro-
catechin may be extracted by washing with a small quantity of water.
* Pflüger's Archiv, xiii., 1876, 289.
+ E. Baumann and C. Preuss, Zeitschrift f. phys. Chemie, iii. 156; Amleitung zur
Harm-Analyse, W. F. Löbisch, Leipzig, 1881, pp. 142, 160; Schmiedeberg. Chem.
Centrbl. (3), 13, 598.
§ 227, 228.] THE TAR ACIDS. 185
This solution will reduce silver solution in the cold, or, if treated with
a few drops of ferric chloride solution, show a marked green colour,
changing on being alkalised by a solution of sodic hydro-carbonate to
violet, and then on being acidified by acetic acid, changing back again to
green. According to Thudichum,” the urine of men and dogs, after the
ingestion of carbolic acid, contains a blue pigment.
§ 227. The Action of Carbolic Acid considered physiologically.—
Researches on animals have elucidated, in a great measure, the mode in
which carbolic acid acts, and the general sequence of effects, but there is
still much to be learnt.
E. Küster t, has shown that the temperature of dogs, when doses of
carbolic acid in solution are injected subcutaneously, or into the veins, is
immediately, or very soon after the operation, raised. With small and
moderate doses, this effect is but slight—from half to a whole degree—
on the day after the injection the temperature sinks below the normal
point, and only slowly becomes again natural. With doses that are just
lethal, first a rise and then a rapid sinking of temperature are observed ;
but with those excessive doses which speedily kill, the temperature at
once sinks without a preliminary rise. The action on the heart is not
very marked, but there is always a slowing of the cardiac pulsations;
according to Hoppe-Seyler the arteries are relaxed. The respiration is
much quickened; this acceleration is due to an excitement of the vagus
centre, since Salkowsky has shown that section of the vagus produces a
retardation of the respiratory wave. Direct application of the acid to
muscles or nerves quickly destroys their excitability without a previous
stage of excitement. The main cause of the lethal action of carbolic acid
—putting on one side those cases in which it may kill by its local corro-
sive action—appears to be paralysis of the respiratory nervous centres.
The convulsions arise from the spinal cord. On the cessation of the
convulsions, the superficial nature of the breathing assists other changes
by preventing the due oxidation of the blood. -
§ 228. Carbolic acid is separated from the body in the forms already
mentioned, a small portion is also excreted by the skin. Salkowsky
states that, with rabbits, he has also found oxalic acid in the urine
as an oxidation product. According to the researches of Binnendijk,
the separation of carbolic acid by the urine commences very quickly
after its ingestion; and, under favourable circumstances, it may be com-
pletely excreted within from twelve to sixteen hours. It must be
remembered that normally a small amount of phenol may be present in
the animal body, as the result of the digestion of albuminous substances
* On the Pathology of the Urine, Lond., 1877, p. 198.
t Archiv f. klin. Chirurgie, Bd. xxii. S. 133, 1879.
# Journal de Pharmacie et de Chimie, 4 Ser. T. xxx., 1880.
I86 POISONS : THEIR EFFECTS AND DETECTION. [$ 229.
or of their putrefaction. The amount excreted by healthy men when
feeding on mixed diet, Engel,” by experiment, estimates to be in the
twenty-four hours 15 mgrms.
§ 229. Post-mortem Appearances.—No fact is better ascertained
from experiments on animals than the following:—That with lethal
doses of carbolic acid, administered by subcutaneous injection, or intro-
duced by the veins, no appearances may be found after death which
can be called at all characteristic. Further, in the cases in which death
has occurred from the outward application of the acid for the cure of
scabies, etc., no lesion was ascertained after death which could—apart
from the history of the case and chemical evidence—with any confidence
be ascribed to a poison.
On the other hand, when somewhat large doses of the acid are taken
by the mouth, very coarse and appreciable changes are produced in the
upper portion of the alimentary tract. There may be brownish,
wrinkled spots on the cheek or lips; the mucous membrane of the mouth,
throat, and gullet is often white, and if the acid was concentrated,
eroded. The stomach is sometimes thickened, contracted, and blanched,
a condition well shown in a pathological preparation (ix. 206, 43 f) in
St. George's Hospital. The mucous membrane, indeed, may be quite as
much destroyed as if a mineral acid had been taken. Thus, in Guy's
Hospital museum (17994%), there is preserved the stomach of a child
who died from taking accidentally carbolic acid. It looks like a piece
of paper, and is very white, with fawn-coloured spots; the rugae are
absent, and the mucous membrane seems to have entirely vanished.
Not unfrequently the stomach exhibits white spots with roundish edges.
The duodenum and upper part of the small intestine is often affected (see
a preparation in St. Bartholomew's Museum, 1949, e), and the action
is not always limited to the first part of the intestine.
The respiratory passages are often inflamed, and the lungs in-
filtrated and congested. As death takes place from an asphyxiated
condition, the veins of the head and brain, and the blood-vessels of the
liver, kidney, and spleen, are gorged with blood, and the right side of
the heart distended, while the left is empty. On the other hand, a
person may die of sudden nervous shock from the ingestion of a large
quantity of the acid, and in such a case the post-mortem appearances
will not then exhibit precisely the characters just detailed. Putrefaction
is retarded according to the dose, and there is often a smell of carbolic
acid.: If any urine is contained in the bladder, it will probably be
dark, and present the characters of carbolic urine, detailed at p. 183.
* Amnal. de Chimie et de Physique, 5 Ser. T. xx. p. 230, 1880.
# In order to detect this odour, it is well to open the head first, lest the putre-
faction of the internal viscera be so great as to mask the odour,
§ 230, 23.I.] THE TAR ACIDS. 187
Tests for Carbolic Acid.
§ 230. 1. The Pinewood Test.—Certain pinewood gives a beautiful
blue colour when moistened first with carbolic acid, and afterwards with
hydrochloric acid, and exposed to the light. Some species of pine give
a blue colour with hydrochloric acid alone, and such must not be used;
others do not respond to the test for carbolic acid. Hence it is necessary
to try the chips of wood first, to see how they act, and with this pre-
caution the test is very serviceable, and, in cautious hands, no error will
be made.
2. Ammonia and Hypochlorite Test.—If to a solution containing
even so small a quantity as 1 part of carbolic acid in 5000 parts of
water, first, about a quarter of its volume of ammonia hydrate be added,
and then a small quantity of sodic hypochlorite solution, avoiding ex-
cess, a blue colour appears; warming quickens the reaction : the blue
is permanent, but turns to red with acids. If there is a smaller
quantity than the above proportion of acid, the reaction may be still
produced feebly after standing for some time.
3. Ferric Chloride.—One part of phenol in 3000 parts of water can
be detected by adding a solution of ferric chloride; a fine violet colour
is produced. This is also a very good test, when applied to a distillate ;
but if applied to a complex liquid, the disturbing action of neutral salts
and other substances may be too great to make the reaction under those
circumstances of service.
4. Bromine.—The most satisfactory test of all is treatment of the
liquid by bromine-water. A precipitate of tri-bromo-phenol (CHs BrºC)
is rapidly or slowly formed, according to the strength of the solution;
in detecting very minute quantities the precipitate must be given time to
form. According to Allen,* a solution containing but go;go of carbolic
acid gave the reaction after standing twenty-four hours.
The properties of the precipitate are as follows:—It is crystalline,
and under the microscope is seen to consist of fine stars of needles; its
smell is peculiar ; it is insoluble in water and acid liquids, but soluble
in alkalies, ether, and absolute alcohol; a very minute quantity of
Water suffices to precipitate it from an alcoholic solution ; it is therefore
essential to the success of the test that the watery liquid to be examined
is either neutral or acid in reaction.
§ 231. Tri-bromo-phenol may be used for the quantitative estimation
of carbolic acid; 100 parts of tri-bromo-phenol are equal to 29-8 of
carbolic acid ; by the action of sodium amalgam, tri-bromo-phenol is
changed back into carbolic acid.
* Commercial Organic Amalusis, vol. i. p. 306.
9 $/Sls, }
I 88 POISONS : THEIR EFFECTS AND DETECTION. [$ 232.
That bromine-water precipitates several volatile and fixed alkaloids
from their solutions is no objection to the bromine test, for it may be
applied to a distillation product, the bases having been previously fixed
by sulphuric acid. Besides, the properties of tri-bromo-phenol are
distinct enough, and therefore there is no valid objection to the test.
It is the best hitherto discovered. There are also other reactions, such
as that Millon's reagent strikes a red—molybdic acid, in concentrated
sulphuric acid, a blue—and potassic dichromate, with sulphuric acid, a
brown colour—but to these there are objections. Again, we have the
Euchlorine test, in which the procedure is as follows:—A test tube is
taken, and concentrated hydrochloric acid is allowed to act therein upon
potassic chlorate. After the gas has been evolved for from 30 to 40
seconds, the liquid is diluted with 1% volume of water, the gas removed
by blowing through a tube, and solution of strong ammonia poured in
so as to form a layer on the top ; after blowing out the white fumes of
ammonium chloride, a few drops of the sample to be tested are added.
In the presence of carbolic acid, a rose-red, blood-red, or red-brown tint
is produced, according to the quantity present. Carbolic acid may be
confounded with cresol or with creasote, but the distinction between pure
carbolic acid, pure cresol, and creasote is plain.
OH
§ 232. Cresol (Cresylic Acid, Methyl-phenol), C.H.K .—There
CH,
are three cresols—Ortho-, meta-, and para-. Ordinary commercial cresol
is a mixture of the three, but contains but little ortho-cresol; the more
important properties of the pure cresols are set out in the following
table:—Pure ortho-, meta-, or para- cresol have been obtained by
synthetical methods; they cannot be said to be in ordinary commerce.
Melting-point. Boiling-point. ºon
Ortho-, . . . 31-31 '5° C. 188:0° Salicylic acid
- (Ortho-oxybenzoic
acid).
Meta-, . . Fluid at ordinary 201:0° Meta-oxybenzoic
temperature. - acid.
Para-, . . 36° 198° Para-oxybenzoic acid.
Commercial cresol is at ordinary temperatures a liquid, and
cannot be obtained in a crystalline state by freezing. Its boiling-point
is from 198" to 203”; it is almost insoluble in strong ammonia, and,
when 16 volumes are added, it then forms crystalline scales. On the
other hand, carbolic acid is soluble in an equal volume of ammonia,
§ 233.] THE TAR ACIDS. 189
and is then precipitated by the addition of 1% volume of water. Cresol
is insoluble in small quantities of pure 6 per cent. Soda solution; with
a large excess, it forms crystalline scales; while carbolic acid is freely
soluble in small or large quantities of alkaline solutions.
Cold petroleum spirit dissolves cresol, but no crystalline scales can
be separated out by a freezing mixture. Carbolic acid, on the contrary,
is but sparingly soluble in cold petroleum, and a solution of carbolic
acid in hot petroleum, when exposed to sudden cold produced by a
freezing mixture, separates out crystals from the upper layer of liquid.
Cresol is miscible with glycerin of specific gravity 1.258 in all propor-
tions; 1 measure of glycerin mixed with 1 measure of cresol is
completely precipitated by 1 measure of water. Carbolic acid, under
the same circumstances, is not precipitated. The density of cresol is
about 1-044. It forms with bromine a tri-bromo-cresol, but this is
liquid at ordinary temperatures, while tri-bromo-phenol is solid. On
the other hand, it resembles carbolic acid in its reactions with ferric
chloride and with nitric and sulphuric acids.
§ 233. Creasote or Kreozote is a term applied to the mixture of crude phenols
obtained from the distillation of wood-tar. It consists of a mixture of substances
of which the chief are guaiacol or oxycresol (C, HsO3), boiling at 200°, and creasol
(CsII,002), boiling at 217°; also in small quantities phlorol (CsII,00), methyl creasol
(C6H12O3), and other bodies. Morson’s English creasote is prepared from Stockholm
tar, and boils at about 217°, consisting chiefly of creasol ; it is not easy, by mere
chemical tests, to distinguish creasote from cresylic acid. Creasote, in its reactions
with sulphuric and nitric acid, bromine and gelatin, is similar to carbolic and
cresylic acids, and its solubility in most solvents is also similar. It is, however,
distinguished from the tar acids by its insolubility in Price's glycerin, specific gravity
1258, whether 1, 2, or 3 volumes of glycerin be employed. But the best test is
its action on an ethereal solution of nitro-cellulose. Creasote mixes freely with the
B.P. collodium, while cresylic acid or carbolic acid at once coagulates the latter.
With complicated mixtures containing carbolic acid, cresol, and creasote, the only
method of applying these tests with advantage is to submit the mixture to fractional
distillation.
Flückiger” tests for small quantities of carbolic acid in creasote, by mixing
a watery solution of the sample with one-fourth of its volume of ammonia hydrate,
wetting the inside of a porcelain dish with this solution, and then carefully blowing
bromine fumes on to the surface. A fine blue colour appears if carbolic acid is present,
but if the sample consists of creasote only, then it is a dirty green or brown. Excess
of bromine spoils the reaction.f
* Arch. der Pharmacie, cziii. p. 30.
t Creasote is, without doubt, poisonous, though but little is known of its action,
and very few experiments are on record in which pure creasote has been employed.
Eulenberg has studied the symptoms in rabbits, by submitting them to vaporised
creasote—i.e. the vapour from 20 drops of creasote diffused through a glass shade
under which a rabbit was confined. There was at once great uneasiness, with a watery
discharge from the eyes, and after seven minutes the rabbit fell on its side, and was
slightly convulsed. The cornea was troubled, and the eyes prominent; a white slime
flowed from the mouth and eyes. After fifteen minutes there was narcosis, with
I90 POISONS: THEIR EFFECTS AND DETECTION. [$ 234, 235.
§ 234. Carbolic Acid in Organic Fluids or in the Tissues of the
Body.—If the routine process given at page 49, where the organic
fluid is distilled in a vacuum after acidifying with tartaric acid, is
employed, phenol or cresol, if present, will certainly be found in the
distillate. If, however, a special search be made for the acids, then the
fluid must be well acidified with sulphuric acid, and distilled in the
usual way. The distillation should be continued as long as possible,
and the distillate shaken up with ether in the apparatus figured at
page 163. On separation and evaporation of the ether, the tar acids,
if present, will be left in a pure enough form to show their reactions. The
same process applies to the tissues, which, in a finely-divided state, are
boiled and distilled with dilute sulphuric acid, and the distillate treated
as just detailed.
Like most poisons, carbolic acid has a selective attraction for certain
organs, so that, unless all the organs are examined, it is by no means
indifferent which particular portion is selected for the inquiry. Hoppe-
Seyler applied carbolic acid to the abdomen and the thighs of dogs,
and when the symptoms were at their height bled them to death, and
separately examined the parts. In one case, the blood yielded ‘00369
per cent. ; the brain, .0034 per cent. ; the liver, 00125; and the kidneys,
-00423 per cent. of their weight of carbolic acid. The liver then
contains only one-third of the quantity found in an equal weight of
blood, and, therefore, the acid has no selective affinity for that organ.
On the other hand, the nervous tissue, and especially the kidneys,
appear to concentrate it. P. G. Menegazzi (L'orosi, xxi., 1898), from
a poisoned rabbit, failed to extract from the tissues, etc., more than
29.2 per cent. of the phenol administered ; which is not surprising,
seeing the chemical changes it is liable to undergo.
§ 235. Examination of the Urine for Phenol or Cresol,—It has
been previously stated (see p. 184) that the urine will not contain these
as such, but as compounds—viz., phenyl or cresyl sulphate of potassium.
By boiling with a mineral acid, these compounds may be broken up,
and the acids obtained, either by distillation or by extraction with ether.
To detect very minute quantities, a large quantity of the urine should
be evaporated down to a syrup, and treated with hydrochloric acid and
lessened reflex action ; the temperature was almost normal. There was rattling
breathing, and in half an hour the animal died, the respiration ceasing, and
fluid blood escaping from the nose. Section after death showed the brain to be
hyperaemic, the mucous membranes of the air-passages to be covered with a thin
layer of fluid blood, and the lungs to be congested; the right side of the heart was
gorged with fluid blood.
The post-mortem appearances and the symptoms generally are, therefore, closely
allied to those produced by carbolic acid. A dark colour of the urine has also been
noticed. -
§ 236.] THE TAR ACIDS. I91
ether. On evaporating off the ether, the residue should be distilled
with dilute sulphuric acid, and this distillate then tested with bromine-
water, and the tri-bromo-phenol or cresol collected, identified, and
weighed.
Thudichum * has separated crystals of potassic phenyl-sulphate
itself from the urine of patients treated endermically by carbolic acid,
as follows:—
The urine was evaporated to a syrup, extracted with alcohol of 90 per
cent., treated with an alcoholic solution of Oxalic acid as long as this
produced a precipitate, and then shaken with an equal volume of ether.
The mixture was next filtered, neutralised with potassic carbonate,
evaporated to a small bulk, and again taken up with alcohol. Some
oxalate and carbonate of potassium were separated, and on evaporation
to a syrup, crystals of potassic phenyl-sulphate were obtained. They
gave to an analysis 46.25 per cent. H3SO, and 18:1 K–theory requiring
462 of H2SO, and 18.4 of K. Alkaline phenyl-sulphates strike a deep
purple colour with ferric chloride. To estimate the amount of phenyl-
sulphate or cresol-sulphate in the urine, the normal sulphates may be
separated by the addition of chloride of barium in the cold, first acidify.
ing with hydrochloric acid. On boiling the liquid a second crop of
sulphate is obtained, due to the breaking up of the compound sulphate,
and from this second weight the amount of acid can be obtained, e.g. in
the case of phenol—Cah, HSO, ; BaSO, ; ; 174: 233.
§ 236. Assay of Disinfectants, Carbolic Acid Powders, etc.—For the assay of
crude carbolic acid, Mr. Charles Lowe f uses the following process:—A thousand
parts of the sample are distilled without any special condensing arrangement; water
first comes over, and is then followed by an oily fluid. When a hundred parts of the
latter, as measured in a graduated tube, have been collected, the receiver is changed.
The volume of water is read off. If the oily liquid floats on the water, it contains
light oil of tar; if it is heavier than the water, it is regarded as hydrated acid, con-
taining 50 per cent. of real carbolic acid. The next portion consists of anhydrous
cresylic and carbolic acids, and 625 volumes are distilled over; the remainder in the
retort consists wholly of cresylic acid and the higher homologues. The relative pro-
portions of carbolic and cresylic acids are approximately determined by taking the
solidifying point, which should be between 15'5° and 24°, and having ascertained
this temperature, imitating it by making mixtures of known proportions of carbolic
and cresylic acids.
E. Wallert has recommended the following process for the estimation of carbolic
acid. It is based on the precipitation of the tar acids by bromine, and, of course, all
phenols precipitated in this way will be returned as carbolic acid. The solutions
necessary are—
1. A solution containing 10 grims, of pure carbolic acid to the litre; this serves
as a standard solution.
* Pathology of the Urine, p. 193.
t Allen's Commercial Organic Analysis, vol. i. p. 311.
# Chem. News, April 1, 1881, p. 152.
I92 POISONS : THEIR EFFECTS AND DETECTION. [$ 237.
2. A solution of bromine in water.
3. Solution of alum in dilute sulphuric acid. A litre of 10 per cent, sulphuric
acid is shaken with alum crystals until saturated.
The actual process is as follows:–10 grims. of the sample are weighed out and
run into a litre flask, water added, and the mixture shaken. The flask being finally
filled up to the neck, some of the solution is now filtered through a dry filter, and
10 c.c. of this filtrate is placed in a 6 or 8 ounce stoppered bottle, and 30 c.c. of the
alum solution added. In a similar bottle 10 c.c. of the standard solution of carbolic
acid are placed, and a similar quantity of alum solution is added, as in the first bottle.
The bromine-water is now run into the bottle containing the standard solution
of carbolic acid from a burette, until there is no further precipitate; the bottle is
stoppered and shaken after every addition. Towards the end of the reaction the
precipitate forms but slowly, and when the carbolic acid is saturated, the slight
excess of bromine-water gives the solution a pale yellow tint. The solution from the
sample is treated in the same way, and from the amount of bromine-water used, the
percentage of the sample is obtained by making the usual calculations. Thus, Sup-
posing that 5 c.c. of the standard required 15 c.c. of the bromine-water for precipita-
tion, and 10 c.c. of the solution of the sample required 17 c.c., the calculation would
be 15 x 2: 17 = 100: a per cent. With most samples of crude carbolic acid, the pre-
cipitate does not readily separate. It is then best to add a little of the precipitate
already obtained by testing the standard solution, which rapidly clears the liquid.
Koppeschaar's volumetric method is more exact, but also more elaborate,
than the one just described. Caustic normal soda is treated with bromine until
permanently yellow, and the excess of bromine is then driven off by boiling. The
liquid now contains 5NaBr-H NaBrO3, and on adding this to a solution containing
carbolic acid, and a sufficient quantity of hydrochloric acid to combine with the
sodium, the following reactions occur :—
(1.) 5NaBr 4. NaBrO3 +6HCl−6NaCl-i-6Br + 3H2O ;
and
(2.) Cºh,0+6Br = CH, Br,0+3HBr.
Any excess of bromine liberated in the first reaction above that necessary for the
second, will exist in the free state, and from the amount of bromine which remains
free the quantity of carbolic acid can be calculated, always provided the strength of
the bromine solution is first known. The volumetric part of the analysis, therefore,
merely amounts to the determination of free bromine, which is best found by causing
it to react on potassium iodide, and ascertaining the amount of free iodine by titra-
tion with a standard solution of sodium thiosulphate. In other words, titrate in
this way the standard alkaline bromine solution, using as an indicator starch paste
until the blue colour disappears. Another method of indicating the end of the
reaction is by the use of strips of paper first soaked in starch solution, and dried, and
then the same papers moistened with zinc iodide, and again dried; the least excess
of bromine sets free iodine, and strikes a blue colour.
Colorimetric Method of Estimation.—A very simple and ever-ready way of
approximately estimating minute quantities of the phenols consists in shaking up
10 grims. of the sample with water, allowing any tar or insoluble impurities to sub-
side. Ten c.c. of the clear fluid are then taken, and half a c.c. of a 5 per cent.
solution of ferric chloride added. The colour produced is imitated by a standard
solution of carbolic acid, and a similar amount of the reagent, on the usual principles
of colorimetric analysis.
§ 237. Carbolic Acid Powders.-Siliceous carbolic acid powders are placed in a
retort and distilled. Towards the end the heat may be raised to approaching red-
ness. The distillate separates into two portions—the one aqueous, the other con-
sisting of the acids—and the volume may be read off, if the distillate be received in
§ 238–240.] . NITRO-BENZENE. I93
a graduated receiver. Carbolic acid powders, having lime as a basis, may be dis-
tilled in the same way, after first decomposing with sulphuric acid. The estimation
of the neutral tar oils in the distillate is easily performed by shaking the distillate
with caustic soda solution, which dissolves completely the tar acids. The volume of
the oils may be directly read off if the receiver is a graduated tube. Allen” has
suggested the addition of a known volume of petroleum to the distillate, which dis-
solves the tar oils, and easily separates, and thus the volume may be more accurately
determined, a correction being of course made by subtracting the volume of petroleum
first added.
§ 238. Carbolic Acid Soap. —A convenient quantity of soap is carefully weighed,
and dissolved in a solution of caustic soda by means of heat. A Saturated solution
of salt is next added, sufficient to precipitate entirely the soap, which is filtered off;
the filtrate is acidified with hydrochloric acid, and bromine-water added. The pre-
cipitated tri-bromo-phenol is first melted by heat, then allowed to cool, and the mass
removed from the liquid, dried, and weighed.
X.—Nitro-Benzene.
§ 239.-Nitro-benzene is the product resulting from the action of
strong nitric acid on benzene. Its chemical formula is C6H5NO2. When
pure, it is of a pale yellow colour, of a density of 1186, and boils at from
205° to 210°. It may be obtained in prismatic crystals by exposure to
a temperature of 3”. Its smell is exactly the same as that from the oil
or essence of bitter almonds; and it is from this circumstance, under
the name of “essence of mirbane,” much used in the preparation of
perfumes and flavouring agents.
In commerce there are three kinds of nitro-benzene—the purest, with
the characters given above; a heavier nitro-benzene, boiling at 210° to
220°; and a very heavy variety, boiling at 222° to 235°. The last is
specially used for the preparation of aniline, or aniline blue. Nitro-
benzene has been used as an adulterant of bitter almond oil, but the
detection is easy (see p. 198). Nitro-benzene was first discovered
by Mitscherlich in 1834, and its poisomous properties were first
pointed out by Casper f in 1859. Its technical use in perfumes, etc.,
dates from about 1848, and in the twenty-eight years intervening
between that date and 1876, Jübell i has collected 42 cases of poisoning
by this agent, 13 of which were fatal. One of these cases was suicidal,
the rest accidental.
§ 240. Effects of Poisoning by Nitro-benzene.—Nitro-benzene is a
very powerful poison, whether taken in the form of vapour or as a liquid.
The action of the vapour on animals has been studied by Eulenberg $
* Op. cit., i. p. 310.
+ Vierteljahrsschrift für ger. Med., Bd. xvi. p. 1, 1856.
† Die Vergiftwmgen mit Blausáure w. Nitro-benzol in forensischer Beziehung,
Erlangen, 1876.
§ Gewerbe Hygiene, S. 607, Berlin, 1876.
I 3
I94 POISONS: THEIR EFFECTS AND DETECTION. [$ 24.I.
and others. One experiment will serve as an illustration. Fifteen
grims, of nitro-benzene were evaporated on warm sand under a glass
shade, into which a cat was introduced. There was immediately ob-
served in the animal much salivation, and quickened and laboured
breathing. After thirty minutes' exposure, on removing the shade to
repeat the dose of 15 grns, the cat for the moment escaped. On being
put back there was again noticed the salivation and running at the eyes,
with giddiness, and repeated rising and falling. The animal at last,
about one hour and forty minutes after the first dose, succumbed with
dyspnoea, and died with progressive paralysis of the respiration. The
membranes of the brain were found gorged with blood, the lungs liver-
coloured, the mucous membrane of the trachea—to the finest subdivisions
of the bronchia—reddened, inflamed, and clothed with a fine frothy
mucus. The left side of the heart was filled with thick black blood.
The bladder contained 8 grms. of clear urine, in which aniline was dis-
covered. There was a notable smell of bitter almonds.
§ 241. The effects of the vapour on man are somewhat different in
their details to those just described. In a remarkable case related by
Dr. Letheby, a man, aged 42, had spilt some nitro-benzene over his
clothes. He went about several hours breathing an atmosphere of nitro-
benzene ; he then became drowsy, his expression was stupid, and his gait
unsteady, presenting all the appearances of intoxication. The stupor
suddenly deepened into coma, and the man died; the fatal course being
altogether about mine hours—viz., four hours before coma, and five
hours of total insensibility.
An interesting case of poisoning by the vapour is recorded by Taylor.”
A woman, aged 30, tasted a liquid used for flavouring pastry, which was
afterwards chemically identified as pure nitro-benzene. She immediately
spat it out, finding that it had an acrid taste, and probably did not
swallow more than a drop. In replacing the bottle, however, she spilt
about a tablespoonful, and allowed it to remain for some minutes; it was
a small room, and the vapour rapidly pervaded it, and caused illness in
herself as well as in a fellow-servant. She had a strange feeling of
numbness in the tongue, and in three hours and a quarter after the
accident was seen by a medical man; she then presented all the appear-
ances of prussic acid poisoning. The eyes were bright and glassy, the
features pale and ghastly, the lips and nails purple as if stained with
blackberries, the skin clammy, and the pulse feeble ; but the mind was
then clear. An emetic was administered, but she suddenly became
unconscious; the emetic acted, and brought up a fluid with an odour of
nitro-benzene. The stomach-pump was also used, but the liquid obtained
had scarcely any odour of nitro-benzene. In about eleven hours con-
* Poisons, Third Edition, p. 665.
§ 242.] NITRO-BENZENE. I95
sciousness returned, and in about seventeen hours she partially recovered
but complained of flashes of light and strange colours before her eyes.
Recovery was not complete for weeks. In this case the small quantity
swallowed would probably of itself have produced no symptoms, and the
effects are to be mainly ascribed to the breathing of the vapour.
§ 242. The liquid, when swallowed, acts almost precisely in the same
way as the vapour, and the symptoms resemble very much those pro-
duced by prussic acid. The great distinction between prussic acid and
nitro-benzene poisoning is that, in the latter, there is an interval between
the taking of the poison and its effects. This is, indeed, one of the
strangest phenomena of nitro-benzene poisoning, for the person, after
taking it, may appear perfectly well for periods varying from a quarter
of an hour to two or three hours, or even longer, and then there may be
most alarming symptoms, followed by rapid death. Poisoning by nitro-
benzene satisfies the ideal of the dramatist, who requires, for the purposes
of his plot, poisons not acting at once, but with an interval sufficiently
prolonged to admit of lengthy rhapsodies and a complicated dénouement.
On drinking the poison there is a burning taste in the mouth, shortly
followed by a very striking blueness or purple appearance of the lips,
tongue, skin, nails, and even the conjunctiva. This curious colour of
the skin has, in one or two instances, been witnessed an hour before any
feeling of illness manifested itself; vomiting then comes on, the vomited
matter smelling of nitro-benzene. The skin is cold, there is great de-
pression, and the pulse is small and weak. The respiration is affected,
the breathing being slow and irregular, the breath smelling strongly of
the liquid, and the odour often persisting for days. A further stage is
that of loss of consciousness, and this comes on with all the suddenness
of a fit of apoplexy. The coma is also similar in appearance to apoplectic
coma, but there have frequently been seen trismus and convulsions of the
extremities. The pupils are dilated and do not react to light, and reflex
sensibility is sometimes completely extinguished. Cases vary a little in
their main features; in a few the blue skin and the deep sleep are the
only symptoms noted. Death, for the most part, occurs after a period of
from eight to twenty-four hours (occasionally as soon as four or five
hours) after taking the poison.
From the following remarkable train of symptoms in a dog, it is
probable, indeed, that nitro-benzene, taken by a human being, might
produce death, after a rather prolonged period of time, by its secondary
effects:—To a half-bred greyhound * were administered 15 grms. of nitro-
benzene, when shortly after there were noticed much salivation, shiver-
ing, and muscular twitchings. The same dose was repeated at the end of
five, of seven, and of eight hours respectively, so that the dog altogether
* Eulenberg, Gewerbe Hygiene, S. 607.
196 POISONS : THEIR EFFECTS AND DETECTION. [$ 243.
took 60 grms., but with no other apparent symptom than the profuse
salivation. On the following day, the dog voided a tapeworm ; vomit-
ing supervened; the heart's action was quickened, and the breathing
difficult; convulsions followed, and the pupils were seen to be dilated.
For eight days the dog suffered from dyspnoea, quickened pulse, shivering
of the legs or of the whole body, tetanic spasms, bloody motions, great
thirst and debility. The temperature gradually sank under 25°, and the
animal finally died. The autopsy showed, as the most striking change,
the whole mucous membrane of the intestinal tract covered with a yellow
layer, which chemical analysis proved to be caused by picric acid, and in
the urine, liver, and lungs aniline was discovered.
$ 243. Fatal Dose.—It is probable, from recorded cases, that 1 grm.
(15:4 grains) would be quite sufficient to kill an adult, and, under
favourable circumstances, less than that quantity. It would seem that
spirituous liquids especially hasten and intensify the action of nitro-
benzene, so that a drunken person, casteris paribus, taking the poison with
spirits, would be more affected than taking it under other conditions.
In a case related by Stevenson,” in which so small a quantity as 1.74
grm, was taken in seven doses, spread over more than forty-eight hours,
there were yet extremely alarming symptoms, and the patient seems to
have had a narrow escape. On the other hand, a woman admitted into the
General Hospital, Vienna, took 100 grns. (about 3% ozs.) and recovered ;
on admission she was in a highly cyanotic condition, with small pulse,
superficial respiration, and dribbling of urine, which contained nitro-
benzol. Artificial respiration was practised, and camphor injections were
administered. Under this treatment consciousness was restored, and the
patient recovered. On the fourth day the urine resembled that of a case
of cystitis (Lancet, Jan. 16, 1894). The quantity of nitro-benzene which
would be fatal, if breathed, is not known with any accuracy.
* This case is not uninteresting. Through a mistake in reading an extremely
illegible prescription, M. S. S., at 21, was supplied by a druggist with the following
mixture :—
B. Benzole-Nit., 3iij.
Ol. Menth. pep., 3ss.
Ol. Olivae, 3x.
gutt. xxx., t, ds.
He took on sugar seven doses, each of 20 minims, equalling in all 23 min. (or by
weight 271 grains = 1 74 grim.) of nitro-benzene—viz., three doses on the first day,
three on the second, and one on the morning of the third day. The first two
days he was observed to be looking pale and ill, but went on with his work until the
seventh dose, which he took on the third day at 9 A.M. About 2 P.M. (or six
hours after taking the seventh dose), he fell down insensible, the body pale blue,
and with all the symptoms already described in the text, and usually seen in nitro-
benzene poisoning. With suitable treatment he recovered. The next morning,
from 8 ounces of urine some nitro-benzene was extracted by shaking with chloroform.
—Thos. Stevenson, M.D., in Guy's Hospital Reports, MS., vol. xxi., 1876.
§ 244-246.] NITRO-BENZENE. - 197
§ 244. Pathological Appearances.—The more characteristic appear-
ances seem to be, a dark brown or even black colour of the blood, which
coagulates with difficulty (an appearance of the blood that has even been
noticed during life), venous hyperaemia of the brain and its membranes,
and general venous engorgement. In the stomach, when the fluid has
been swallowed, the mucous membrane is sometimes reddened diffusely,
and occasionally shows ecchymoses of a punctiform character.
§ 245. The essential action of nitro-benzene is of considerable
physiological interest. The blood is certainly in some way changed, and
gives the spectrum of acid haematin.” Filehne has found that the blood
loses, in a great degree, the power of carrying and imparting oxygen to
the tissues, and its content of carbon dioxide is also increased. Thus,
the normal amount of oxygen gas which the arterial blood of a hound
will give up is 17 per cent. ; but in the case of a dog which had been
poisoned with nitro-benzene, it sank to l per cent. During the dyspnoea
from which the dog suffered, the carbon dioxide exhaled was greater
than the normal amount, and the arterial blood (the natural content of
which should have been 30 per cent. of this gas) only gave up 9 per
cent. Filehne seeks to explain the peculiar colour of the skin by the
condition of the blood, but the explanation is not altogether satisfactory.
Some part of the nitro-benzene, without doubt, is reduced to aniline in
the body—an assertion often made, and as often contradicted—but it has
been found in too many cases to admit of question. It would also seem
from the experiment on the dog (p. 196), that a conversion into picric
acid is not impossible. A yellow colour of the skin and conjunctivae, as
if picric-acid-stained, has been noticed in men suffering under slow
poisoning by nitro-benzene.
§ 246. Detection and Separation of Nitro-benzene from the
Animal Tissues.—It is evident from the changes which nitro-benzene
may undergo that the expert, in any case of suspected nitro-benzene
poisoning, must specially look (1) for nitro-benzene, (2) for aniline, and
(3) for picric acid. The best general method for the separation of nitro-
benzene is to shake up the liquid (or finely-divided solid) with light
benzoline (petroleum ether), which readily dissolves nitro-benzene. On
evaporation of the petroleum ether, the nitro-benzene is left, perhaps
mixed with fatty matters. On treating with cold water, the fats rise to
the surface, and the nitro-benzene sinks to the bottom ; So that by means
of a separating funnel, the nitro-benzene may be easily removed from
animal fats. The oily drops, or fine precipitate believed to be nitro-
benzene, may be dissolved in spirit and reduced to aniline by the use of
nascent hydrogen, developed from iron filings by hydrochloric acid, and
* Filehne, W., “Ueber die Giftwirkungen des Nitrobenzols,” Arch, für exper.
Pathol, w, Pharm., ix. 329.
198 POISONS: THEIR EFFECTS AND DETECTION. [$ 247.
the fluid tested with bleaching-powder; or the aniline itself may be
recovered by alkalising the fluid, and shaking up with ether in the
separation tube (p. 163); the ether dissolves the aniline, and leaves it,
on spontaneous evaporation, as an oily yellowish mass, which, on the
addition of a few drops of sodic hypochlorite, strikes a blue or violet-
blue—with acids, a rose-red—and with bromine, a flesh-red. It gives
alkaloidal reactions with such general reagents as platinum chloride,
picric acid, etc. Aniline itself may be extracted from the tissues and
fluids of the body by petroleum ether, but in any special search it will
be better to treat the organs as in Stas’ process—that is, with strong
alcohol, acidified with sulphuric acid. After a suitable digestion in this
menstruum, filter, and then, after evaporating the alcohol, dissolve the
alcoholic extract in water; alkalise the aqueous solution, and extract
the aniline by shaking it up with light benzoline. On separating the
benzoline, the aniline will be left, and may be dissolved in feebly-acid
water, and the tests before enumerated tried.
Malpurgo * recommends the following test for nitro-benzene:—2
drops of melted phenol, 3 drops of water, and a fragment of caustic
potash are boiled in a small porcelain dish, and to the boiling liquid the
aqueous solution to be tested is added. On prolonged boiling, if nitro-
benzene is present, a crimson ring is produced at the edges of the
liquid ; this crimson colour, on the addition of a little bleaching-powder,
turns emerald-green.
Oil of bitter almonds may be distinguished from nitro-benzene by
the action of manganese dioxide and sulphuric acid; bitter almond oil
treated in this way loses its odour, nitro-benzene is unaltered. To apply
the test, the liquid must be heated on the water-bath for a little time.
XI.-Dinitro-Benzol.
§ 247. Dinitro-benzol, C.H. (NO2), (ortho-, meta-, para-).—The ortho-
compound is produced by the action of nitric acid on benzol, aided by
heat in the absence of strong sulphuric acid to fix water. Some of the
para-dinitro-benzol is at the same time produced. The meta-compound
is obtained by the action of fuming nitric acid on nitro-benzol at a boiling
temperature.
The physical properties of the three dinitro-benzols are briefly as
follows:—
Ortho-d. is in the form of needles; m.p. 118°.
Meta-d. crystallises in plates; m.p. 90°.
* Zeit, anal. Chem..., xxxii. 235.
§ 248.] DINITRO-BENZOL. I99
Para-d. crystallises, like the ortho-compound, in needles, but the
melting-point is much higher, 171° to 172°.
Just as nitro-benzol by reduction yields aniline, so do the nitro-
benzols on reduction yield ortho-, meta-, or para-phenylene diamines.
Meta-phenylene diamine is an excellent test for nitrites; and, since
the commercial varieties of dinitro-benzol consist either mainly or in part
of meta-dinitro-benzol, the toxicological detection is fairly simple, and is
based upon the conversion of the dinitro-benzol into meta-phenylene-
diamine.
Dinitro-benzol is at present largely employed in the manufacture of
explosives, such as roburite, sicherheit, and others. It has produced
much illness among the workpeople in manufactories, and amongst
miners whose duty it has been to handle such explosives.
§ 248. Effects of Dinitro-benzol.—Huber * finds that if dinitro-
benzol is given to frogs by the mouth in doses of from 100 to 200
mgrms., death takes place in a few hours. Doses of from 2-5 to 5
mgrms. cause general dulness, and ultimately complete paralysis, and
death in from one to six days.
Rabbits are killed by doses of 400 mgrms., in time varying from
twenty-two hours to four days.
In a single experiment on a small dog, the weight of which was
5525 grms., the dog died in six hours after a dose of 600 mgrms.
It is therefore probable that a dose of 100 mgrms. per kilo. would
kill most warm-blooded animals.
A transient exposure to dinitro-benzol vapours in man causes serious
symptoms; for instance, in one of Huber's cases, a student of chemistry
had been engaged for one hour and a half only in preparing dinitro-
benzol, and soon afterwards his comrades remarked that his face was of
a deep blue colour. On admission to hospital, on the evening of the
same day, he complained of slight headache and sleeplessness; both
cheeks, the lips, the muscles of the ear, the mucous membrane of the
lips and cheeks, and even the tongue, were all of a more or less intense
blue-grey colour. The pulse was dicrotic, 124; T. 37.2°. The next
morning the pulse was slower, and by the third day the patient had
recovered.
Excellent accounts of the effects of dinitro-benzol in roburite factories
have been published by Dr. Ross f and Professor White,f of Wigan.
Mr. Simeon Snell $ has also published some most interesting cases of
illness, cases which have been as completely investigated as possible.
* “Beitrage zur Giftwirkung des Dinitrobenzols,” A. Huber, Virchow's Archiv,
Bd. cxxvi. S. 240, 1891.
t Medical Chronicle, 1889, 89. † Practitioner, 1889, ii. 15.
Š Brit. Med. Journ., March 3, 1894.
2OO POISONS : THEIR EFFECTS AND DETECTION. [Š 249.
As an example of the symptoms produced, one of Mr. Snell's cases may
be here quoted.
C. F. W., aged 38, consulted Mr. Snell for his defective sight on
April 9, 1892. He had been a mixer at a factory for the manufacture
of explosives. He was jaundiced, the conjunctiva yellow, and the lips
blue. He was short of breath, and after the day's work experienced
aching of the forearms and legs and tingling of the fingers. The urine
was black in colour, of sp. gr. 1024; it was examined spectroscopically
by Mr. MacMunn, who reported the black colour as due neither to
indican, nor to blood, nor bile, but to be caused by some pigment be-
longing to the aromatic series. The patient's sight had been failing

2O 20
Diagram of Visual Field.
since the previous Christmas. Vision in the right eye was ºr, left # 3
both optic papillae were somewhat pale. In each eye there was a central
scotoma for red, and contraction of the field (see diagram). The man
gradually gave up the work, and ultimately seems to have recovered.
It is, however, interesting to note that, after having left the work for
some weeks, he went back for a single day to the “mixing,” and was
taken very ill, being insensible and delirious for five hours.
§ 249. The Blood in Nitro-benzol Poisoning.—The effect on the
blood has been specially studied by Huber.” The blood of rabbits
poisoned by dinitro-benzol is of a dark chocolate colour, and the micro-
scope shows destruction of the red corpuscles; the amount of destruction
may be gathered from the following:—the blood corpuscles of a rabbit
before the experiment numbered 5,888,000 per cubic centimetre; a day
* Op. cit.
§ 250.] DINITRO-BENZOL. 2O I
after the experiment 4,856,000; a day later 1,004,000; on the third
day the rabbit died.
In one rabbit, although the corpuscles sank to 1,416,000, yet re-
covery took place.
Dr. MacMunn * has examined specimens of blood from two of Mr.
Snell's patients; he found a distinct departure from the normal; the red
corpuscles were smaller than usual, about 5 or 6 p. in diameter, and the
appearances were like those seen in pernicious anaemia. Huber, in some
of his experiments on animals, found a spectroscopic change in the
blood, viz., certain absorption bands, one in the red between C and D,
and two in the green between D and E ; the action of reducing agents
on this dinitro-benzol blood, as viewed in a spectroscope provided with
a scale in which C = 48, D = 62, and E = 80°5, was as follows:–
Dinitro-Bands.
In Red. In Green.
2–’->
50–52 62–66 70–77
After NH4SO1, º tº 53–55 62–66 70–77
,, NH3, . g g 54–58 60–65 70–77
,, NH4SO-H-NH2, te 52–55 60–65 70–77
Taking the symptoms as a whole, there has been noted :-a blue
colour of the lips, not unfrequently extending over the whole face, and
even the conjunctivae have been of a marked blue colour, giving the
sufferer a strange livid appearance. In other cases there have been
jaundice, the conjunctivae and the skin generally being yellow, the lips
blue. Occasionally gastric symptoms are present. Sleeplessness is
common, and not unfrequently there is some want of muscular co-
ordination, and the man staggers as if drunk. In more than one case
there has been noticed sudden delirium. There is in chronic cases always
more or less anaemia, and the urine is remarkable in its colour, which
ranges from a slightly dark hue up to positive blackness. In a large
proportion of cases there is ophthalmic trouble, the characteristics of
which (according to Mr. Snell) are “failure of sight, often to a consider-
able degree, in a more or less equal extent on the two sides; concentric
attraction of visual field with, in many cases, a central colour Scotoma ;
enlargement of retinal vessels, especially the veins; some blurring,
never extensive, of edges of disc, and a varying degree of pallor of its
surface—the condition of retinal vessels spoken of being observed in
workers with the dimitro-benzol, independently of complaints of defective
sight. Cessation of work leads to recovery.”
§ 250. Detection of Dinitro-benzol.—Dimitro-benzol may be detected
in urine, in blood, and in fluids generally, by the following process:—
Place tinfoil in the fluid, and add hydrochloric acid to strong acidity;
* Op. cit.
2O2 POISONS: THEIR EFFECTS AND DETECTION. [$ 251, 252.
after allowing the hydrogen to be developed for at least an hour, make
the fluid alkaline by caustic soda, and extract with ether in a separating
tube; any metaphenylene - diamine will be contained in the ether;
remove the ether into a flask, and distil it off; dissolve the residue in
a little water.
Acidify a solution of sodium nitrite with dilute sulphuric acid ; on
adding the solution, if it contains metaphenylene-diamine, a yellow to
red colour will be produced, from the formation of Bismarck brown
(triamido-phenol).
XII.-Hydrocyanic Acid.
§ 251. Hydrocyanic Acid (hydric cyanide)—specific gravity of liquid
0-7058 at 18° C., boiling-point 26'5" (80° F.), HCy = 27.—The anhy-
drous acid is not an article of commerce, and is only met with in the
laboratory. It is a colourless, transparent liquid, and so extremely vola-
tile that, if a drop fall on a glass plate, a portion of it freezes. It has a
very peculiar peach-blossom odour, and is intensely poisonous. It
reddens litmus freely and transiently, dissolves red oxide of mercury
freely, forms a white precipitate of argentic cyanide when treated with
silver nitrate, and responds to the other tests described hereafter.
§ 252. Medicinal Preparations of Prussic Acid.—The B.P. acid is
a watery solution of prussic acid; its specific gravity should be 0.997,
and it should contain 2 per cent. of the anhydrous acid; 2 per cent, is
also the amount specified in the pharmacopoeias of Switzerland and
Norway, and in that of Borussica (VI. ed.); the latter ordains, however,
a spirituous solution, and the Norwegian an addition of 1 per cent. of
concentrated sulphuric acid. The French prussic acid is ordered to be
prepared of a strength equalling 10 per cent.
The adulterations or impurities of prussic acid are hydrochloric, sul-
phuric,” and formic acids. Traces of silver may be found in the French
acid, which is prepared from cyanide of silver. Tartaric acid is also
occasionally present. Hydrochloric acid is most readily detected by
neutralising with ammonia, and evaporating to dryness in a water-bath ;
the ammonium cyanide decomposes and volatilises, leaving as a saline
residue chloride of ammonium. This may easily be identified by the
precipitate of chloride of silver, which its solution gives on testing with
silver mitrate, and the deep brown precipitate with Nessler solution.
Sulphuric acid is, of course, detected by chloride of barium ; formic acid
by boiling a small quantity with a little mercuric oxide; if present, the
* A trace of sulphuric or hydrochloric acid should not be called an adulteration,
for it greatly assists the preservation, and therefore makes the acid of greater thera-
peutic efficiency.
§ 253.] HYDROCYANIC ACID. 2O3
oxide will be reduced, and metallic mercury fall as a grey precipitate.
Silver, tartaric acid, and any other fixed impurities are detected by
evaporating the acid to dryness, and examining any residue which may
be left. It may be well to give the various strengths of the acids of
commerce in a tabular form :—
Per cent.
British Pharmacopoeia, Switzerland, and Bor. (v.j), & 2
France, e & & * • e § 10
Wauquelin's Acid, © º e º e º 3°3
Scheele's 3 3 e º tº o e . 4 to 5 *
Riner's 3 3 º © ſe © º tº 10
Robiquet's , , º g e º e * 50
Schraeder's , , " * e e - e e 1'5
Duflos’ } } º e & - e e 9
Pfaff’s 3 y º tº e & º º 10
Koller’s 3 5 o tº g tº e & 25
In English commerce, the analyst will scarcely meet with any acid
stronger than Scheele's 5 per cent.f
Impure oil of bitter almonds contains hydric cyanide in variable
quantity, from 5 per cent. up to 14 per cent. There is an officinal
preparation obtained by digesting cherry-laurel leaves in water, and then
distilling a certain portion over. This Aqua Lauro-cerasi belongs to the
old school of pharmacy, and is of uncertain strength, but varies from 7
to 1 per cent. of HCN.
§ 253. Poisoning by Prussic Acid. – Irrespective of suicidal or
criminal poisoning, accidents from prussic acid may occur—
1. From the use of the cyanides in the arts.
2. From the somewhat extensive distribution of the acid, or rather
of prussic-acid-producing substances in the vegetable kingdom.
1. In the Arts.—The galvanic silvering f and gilding of metals,
photography, the colouring of black silks, the manufacture of Berlin
blue, the dyeing of woollen cloth, and in a few other manufacturing
processes, the alkaline cyanides are used, and not unfrequently fumes of
prussic acid developed.
2. In the Animal Kingdom.—One of the myriapods (Chilognathem)
contains glands at the roots of the hairs, which secrete prussic acid ;
when the insect is seized, the poisomous secretion is poured out from the
So-called foramina repugnatoria.
3. In the Vegetable Kingdom.—A few plants contain cyanides, and
* Strength very uncertain.
t Kahlbaum now lists a 12 per cent, solution.
f The preparation used for the silvering of copper vessels is a solution of cyanide
of silver in potassic cyanide, to which is added finely powdered chalk. Manipu-
lations with this fluid easily develop hydrocyanic acid fumes, which, in one case
related by Martin (Aertzl. Intelligenzbl., p. 135, 1872), were powerful enough to
produce symptoms of poisoning.
2O4. POISONS : THEIR EFFECTS AND DETECTION. [$ 253.
many contain amygdalin, or bodies formed on the type of amygdalin. In
the presence of emulsin (or similar principles) and water, this breaks up
into prussic acid and other compounds—an interesting reaction usually
represented thus—
CooHo, NOil + 2H,0-> CNH + C, H2O + 2C HigO,
1 equivalent of amygdalin—i.e. 457 parts—yielding 1 equivalent of
CNH or 27 parts; in other words, 100 parts of amygdalin yield theo-
retically 5'909 parts of prussic acid,” so that, the amount of either being
known, the other can be calculated from it.
Dunstan and Henry f have discovered three glucosides:—
“dhurrin’ in the young plants of the great millet, Sorghum vulgare;
“lotusin” in Lotus arabiens, a legume indigenous to Egypt; and
“phaseo-lunatin’” in the beans of the wild Phaseolus lunatus.
Lotusin, Cºsha, OlgN, is a maltose-cyan-hydrin, one molecule yielding
on hydrolysis, 1 molecule of hydric cyanide, 2 of dextrose, and 1 of
lotoflavin.
Dhurrin, C17H17O, N, yields on hydrolysis, hydric cyanide, hydroxy-
benzaldehyde, and dextrose,
Phaseo-lunatin, Clo Hay06 N, may be obtained in rosettes of needle-like
crystals, m.p. 141.0°. Hydrolysis breaks the glucoside up into hydric
cyanide, acetone, and dextrose, -
Clo Hº O.M + H2O -> HCN + C.H1,064-(CH2)9CO.
F. B. Power and F. H. Lees I have isolated from the seeds
of Gynocardata odorata a glucoside which they name gynocardin,
C18H1909 N, on hydrolysis yielding hydric cyanide, dextrose, and an
acid.
Many cases of death occurring among cattle fed on immature
Sorghum have been shown by J. C. Brunnich Š to be due to “dhurrin.
Greshoffſ has discovered an amygdalin-like glucoside in the two
tropical trees Pygeum parviflorum and P. latifolium. The same author
states that the leaves of Gymnema latifolium, one of the Asclepiads,
yields to distillation benzaldehyde hydrocyanide. Both Lasia and
Cyrtosperma, plants belonging to the natural family of the Orontads,
* According to Liebig and Wohler, 17 grms. of amygdalin yield 1 of prussic acid
(i.e. 5.7 per cent.) and 8 of oil of bitter almonds. Thirty-four parts of amygdalin,
mixed with 66 of emulsin of almonds, give a fluid equalling the strength of acid of
most pharmacopoeias, viz., 2 per cent.
+ Proc. Roy. Soc., lxviii., 1901; lxxii., 1903.
: Journ. Chem. Soc., lxxxix., 1905. § Ib., lxxxiii., 1903.
| M. Greshoff– “Erster Bericht tiber die Untersuchung von Pflanzenstoffen
Niederländisch-Indiens.” Mittheilungen aws dem chemisch-pharmakologischen
Laboratorium des botan. Gartens des Staates, vii., Batavia, 1890, Niederländisch.
Dr. Greshoff's research indicates that there are several other cyanide-yielding plants
than those mentioned in the text.
§ 254.] HYDROCYANIC ACID. 2O5
contain in their flowers potassic cyanide. Pangium edule, according to
Greshoff, contains so much potassic cyanide that he was able to prepare
a considerable quantity of that salt from one sample of the plant. An
Indian plant (Hydnocarpus inebrians) also contains a cyanide, and has
been used for the purpose of destroying fish. Among the Tiliads,
Greshoff found that Echinocarpus Sigun yielded hydrocyanic acid on
distillation. Even the common linseed contains a glucoside which
breaks up into sugar, prussic acid, and a ketone.
The following plants, with many others, all yield, by appropriate treat-
ment, more or less prussic acid:—Bitter almonds (Amygdalus communis);
the Amygdalus persica ; the cherry laurel (Prunus laurocerasus); the
kernels of the plum (Prunus domestica); the bark, leaves, flowers, and
fruit of the wild service-tree (Prunus padus); the kernels of the common
cherry and the apple; the leaves of the Prunus capricida; the bark of
the Pr. virginiana; the flowers and kernels of the Pr. spinosa; the
leaves of the Cerasus acida; the bark and almost all parts of the
Sorbus aucuparia, S. hybrida, and S. torminalis; the young twigs of
the Crataegus Oayacantha; the leaves and partly also the flowers
of the shrubby Spiraeae, such as Spiraea aruncus, S. Sorbifolia,
and S. japonica ; * together with the roots of the bitter and sweet
Cassava.
In only a few of these, however, has the exact amount of either
prussic acid or amygdalin been determined ; 1 grnm. of bitter almond
pulp is about equal to 2% mgrms. of anhydrous prussic acid. The
kernels from the stones of the cherry, according to Geiseler, yield 3
per cent. of amygdalin ; therefore, 1 grnm. equals 1.7 mgrm. of HCN.
§ 254. The wild service-tree (Prunus padus) and the cherry-laurel
(Prunus laurocerasus) contain, not amygdalin but a compound of
amygdalin with amygdalic acid; to this has been given the name of
laurocerasin. It was formerly known as amorphous amygdalin; its
formula is Cao Hs;NO24; 933 parts are equivalent to 27 of hydric cyanide
—that is, 100 parts equal to 2.89.
In the bark of the service-tree Lehmann found 7 per cent. of
laurocerasin (= 02 HCN), and in the leaves of the cherry-laurel 1:38
per cent, (= 039 HCN).
Francis,t in a research on the prussic acid in cassava root, gives as
the mean in the sweet cassava 0168 per cent., in the bitter '0275 per
cent., the maximum in each being respectively 0238 per cent. and
‘0442 per cent. The bitter-fresh cassava root has long been known as
a very dangerous poison; but the sweet has hitherto been considered
* The bark and green parts of the Prunus avium, L., Prunus mahaleb, L., and
herbaceous Spiraeae yield no prussic acid.
t “On Prussic Acid from Cassava,” Analyst, April 1877, p. 5.
2O6 POISONS: THEIR EFFECTS AND DETECTION. [$ 255.
harmless, although it is evident that it also contains a considerable
quantity of prussic acid.
The kernels of the peach contain about 2.85 per cent. amygdalin
(= ‘17 HCN); those of the plum '96 per cent. (= 056 HCN); and
apple pips 6 per cent. (= 035 per cent. HCN). A. Hébert * has
found a few milligrammes of HCN in 100 grammes of the young
shoots of Ribes rubrum; 0.04 per cent. in the embryo of the fruit of
Priobotrya japonica, and from 0.01 per cent. to 0.001 per cent. in
various parts of Aquilegia vulgaris at the commencement of vegetation.
It is of great practical value to know, even approximately, the
quantity of prussic acid contained in various fruits, since it has been
adopted as a defence in criminal cases that the deceased was poisoned
by prussic acid developed in substances eaten.
§ 255. Statistics.-Poisoning by the cyanides (prussic acid or
cyanide of potassium) occupies the third place among poisons in order
of frequency in this country, and accounts for about 40 deaths
annually. -
In the ten years ending 1903 there were recorded no less than 536
cases of accidental, suicidal, or homicidal poisoning by prussic acid and
potassic cyanide. The further statistical details may be gathered from
the following tables:—
DEATHS IN ENGLAND AND WALES DURING THE TEN YEARS 1894–
1903 FROM PRUSSIC ACID AND POTASSIC CYANIDE.
PRUSSIC ACID (ACCIDENT PRUSSIC ACID (SUICIDE).
OR NEGLIGENCE).
Males, º - e s , 272
Males, . © e e º . 17 Females, . © e . . . 22
Females, - e e e ... 2 -*e
- Total, . 294
Total, . 19
CYANIDE OF POTASSIUM (ACCIDENT PoTAssIUM CYANIDE (SUICIDE).
oR NEGLIGENCE).
Males, e - e o . 166
Males, . - e º - . 30 Females, . e & • . 21
Females, e e º º ... 5 -*.
*E- Total, . 187
Total, . 35 •
To these figures must be added 1 case of murder by prussic acid.
In order to ascertain the proportion in which the various forms of
commercial cyanides cause death, and also the proportion of accidental,
suicidal, and criminal deaths from the same cause, Falck collated
twelve years of statistics from medical literature with the following
result:—
* Bull. Soc. Chim., iii. 19, 1898.
§ 256.] HYDROCYANIC ACID. 2O7
In 51 cases of cyanide poisoning, 29 were caused by potassic cyanide,
9 by hydric cyanide, 5 by oil of bitter almonds, 3 by peach stones
(these 3 were children, and are classed as “domestic,” that is, taking
the kernels as a food), 3 by bitter almonds (1 of the 3 suicidal and
followed by death, the other 2 “domestic"), 1 by tartaric acid and
potassic cyanide (a suicidal case, an apothecary), and 1 by ferro-cyanide
of potassium and tartaric acid. Of the 43 cases first mentioned, 21
were suicidal, 7 criminal, 8 domestic, and 7 medicinal; the 43 patients
were 24 men, 14 children, and 5 women.
The cyanides are very rarely used for the purpose of murder: a
poison which has a strong smell and a perceptible taste, and which
also kills with a rapidity only equalled by deadly bullet or knife wounds,
betrays its presence with too many circumstances of a tragic character
to find favour in the dark and secret schemes of those who desire to
take life by poison. In 793 poisoning cases of a criminal character in
France, 4 only were by the cyanides.
Hydric and potassic cyanides were once the favourite means of
self-destruction employed by suicidal photographers, chemists, scientific
medical men, and others in positions where such means are always at
hand; but, of late years, the popular knowledge of poisons has
increased, and self-poisoning by the cyanides scarcely belongs to a
particular class. A fair proportion of the deaths are also due to
accident or unfortunate mistakes, and a still smaller number to the
immoderate or improper use of cyanide-containing vegetable products.
§ 256. Accidental and Criminal Poisoning by Prussic Acid.—The
poison is almost always taken by the mouth into the stomach, but
occasionally in other ways—such, for example, as in the case of the
illustrious chemist, Scheele, who died from inhalation of the vapour of
the acid which he himself discovered, owing to the breaking of a flask.
There is also the case related by Tardieu, in which cyanide of potassium
was introduced under the nails; and that mentioned by Carriere, * in
which a woman gave herself, with suicidal intent, an enema containing
cyanide of potassium. It was been shown by experiments, in which
every care was taken to render it impossible for the fumes to be
inhaled, that hydrocyanic acid applied to the eye of warm-blooded
animals may destroy life in a few minutes.f
With regard to errors in dispensing, the most tragic case on record
is that related by Arnold : {−A pharmaceutist had put in a mixture
* “Empoisonnement par le cyanure de potassium,_guérison,” Bullet. général
de Thérap., 1869, No. 30.
t N. Gréhaut, Compt. rend. Soc. Biol. [9], xi. 64, 65.
# Arnold, A. B., “Case of Poisoning by the Cyanide of Potassium,” Amer.
Journ, of Med. Scien., 1869.
2O8 POISONS: THEIR EFFECTS AND DETECTION. [$257, 258.
for a child potassic cyanide instead of potassic chlorate, and the child
died after the first dose : the chemist, however, convinced that he had
made no mistake, to show the harmlessness of the preparation, drank
some of it, and there and then died ; while Dr. Arnold himself, in-
cautiously tasting the draught, fell insensible, and was unconscious for
six hours.
§ 257. Fatal Dose.--Notwithstanding the great number of persons.
who in every civilised country fall victims to the cyanides, it is yet
somewhat doubtful what is the minimum dose likely to kill an adult
healthy man. The explanation of this uncertainty is to be sought
mainly in the varying strength of commercial prussic acid, which
varies from 1.5 (Schraeder's) to 50 per cent. (Robiquet's), and also in
the varying condition of the person taking the poison, more especially
whether the stomach be full or empty. In by far the greater number,
the dose taken has been much beyond that necessary to produce death,
but this observation is true of most poisonings.
The dictum of Taylor, that a quantity of commercial prussic acid,
equivalent to 1 English grain (65 mgrm.) of the anhydrous acid, would,
under ordinary circumstances, be sufficient to destroy adult life, has
been generally accepted by all toxicologists. The minimum lethal dose
of potassic cyanide is similarly put at 2:41 grains (157 grn.). As to
bitter almonds, if it be considered that as a mean they contain 2.5 per
cent. of amygdalin, then it would take 45 grns., or about 80 almonds,
to produce a lethal dose for an adult; with children less—in fact, 4 to
6 bitter almonds are said to have produced poisoning in a child.
§ 258. Action of Hydric and Potassic Cyanides on Living Organisms.
—Both hydric cyanide and potassic cyanide are poisonous to all living
forms, vegetable or animal, with the exception of certain fungi. The
cold-blooded animals take a larger relative dose than the warm-blooded,
and the mammalia are somewhat more sensitive to the poisonous action
of the cyanides than birds; but all are destroyed in a very similar
manner, and without any essential difference of action. The symptoms
produced by hydric and potassic cyanide are identical, and, as regards
general symptoms, what is true as to the one is also true as to the other.
There is, however, one important difference in the action of these two
substances, if the mere local action is considered, for potassic cyanide is
very alkaline, possessing even caustic properties. For instance, the
gastric mucous membrane of a woman, who had taken an excessive dose
of potassic cyanide on an empty stomach, was so inflamed and swollen,
that its state was similar to that induced by a moderate quantity of
solution of potash. On the other hand, the acid properties of hydric
cyanide are very feeble, and its effect on mucous membranes or on the
skin in no way resembles that of the mineral acids.
§ 258A, 259.] HYDROCYANIC ACID. 2O9
It attacks the animal system in two ways: the one, a profound
interference with the ordinary metabolic changes; the other, a paralysis
of the nervous centres. Schönbein discovered that it affected the blood
corpuscles in a peculiar way; normal blood decomposes with great ease
hydrogen peroxide into oxygen and water. If to normal venous blood
a little peroxide of hydrogen be added, the blood at once becomes bright
red; but if a trace of prussic acid be present, it is of a dark brown
colour. The blood corpuscles, therefore, lose their power of conveying
oxygen to all parts of the system, and the phenomena of asphyxia are
produced. Geppert * has proved that this is really the case by showing,
in a series of researches, that, under the action of hydric cyanide, less
oxygen is taken up, and less carbon dioxide formed than normal, even if
the percentage of oxygen in the atmosphere breathed is artificially
increased. The deficiency of oxygen is in part due to the fact that
substances like lactic acid, the products of incomplete combustion, are
formed instead of CO2. -
At the same time the protoplasm of the tissues is paralysed, and
unable to take up the loosely bound oxygen presented. This explains a
striking symptom which has been noticed by many observers, that is, if
hydrocyanic acid be injected into an animal, the venous blood becomes
of a bright red colour; in warm-blooded animals this bright colour is
transitory, but in cold-blooded animals, in which the oxidation process is
slower, the blood remains bright red.
§ 258A. Effect of Prussic Acid on Lower Organisms.-In 1 to
430 dilution prussic acid annihilates the function of Drosera. In 1 per
1000 infusoria soon die, algae live longer. In a certain degree of dilution
yeast-cells are paralysed but not killed, for on removal to a nutrient
fluid, free from the acid, their activity is resumed.
§ 259. Symptoms observed in Animals. –The main differences
between the symptoms induced in cold-blooded and warm-blooded
animals, by a fatal dose of hydric cyanide, are as follows:—
The respiration in frogs is at first somewhat dyspnoeic, then much
slowed, and at length it ceases. The heart, at first slowed, later contracts
irregularly, and at length gradually stops; but it may continue to beat
for several minutes after the respiration has ceased. But all these
progressive symptoms are without convulsion. Among warm-blooded
animals, on the contrary, convulsions are constant, and the sequence of
the symptoms appears to be—dyspnoea, slowing of the pulse, giddiness,
falling down, then convulsions with expulsion of the urine and faeces;
dilatation of the pupils, exophthalmus, and finally cessation of the pulse
and breathing. The convulsions also frequently pass into general
* Geppert, Ueber das Wesen der CNH. Vergift ; mit einer Tafel, Berlin, 1889;
Sep.-Abdr, aws 2tschr, f. klin. Med., Bd. xv.
I 4.
2 IO POISONS : THEIR EFFECTS AND DETECTION. [$ 260.
paralysis, with loss of reflex movements, weak, infrequent breathing,
irregular, quick, and very frequent pulse, and considerable diminution
of temperature.
The commencement of the symptoms in animals is extremely rapid,
the rapidity varying according to the dose and concentration of the acid.
It was formerly thought that the death from a large dose of the con-
centrated acid followed far more quickly than could be accounted for
by the blood carrying the poison to the nervous centres; but Blake was
among the first to point out that this doubt was not supported by facts
carefully observed, since there is always a sufficient interval between the
entry of the poison into the body and the first symptoms, to support the
theory that the poison is absorbed in the usual manner. Even when
Preyer injected a cubic centimetre of 60 per cent. acid into the jugular
vein of a rabbit, twenty-nine seconds elapsed before the symptoms
commenced. Besides, we have direct experiments showing that the acid
—when applied to wounds in limbs, the vessels of which are tied, while
the free nervous communication is left open—only acts when the ligature .
is removed. Magendie describes, in his usual graphic manner, how he
killed a dog by injecting into the jugular vein prussic acid, and “the
dog died instantly, as if struck by a cannon ball,” but it is probable that
the interval of time was not accurately noted. A few seconds pass very
rapidly, and might be occupied even by slowly pressing the piston of
the syringe down, and in the absence of accurate measurements, it is
surprising how comparatively long intervals of time are unconsciously
shortened by the mind. In any case, this observation by Magendie has
not been confirmed by the accurate tests of the more recent experi-
menters; and it is universally acknowledged that, although with strong
doses of hydric cyanide injected into the circulation—or, in other words,
introduced into the system—in the most favourable conditions for its
speediest action, death occurs with appalling suddenness, yet that it
takes a time sufficiently long to admit of explanation in the manner
suggested. This has forensic importance, which will be again alluded
to. Experiments on animals show that a large dose of a dilute acid
kills quite as quickly as an equivalent dose of a stronger acid, and in
some cases it even seems to act more rapidly. If the death does not
take place within a few minutes, life may be prolonged for hours, and
even, in rare cases, days, and yet the result be death. Coullon poisoned
a dog with prussic acid; it lived for nineteen days, and then died ; but
this is quite an exceptional case, and when the fatal issue is prolonged
beyond an hour, the chance of recovery is considerable.
§ 260. The length of time dogs poisoned by fatal doses survive, gener-
ally varies from two to fifteen minutes. The symptoms are convulsions,
insensibility of the cornea, cessation of respiration, and, finally, the heart
§ 261.] HYDROCYANIC ACID. 2 I I
stops—the heart continuing to beat several minutes after the cessation
of the respirations.” When the dose is short of a fatal one, the
symptoms are as follows:—Evident giddiness and distress; the tongue
is protruded, the breath is taken in short, hurried gasps, there is saliva-
tion, and convulsions rapidly set in, preceded, it may be, by a cry. The
convulsions pass into paralysis and insensibility. After remaining in
this state some time, the animal again wakes up, as it were, very often
howls, and is again convulsed; finally, it sinks into a deep sleep, and
wakes up well.
Preyer noticed a striking difference in the symptoms after section of
the vagus in animals, which varied according to whether the poison was
administered by the lungs, or subcutaneously. In the first case, if the
dose is small, the respirations are diminished in frequency; then this is
followed by normal breathing; if the dose is larger, there is an increase
in the frequency of the respirations. Lastly, if a very large quantity is
introduced into the lungs, death quickly follows, with respirations
diminished in frequency. On the other hand, when the poison is
injected subcutaneously, small doses have no influence on the breathing;
but with large doses, there is an increase in the frequency of the respira-
tions, which sink again below the normal standard.
§ 261. Symptoms in Man.—When a fatal but not excessive dose of
either potassic or hydric cyanide is taken, the sequence of symptoms is
as follows:–Salivation, with a feeling of constriction in the throat,
nausea, and occasionally vomiting. After a few minutes a peculiar con-
stricting pain in the chest is felt, and the breathing is distinctly affected.
Giddiness and confusion of sight rapidly set in, and the person falls to
the ground in convulsions similar to those of epilepsy. The convulsions
are either general, or attacking only certain groups of muscles; there is
often true trismus, and the jaws are so firmly closed that nothing will
part them. The respiration is peculiar—the inspiration is short, the
expiration prolonged,f and between the two there is a long interval, ever
becoming more protracted as death is imminent. The skin is pale, or
blue, or greyish-blue; the eyes are glassy and staring, with dilated
pupils; the mouth is covered with foam, and the breath smells of the
poison; the pulse, at first quick and small, sinks in a little while in
frequency, and at length cannot be felt. Involuntary evacuation of
faeces, urine, and semen is often observed, and occasionally there has
been vomiting, and a portion of the vomit has been aspirated into the
* N. Gréhaut, Compt. Rend., t, ciz, pp. 502, 503.
† In a case quoted by Seidel (Maschka's Handbuch, p. 321), a man, 36 years of
age, four or five minutes after swallowing 150 mgrms. anhydrous HCN in spirits, lay
apparently lifeless, without pulse or breathing. After a few minutes was noticed an
extraordinary deep expiration, by which the ribs were drawn in almost to the spine,
and the chest made quite hollow.
2 I 2 POISONS: THEIR EFFECTS AND DETECTION. [$ 262.
air-passages. Finally, the convulsions pass into paralysis, abolition of
reflex sensibility, and gradual ceasing of the respiration. With large
doses these different stages may occur, but the course is so rapid that
they are merged the one into the other, and are undistinguishable. The
shortest time between the taking of the acid and the commencement of
the symptoms may be put at about ten seconds. If, however, a large
amount of the vapour is inhaled at once, this period may be rather
lessened. The interval of time is so short that any witnesses generally
unintentionally exaggerate, and aver that the effects were witnessed
before the swallowing of the liquid—“As the cup was at his lips”—
“He had hardly drunk it,” etc. There is probably a short interval of
consciousness, then come giddiness, and, it may be, a cry for assistance;
and lastly, there is a falling down in convulsions, and a speedy death.
Convulsions are not always present, the victim occasionally appears to
sink lifeless at once. Thus, in a case related by Hufeland, a man was
seen to swallow a quantity of acid, equivalent to 40 grains of the pure
acid—that is, about forty times more than sufficient to kill him. He
staggered a few paces, and then fell dead, without sound or convulsion.
§ 262. The very short interval that may thus intervene between the
taking of a dose of prussic acid and loss of consciousness, may be utilised
by the sufferer in doing various acts, and thus this interval becomes of
immense medico-legal importance. The question is simply this:–What
can be done by a person in full possession of his faculties in ten seconds?
We have found from experiment that, after drinking a liquid from a
bottle, the bottle may be corked, the individual can get into bed, and
arrange the bedclothes in a suitable manner; he may also throw the
bottle away, or out of the window ; and, indeed, with practice, in that
short time a number of rapid and complicated acts may be performed.
This is borne out both by experiments on animals and by recorded
Ca,S6S. -
In Mr. Nunneley's numerous experiments on dogs, one of the
animals, after taking poison, “went down three or four steps of the
stairs, saw that the door at the bottom was closed, and came back again.”
A second went down, came up, and went again down the steps of a long
winding staircase, and a third retained sufficient vigour to jump over
another dog, and then leap across the top of a staircase.
In a remarkable case related by Dr. Guy,” in which a young man,
after drinking more wine than usual, was seized by a sudden impulse to
take prussic acid, and drank about 2 drachms, producing symptoms
which, had it not been for prompt treatment, would, in all probability,
have ended fatally—the interval is again noteworthy. After taking the
poison in bed, he rose, walked round the foot of a chest of drawers,
* Forensic Medicine, 4th ed., p. 615.
§ 263.] HYDROCYANIC ACID. 2 I 3
standing within a few yards of the bedside, placed the stopper firmly
in the bottle, and then walked back to bed with the intention of getting
into it; but here a giddiness seized him, and he sat down on the edge,
and became insensible. -
A case related by Taylor is still stronger. A woman, after swallowing
a fatal dose of essence of almonds, went to a well in the yard, drew
water, and drank a considerable quantity. She then ascended two
flights of stairs and called her child, again descended a flight of stairs,
fell on her bed, and died within half an hour from the taking of the
poison.
Nevertheless, these cases and similar ones are exceptional, and only
show what is possible, not what is usual, the rule being that after fatal.
doses no voluntary act of significance—save, it may be, a cry for assist-
ance—is performed.*
Symptoms of poisoning by prussic acid produced from eating
substances containing the cyanide glucosides may occur, and death
result hours after the ingestion of such substances, as illustrated by the
following interesting cases described by Dr. A. Robertson and A. J.
Wynne.f
In March 1905 a steamer brought to Rotterdam a cargo of “kratok”
beans (Phaseolus lunatus) for the purpose of feeding cattle. A workman
(Baris) employed in unloading took some of the beans and gave some
to a family named Van Oostende, Sunday, March 11, 12.30. Baris ate
some of the beans which had been boiled; in the evening he felt unwell,
became faint, had convulsions, and died about eleven hours after the meal.
The Van Oostende family, six in number, four children and two adults,
partook of the beans about 12 noon of the same day; all became ill
three hours afterwards; three of the children died, the rest recovered.
The beans had been softened by soaking in warm water and salt and had
then been boiled; the three children who died had no diarrhoea, those
who recovered had diarrhoea. -
The unboiled beans yielded about 0.21 per cent. HCN ; from the boiled
beans only traces of HCN could be obtained save by incubating for twenty-
four hours in neutral solution with emulsin, then 0.09 per cent. of HCN
was obtained ; from the intestines of the three children 39, 4:9,
and 6.7 mgrms, of HCN were separated.
§ 263. Chronic poisoning by hydric cyanide is said to occur
among photographers, gilders, and those who are engaged daily in the
preparation or handling of either hydric or potassic cyanides. The
* Dr. J. Autal, a Hungarian chemist, states that cobalt nitrate is an efficacious
antidote to poisoning by either HCN or KCN. The brief interval between the taking
of a fatal dose and death can, however, be rarely utilised.—Lancet, Jan. 16, 1894.
+ Zeit. f. anal. Chemie, 1905.
2 I4 POISONS: THEIR EFFECTS AND DETECTION. [$ 264.
symptoms are those of feeble poisoning, headache, giddiness, noises in
the ears, difficult respiration, pain over the heart, a feeling of con-
striction in the throat, loss of appetite, nausea, obstimate constipation,
full pulse, with pallor and offensive breath. Koritschoner * has made
some observations on patients who were made to breathe at intervals,
during many weeks, prussic acid vapour, with the idea that such a
treatment would destroy the tubercle bacilli. Twenty-five per cent. of
those treated in this way suffered from redness of the pharynx, Saliva-
tion, headache, nausea, vomiting, slow pulse, and even albuminuria.
§ 264. Post-mortem. Appearances.f-If we for the moment leave
out of consideration any changes which may be seen in the stomach
after doses of potassic cyanide, then it may be affirmed that the
pathological changes produced by hydric and potassic cyanides mainly
coincide with those produced by suffocation. The most striking
appearance is the presence of bright red spots; these bright red
spots or patches are confined to the surface of the body, the blood
in the deeper parts being of the ordinary venous hue, unless, indeed,
an enormous dose has been taken ; in that case the whole mass of
blood may be bright red; this bright colour is due, according to
Kobert, to the formation of cyanmethaemoglobin. The lungs and
right heart are full of blood, and there is a backward engorgement
produced by the pulmonic block. The veins of the neck and the
vessels of the head generally are full of blood, and, in like manner,
the liver and kidneys are congested. In the mucous membrane of
the bronchial tubes there is a bloody foam, the lungs are gorged, and
often oedematous in portions; ecchymoses are seen in the pleura and
other serous membranes; and everywhere, unless concealed by putre-
faction or some strong-smelling ethereal oil, there is an odour of hydric
cyanide.
Casper has rightly recommended the head to be opened and
examined first, so as to detect the odour, if present, in the brain.
The abdominal and chest cavities usually possess a putrefactive smell,
but the brain is longer conserved, so that, if this course be adopted,
there is a greater probability of detecting the odour.
The stomach in poisoning by hydric cyanide is not inflamed, but
if alcohol has been taken at the same time, or previously, there may be
more or less redness.
In poisoning by potassic cyanide, the appearances are mainly the
* Wiener klin. Woch., 1891."
+ Hydric cyanide has, according to C. Brame, a remarkable antiseptic action,
and if administered in sufficient quantity to animals, preserves them after death for
a month. He considers that there is some more or less definite combination with
the tissues. *
§ 265.] HYDROCYANIC ACID. 2 I 5
same as those just detailed, with, it may be, the addition of caustic
local action. There may, however, be, as in the case of a gentleman who
drank accidentally a considerable dose of potassic cyanide just after
a full meal, not the slightest trace of any redness, still less of corrosion.
Here the contents of the stomach protected the mucous membrane, or
possibly the larger amount of acid poured out during digestion suffi-
ciently neutralised the alkali. Potassic cyanide, in very strong solu-
tion, may cause erosions of the lips, and the caustic effect may be
traced in the mouth, throat, gullet, to the stomach and duodenum ;
but this is unusual, and the local effects are, as a rule, confined to the
stomach and duodenum. The mucous membrane is coloured blood-
red, reacts strongly alkaline,” is swollen, and it may be even ulcerated.
The upper layers of the epithelium are also often dyed with the
colouring-matter of the blood, which has been dissolved out by the
cyanide. This last change is a post-mortem effect, and can be imitated
by digesting the mucous membrane of a healthy stomach in a solution
of cyanide. The intensity of these changes is, of course, entirely
dependent on the dose and emptiness of the stomach. If the dose is
so small as just to destroy life, there may be but little redness or
swelling of the stomach, although empty at the time of taking the
poison. In those cases in which there has been vomiting, and a part
of the vomit has been drawn into the air-passages, there may be also
inflammatory changes in the larynx. If essence of almonds has been
swallowed, the same slight inflammation may be seen which has been
observed with other essential oils, but no erosion, no strong alkaline
reaction, nor anything approaching the effects of the caustic cyanide.
In poisoning by bitter almonds no inflammatory change in the
mucous membrane of the coats of the stomach would be anticipated,
yet in one recorded case there seems to have been an eroded and
inflamed patch.
§ 265. Tests for Hydrocyanic Acid and Cyanide of Potassium.—
(1) The addition of silver nitrate to a solution containing prussic acid,
or a soluble cyanide,f produces a precipitate of argentic cyanide. 100
parts of argentic cyanide are composed of 80-60 Ag and 1914 CN,
* The following case came under the senior author's own observation :-A stout
woman, 35 years of age, the wife of a French polisher, drank, in a fit of rage, a solu-
tion of cyanide of potassium. It was estimated that about 15 grains of the solid sub-
stance were swallowed. She died within an hour. The face was flushed, the body not
decomposed; the mouth smelt strongly of cyanide ; the stomach had about an ounce
of bloody fluid in it, and was in a most intense state of congestion. There was com-
mencing fatty degeneration of the liver, the kidneys were flabby, and the capsule
adherent. The contents of the stomach showed cyanide of potassium, and the blood
was very fluid. The woman was known to be of intemperate habits.
† In the case of testing in this way for the alkaline cyanides, the solution must
contain a little free nitric acid.
2 I6 POISONS: THEIR EFFECTS AND DETECTION. [$ 265.
equivalent to 20-1 HCN. It is a white anhydrous precipitate, soluble
either in ammonia or in a solution of cyanide of potassium. It is
soluble in hot dilute nitric acid, but separates on cooling. A particle
of silver cyanide, moistened with strong ammonia, develops needles;
silver chloride treated similarly, octahedral crystals. It is insoluble
in water. Upon ignition it is decomposed into CN and metallic silver,
mixed with a little paracyanide of silver.
A very meat process for the identification of cyanide of silver is the
following:—Place the perfectly dry cyanide in a closed or sealed tube,
containing a few crystals of iodime. On heating slightly, iodide of
cyanogen is sublimed in beautiful needles. These crystals again may
be dissolved in a dilute solution of potash, a little ferrous sulphate
added, and hydrochloric acid, and in this way Prussian blue produced.
If the quantity to be tested is small, the vapour of the acid may be
evolved in a very short test tube, the mouth of which is closed by the
ordinary thin discs of microscopic glass, the under surface of which is
moistened with a solution of mitrate of silver; the resulting crystals
of silver cyanide are very characteristic, and readily identified by the
microscope.
(2) If, instead of silver nitrate, the disc be moistened with a solu-
tion of sulphate of iron (to which has been added a little potash), and
exposed to the vapour a short time, and then some dilute hydrochloric
acid added, the moistened surface first becomes yellow, then green, lastly,
and permanently, blue. No other blue compound of iron (with the
exception of Prussian blue) is insoluble in dilute hydrochloric acid.
(3) A third, and perhaps the most delicate of all, is the so-called
sulphur test. A yellow sulphide of ammonium, containing free sulphur,
is prepared by saturating ammonia by SH2, first suspending in the fluid
a little finely-precipitated sulphur (or an old, ill-preserved solution of
sulphide of ammonium may be used). Two watch-glasses are now taken;
in the one the fluid containing prussic acid is put, and the second (pre-
viously moistened with the sulphide of ammonium described) is inverted
over it. The glasses are conveniently placed for a few minutes in the
water-oven; the upper one is then removed, the moist surface evaporated
to dryness in the water-bath, a little water added, and then a small
drop of solution of chloride of iron. If hydrocyanic acid is present,
the sulphocyanide of iron will be formed of a striking blood-red colour.
(4) The reaction usually called Schönbein’s, or Pagenstecher and
Schönbein’s “ (but long known,i and used before the publication of their
* Neues Repert. de Pharm., xviii. 356.
+ This reaction (with tincture of guaiacum and copper) has been long known.
“I remember a pharmaceutist, who attended my father's laboratory, showing me
this test in 1828 or 1829.”—Mohr’s Toxicologie, p. 92.
§ 266.] HYDROCYANIC ACID. 217
paper), consists of guaiacum paper, moistened with a very dilute solution
of sulphate of copper (1: 2000). This becomes blue if exposed to the
vapour of hydrocyanic acid. Unfortunately, the same reaction is pro-
duced by ammonia, ozone, nitric acid, hypochlorous acid, iodine, bromine,
chromate of potash, and other oxidising agents, so that its usefulness is
greatly restricted.
(5) A very delicate test for prussic acid is as follows:—About one-
half centigrom. of ammonia, ferrous sulphate (or other pure ferrous
salt), and the same quantity of uranic nitrate, are dissolved in 50 c.c. of
water, and 1 c.c. of this test liquid is placed in a porcelain dish. On
now adding a drop of a liquid containing the smallest quantity of
prussic acid, a grey-purple colour, or a distinct purple precipitate is
produced.*
(6) A hot solution of potassic cyanide, mixed with picric acid,
assumes a blood-red colour, due to the formation of picro-cyanic acid.
Free HCN does not give this reaction, and therefore must first be
neutralised by an alkali.
(7) Schönbein's Test.—To a few drops of defibrinated ox-blood are
added a few drops of the carefully-neutralised distillate supposed to
contain prussic acid, and then a little neutral peroxide of hydrogen is
added. If the distillate contains no prussic acid, then the mixture
becomes of a bright pure red and froths strongly ; if, on the other hand,
a trace of prussic acid be present, the liquid becomes brown and does not
froth, or only slightly does so.
(8) Kobert's Test.—A 1–4 per cent. solution of blood, to which
a trace of ferridcyanide of potassium is added, is prepared, and the
neutralised distillate added to this solution. If hydric cyanide be
present, then the liquid becomes of a bright red colour, and, examined
spectroscopically, instead of the spectrum of methaemoglobin, will be
seen the spectrum of cyanmethaemoglobin. Kobert proposes to examine
the blood of the poisoned, for the purpose of diagnosis, during life. A
drop of blood from a healthy person, and a drop of blood from the
patient, are examined side by side, according to the process just given.
(9) An extremely delicate test has been suggested by F. Weehuizen
(Chem. Centr., 1905, i. 1191). To the solution supposed to contain HCN
is added an alkaline solution of phenolphthalin and weak copper sulphate
solution (1:2000); if HCN is present, phenolphthalin is oxidised in the
cold to phenolphthalein and the liquid turns red; it is said to be sensitive
even if 1 part of HCN is diluted up to 500,000 parts.
§ 266. Separation of Hydric Cyanide or Potassic Cyanide from
Organic Matters, such as the Contents of the Stomach, etc.—It is
* M. Carey Lea, Amer. Journ, of Science [3], ix. pp. 121–123; J. C. Society,
vol. i. p. 112, 1876.
2 I 8 POISONS: THEIR EFFECTS AND DETECTION. [$ 266.
very necessary, before specially searching for hydric cyanide in the
contents of the stomach, to be able to say, by careful and methodical
examination, whether there are or are not any fragments of bitter
almonds, of apples, peaches, or other substance likely to produce hydric
cyanide. If potassic cyanide has been taken, simple distillation will
always reveal its presence, because it is found partly decomposed into
hydric cyanide by the action of the gastric acids. Nevertheless, an acid
should always be added, and if, as in the routine process given at p. 51,
there is reasonable doubt for suspecting that there will be no cyanide
present, it will be best to add tartaric acid (for this organic acid will in
no way interfere with subsequent operations), and distil, as recommended,
in a vacuum. If, however, from the odour and from the history of the
case, it is pretty sure to be a case of poisoning by hydric or potassic
cyanide, then the substances, if fluid, are at once placed in a retort or
flask, and acidified with a suitable quantity of sulphuric acid, or if the
tissues or other solid matters are under examination, they are finely
divided, or pulped, and distilled, after acidifying with sulphuric acid as
before.* It may be well here, as a caution, to remark that the analyst
must not commit the unpardonable error of first producing a cyanide
by reagents acting on animal matters, and then detecting as a poison
the cyanide thus manufactured. If, for example, a healthy liver is
carbonised by nitric acid, Saturated with potash, and then burnt up,
cyanide of potassium is always one of the products; and, indeed, the
ashes of a great variety of nitrogenous organic substances may contain
cyanides—cyanides not pre-existing, but manufactured by combination.
By the action of nitric acid even on sugar, f hydric cyanide is produced.
The old method of distillation was to distil by the gentle heat of a
water-bath, receiving the distillate in a little weak potash water, and not
prolonging the process beyond a few hours. The experiments of Sokoloff,
however, throw a grave doubt on the suitability of this simple method
for quantitative results.
N. Sokoloff f recommends the animal substances to be treated by
water strongly acidified with hydric sulphate, and then to be distilled in
the water-bath for from two to three days; or to be distilled for twenty-
four hours, by the aid of an oil-bath, at a high temperature. He gives
the following example of quantitative analysis by the old process of
merely distilling for a few hours, and by the new :—
Old Process.--(1) Body of a hound—age, 2 years; weight, 5180
grms. ; dose administered, 57 mgrms. HCN ; death in fifteen minutes.
* Domenico Ganassini (Bull. de Soc. med, chir. de Pavia, 29) prefers in all
cases tartaric as the acidifying acid.
| Chemical News, lxviii. p. 75.
† Ber. d. deutsch. chem. Gesellsch., Berlin, ix. p. 1023.
§ 267.] HYDROCYANIC ACID. 2 I9
After five days there was found in the saliva 0-6 mgrm., stomach 3-2
mgrms., in the rest of the intestines 2-6 mgrms., in the muscles 4-1,–
total, 10°5.
(2) Weight of body, 4000 grims. ; dose given, 38 mgrms. ; death in
eleven minutes. After fifteen days, in the saliva 0:8, in the stomach
7-2, in the rest of the intestines 2-2, in the muscles 3-2,-total, 13°4.
New Process.—Weight of body, 5700 grims. ; dose, 57 mgrms. ;
death in twenty-four minutes. After fifteen days, in the saliva 1-1
mgrm., in the stomach 2-6, in the rest of the intestines 9-6, in the
muscles 319, and in the whole, 45.2 mgrms. Duration of process,
thirteen hours.
From a second hound, weighing 6800 grms. ; dose, 67 mgrms. ; 25-1
mgrms, were separated three days after death.
From a third hound, weighing 5920 grms. ; dose, 98 mgrms. ; after
forty days, by distillation on a sand-bath, there were separated 2-8
mgrms. from the saliva, 4-8 from the stomach, 16-8 from the intestines,
23-6 from the muscles, total, 48 mgrms.
It would also appear that he has separated 51.2 mgrms, of anhydrous
acid from the corpse of a dog which had been poisoned by 57 mgrms, of
acid, and buried sixty days.”
From another canine corpse, three days laid in an oven, and left
for twenty-seven days at the ordinary temperature, 5-1 mgrms. were
recovered out of a fatal dose of 38 mgrms.
The estimation was in each case performed by titrating the distillate
with argentic nitrate, the sulphur compounds having been previously
got rid of by saturating the distillate with KHO, and precipitating by
lead acetate.
Wenturoli f has, on the contrary, got good quantitative results with-
out distillation at all. A current of pure hydrogen gas is passed through
the liquid to be tested and the gas finally made to bubble through silver
nitrate. He states that the whole of the hydric cyanide present is
carried over in an hour. Metallic cyanides must be decomposed by
sulphuric acid or tartaric acid. Mercury cyanide must be decomposed
with SH, the solution acidified with tartaric acid, neutralised with
freshly precipitated calcic carbonate to fix any ferro- or ferri-cyanides
present, and hydrogen passed in and the issuing gases led first through
a solution of bismuth nitrate to remove SH3 and then into the silver
solution.
§ 267. How long after Death can Hydric or Potassic Cyanides be
Detected?—Sokoloff appears to have separated prussic acid from the
* Without wishing to discredit the statements of M. Sokoloff, we may point out
that a loss of half-a-dozen mgrms, only appears rather extraordinary.
† L’Orosi, xv. 85–88.
22O POISONS: THEIR EFFECTS AND DETECTION. [$ 268 269.
body of hounds at very long periods after death—in one case sixty days.
Dragendorff recognised potassic cyanide in the stomach of a hound after
it had been four weeks in his laboratory,” and in man eight days after
burial. Casper also, in his 211th case, states that more than 18 mgrms.
of anhydrous prussic acid were obtained from a corpse eight days after
death.i Dr. E. Tillner } has recognised potassic cyanide in a corpse four
months after death. Lastly, Struve S put 300 grims, of flesh, 400 of
common water, and 2.378 of KCy in a flask, and then opened the flask
after 547 days. The detection was easy, and the estimation agreed with .
the amount placed there at first. So that, even in very advanced stages
of putrefaction, and at periods after death extending beyond many
months, the detection of prussic acid cannot be pronounced impossible.
§ 268. Estimation of Hydrocyanic Acid or Potassic Cyanide.—In
all cases, the readiest method of estimating prussic acid (whether it be
in the distillate from organic substances or in aqueous solution) is to
saturate it with soda or potash, and titrate the alkaline cyanide thus
formed with nitrate of silver. The process is based on the fact that
there is first formed a soluble compound (KCy, AgCy), which the
slightest excess of silver breaks up, and the insoluble cyanide is at once
precipitated. If grains are used, 17 grains of nitrate of silver are
dissolved in water, the solution made up to exactly 1000 grain measures,
each grain measure equalling '0054 grain of anhydrous hydrocyanic acid.
If grammes are employed, the strength of the nitrate of silver solution
should be 1.7 grn, to the litre ; each c.c. then = .0054 hydrocyanic acid,
or -01302 grn. of potassic cyanide.
Essential oil of bitter almonds may also be titrated in this way,
provided it is diluted with sufficient spirit to prevent turbidity from
separation of the essential oil. If hydrocyanic acid is determined gravi-
metrically (which is sometimes convenient, when only a single estimation
is to be made), it is precipitated as cyanide of silver, the characters of
which have been already described.
§ 269, Case of Poisoning by Bitter Almonds.-Instances of poisoning by bitter
almonds are very rare. The following interesting case is recorded by Maschka:—
A maid-servant, 31 years of age, after a quarrel with her lover, ate a quantity of
bitter almonds. In a few minutes she sighed, complained of being unwell and faint ;
she vomited twice, and, after about ten minutes more had elapsed, fell senseless and
was convulsed. An hour afterwards, a physician found her insensible—the eyes rolled
upwards, the thumb clenched within the shut fists, and the breathing rattling, the
pulse very slow. She died within an hour and a half from the first symptoms.
The autopsy showed the organs generally healthy, but all, save the liver, exhaling
a faint smell of bitter almonds. The right side of the heart was full of fluid dark
* Dragendorff, G., Beitr. 2wr gericht. Chem., p. 59.
+ Casper's Pract. Handbuch der gerichtlichen Medicin, p. 561.
+ Vierteljahr. f. gerichtl. Med., Berlin, 1881, p. 193.
§ Zeitschrift f. anal. Chemie, von Fresenius, xii. p. 4, 1873.
§ 270, 271.] POISONOUS CYANIDES. 22 I
blood, the left was empty. Both lungs were rich in blood, which smelt of prussic
acid. The stomach was not inflamed—it held 250 grms, of a yellow fluid, containing
white flocks smelling of bitter almond oil. In the most dependent portion of the
stomach there was a swollen patch of mucous membrane, partially denuded of
epithelium. The mucous membrane of the duodenum was also swollen and slightly
red. The contents of the stomach were acid, and yielded, on distillation, hydride of
benzole and hydric cyanide. Residues of the almonds themselves were also found,
and the whole quantity taken by the woman from various data was calculated to be
1200 grains of bitter almonds, equal to 43 grains of amygdalin, or 2.5 grains of pure
hydric cyanide.
Poisonous Cyanides other than Hydric and Potassic Cyanides.
§ 270. The action of both sodic and ammonic cyanides is precisely similar to that
of potassic cyanide. With regard to ammonic cyanide, there are several experiments
by Eulenberg,” showing that its vapour is intensely poisonous.
A weak stream of ammonic cyanide vapour was passed into glass shades, under
which pigeons were confined. After a minute, symptoms of distress commenced, them
followed convulsions and speedy death. The post-mortem signs were similar to those
produced by prussic acid, and this substance was separated from the liver and lungs.
§ 271. With regard to the double cyanides, all those are poisonous from which hydric
cyanide can be separated through dilute acids, while those which, like potassic ferro-
cyanide, do not admit of this decomposition, may often be taken with impunity, and
are only poisonous under certain conditions.
Sonnenschein records the death of a colourist, after he had taken a dose of potassic
ferro-cyanide and then one of tartaric acid ; and Volz describes the death of a man,
who took potassic ferro-cyanide and afterwards equal parts of mitric and hydrochloric
acids. In this latter case, death took place within the hour, with all the symptoms
of poisoning by hydric cyanide ; so that it is not entirely true, as most text-books
declare, that ferro-cyanide is in no degree poisonous. Carbon dioxide will decom-
pose potassic ferro-cyanide at 72°–74°, potass ferrous cyanide being precipitated—
K, Fe(CN)6. A similar action takes place if ferro-cyanide is mixed with a solution
of peptone and casein, and digested at blood-heat t (from 37° to 40° C.), so that it is
believed than when ferro-cyanide is swallowed HCN is liberated, but the quantity
is usually so small at any given moment that no injury is caused : but there are
conditions in which it may kill speedily.f
Mercuricºcyanide, it has been often said, acts precisely like mercuric chloride
(corrosive sublimate), and a poisonous action is attributed to it not traceable to
* Gewerbe Hygiene, p. 385. + Autenrieth, Arch. Pharm., ccxxxi. 99–109.
† The presence of ferro-cyanide is easily detected. The liquid is, if necessary,
filtered and then acidified with hydrochloric acid and a few drops of ferric chloride
added ; if the liquid contains ferro-cyanide, there is immediate production of Prus-
sian blue. It may happen that potassic or sodic cyanide has been taken as well as
ferro-cyanide, and it will be necessary then to devise a process by which only the
prussic acid from the simple cyanide is distilled over. According to Autenrieth, if
sodium hydrocarbonate is added to the liquid in sufficient quantity and the liquid
distilled, the hydric cyanide that comes over is derived wholly from the sodium or
potassium cyanide. Should mercury cyanide and ferro-cyanide be taken together,
then this process requires modification ; bicarbonate of soda is added as before, and
then a few c.c. of water saturated with hydric sulphide ; under these circum-
stances, only the hydric cyanide derived from the mercury cyanide distils over.
If the bicarbonate of soda is omitted, the distillate contains hydric cyanide derived
from the ferro-cyanide.
222 POISONS : THEIR EFFECTS AND DETECTION. [$ 271.
cyanogen ; but this is erroneous teaching. Bernard * declares that it is decom-
posed by the gastric juice, and hydric cyanide set free; while Pelikan puts it in
the same series as ammonic and potassic cyanides. Lastly, Tolmatscheff, t by direct
experiment, has found its action to resemble closely that of hydric cyanide.j:
Silver cyanide acts, according to the experiments of Nunneley, also like hydric
cyanide, but very much weaker.
Hydric sulphocyanide in very large doses is poisonous.
Potassic sulphocyanide, according to Dubreuil and Legros, Š if subcutaneously
injected, causes first local paralysis of the muscles, and later, convulsions.
Cyanogen chloride (CNCl) and also the compound (C3N2Cl3)—the one a liquid,
boiling at 15°, the other a solid, which may be obtained in crystals—are both
poisonous, acting like hydric cyanide.
Cyanogen iodide (CNI), according to Kobert, is four times weaker than prussic
acid, but it is a powerful poison for unicellular organisms. The nitriles have but
slight toxic action. Aceto-nitrile is a good medium for bacterial growth. The iso-
nitriles, on the contrary, are powerful poisons.
Methyl cyanide is a liquid obtained by distillation of a mixture of calcic methyl
sulphate and potassic cyanide. It boils at 77°, and is intensely poisonous. Eulen-
berg || has made several experiments on pigeons with this substance. One example
will suffice :—A young pigeon was placed under a glass shade, into which methyl
cyanide vapour, developed from calcic methyl sulphate and potassic cyanide, was
admitted. The pigeon immediately became restless, and the faeces were expelled.
In forty seconds it was slightly convulsed, and was removed after a few minutes'
exposure. The pupils were then observed not to be dilated, but the respiration had
ceased ; the legs were feebly twitching ; the heart still beat, but irregularly ; a turbid
white fluid dropped out of the beak, and after six minutes life was extinct.
The pathological appearances were as follows:–In the beak much watery fluid ;
the membranes covering the brain weakly injected ; the plexus venosus spinalis
strongly injected ; in the region of the cervical vertebra a small extravasation
between the dura mater and the bone; the right lung of a clear cherry-red colour,
and the left lung partly of the same colour; the parenchyma presented the same hue
as the surface; on section of the lungs a whitish froth exuded from the cut surface.
In the cellular tissue of the trachea, there were extravasations 5 mm. in diameter ;
the mucous membrane of the air-passages was pale ; the right ventricle and the left
auricle of the heart were filled with coagulated and fluid dark red blood ; liver and
kidneys normal; the blood dark red and very fluid, becoming bright cherry-red on
exposure to the air ; blood corpuscles unchanged. Cyanogen was separated, and
identified from the lungs and the liver.
Cyanuric acid (CAOSM3H3), one of the decomposition products obtained from urea,
is poisonous, the symptoms and pathological effects closely resembling those due to
hydric cyanide. In experiments on animals, there has been no difficulty in detecting
prussic acid in the lungs and liver after poisoning by cyanuric acid.
Reid Hunt" has determined the toxic dose of many nitriles when subcutaneously
* Substances Toadines, pp. 66–103.
+ “Einige Bemerkungen über die Wirkung von Cyanquecksilber,” in Hoppe-
Seyler's Med. Chem. Untersuchungen, 2 Heft, p. 279.
† Mercury cyanide may be detected in a liquid after acidifying with tartaric acid,
and adding a few c.c. of SH2 water and then distilling. S. Lopes suggests another
process: the liquid is acidified with tartaric acid, ammonium chloride added in
excess, and the liquid is distilled. A double chloride of ammonium and mercury is
formed, and HCN distils over with the steam.—J. Pharm., xxvii. 550-553.
§ Compt. Rend., t. lxiv. p. 561, 1867. | Gewerbe Hygiene, p. 392.
* Arch. Inter. de Pharm. et de Thérapie, xii., 1904.
§ 271.] POISONOUS CYANIDES. 223
injected into mice. The nitriles were either dissolved in water or in diluted alcohol.
The results may be seen from the following table :-

ſº bſ:
, à #7 | #
É # #2 || 3:3
# # ##|###
& - ?-, 3. 5 g © ;
Prussic acid . & * HCN 27 | 0-005 || 1 1
Aceto nitrile . g º CHACN 41 || 0 °7 140 92°2
Formal cyanhydrine . CH2(OH)CN 57 || 0-015 3 1-42
Chloral cyanhydrine . CC,CH(OH)CN 188°5 || 0:023 4-6 || 0-66
Benzo nitrile . & * CeB,CN . 103 || 0 |18 || 36 9:5
Benzyl nitrile g ſº C6H3CH3CN 117 || 0-032 6'4 | 1.47
Mandelic nitrile . . Csh;CH(OH)CN 133 || 0 °023 || 4 -6 || 0-93
& g * r * CN !
Diethylaminoaceto nitrile CH < : * } *
** 2 148 °5 || 0 °031 || 6 || 1:09
hydrochloride N(C2H5)3FICl
CN
Diethylaminoaceto nitrile / * • Q ſº : *
iodo methylate . . cº 9. 254 0 °25 50 5°31
\N(C.H.),
NI
2CN
Diethylamino-lactic nitrile | CH3CH 126 || 0 °022 || 4 °4 || 0 °94
\N(C.H.),
CN
Diethylamino-lactic nitrile / * $
iodo methylate . e oned CH, 266 || 0 °4 80 8:1
\N(C.H.),
NI
2CN
Phenylaminoaceto nitrile CH, 132 || 0-055 11 2.25
NNHCH,
tº.* *|CHCH.)NHCH,CN(0)|| 146 |0.091 | 18.2 || 3:36
Tolylaminoaceto nitrile -
(meta-) . e * 146 || 0 "1 20-0 || 3.7
. CN
Diethylamino - phenyl- t / g *
aceto nitrile. g & CºHACH 188 || 0 °025 5 0.73
N(C2H5)2
CN
gº tº . . . /
Piperidoaceto nitrile . CH2 124 || 0 °058 11 6 2.52
\NCH,
Sodium nitro prusside . . Fe(CN)2(NO)Na2+2HO2 298 || 0:012 || 2:4 || 0:217
ºr-------
224 POISONS : THEIR EFFECTS AND DETECTION. [$ 272.
He ascribes the toxic properties of these nitriles to the splitting off of HCN.
The different stability of the compounds, the ease with which they are absorbed and
excreted, and the variations in distribution in the body, account for the differences in
toxicity that they exhibit.
The same author has made experiments on the antagonistic action of certain
thiosulphates and other sulpho compounds when injected a short time before the
nitrile. The results of a few of these experiments may be seen from the following
table, the figures indicating how many fatal doses of the nitrile have been neutral-
ised by the sulpho compound.

§ | #3 |s à || 3 || 3 |## | 3 |# lº
.# | ## |## |; 3 , |&#: | 3 |* |$.-:
* = | * 5 || 5 | ##| || 3: |#33 gº tº |3.3
$ 5 || 3 3 || 3 tº 9 : e § #:5 ; F £h º, E
º'E | 3 || | # 8, $ 5, #5 | E3 = | #5 5.3 |##
.5 s º 8 2 * , 3. * * a gº 3's cº § - & 3 | * *
** | *ē, 5.5; ºg | * * |23 = | | | |##|# 3
#ā ā; |###| ##| 35 |###| #5 |##|āā
§§ 3 ; ; ; 5 ||= .5 | ##| | Els sº ##| ||= < |3%
# | # * | * > * * : gº 80 2, 3 tº tº "c c | P: ;-
F. g . ; ; = E * | 33 ° 5, #3 || @ 3 | tº 3 |* 5 3 &
5 : 5 # ſº | * * 3 * |3: ..., | 3 || |5 * * :
E #| 5 # |#3 3 & # 35 | # 3 || 3 ||3: ;
‘g 5 ##| |#3 |ÉÉ # s : G = | 3 ° |# |fl =
CD 33. 3 || 3 <d * to <! §
Prussic acid HCN 1-8 2'4 2'4 0 . 0 2 || 1:4
Aceto mitrile . CH3CN 2 º 0 0'02 C. C. ... 0 || 4’3
4 °3
Formal cyanhydrine CH2(OH)CN 19 |about 3| 2.6 3-3 2°6 8 less || 3-3 || 2:5
than 2
Chloral cyanhydrine | CCl3CH(OH)CN | 2:7 Ca'3 less º 1°3 1 ‘3 || 1'4 || 1.3
than 2
Benzo nitrile . C6H5ON () * @ 9 0 e ‘º º e & 9 tº ſº º 0 0
Benzyl mitrile C6H5CH2CN 2.6 tº: 1.7 17 % º 2
han 2
Mandelic nitrile. CºEI50H(OH)CN | 2:8 ... 2°4 2.2 0 º 2 || 2-2
:
**-*.
2.6
1-7
XIII.—Phosphorus.
§ 272. Phosphorus.-Atomic weight 31, specific gravity 1.82 to
1840. Phosphorus melts at from 44.4° to 44.5° to a pale yellow oily
fluid. The boiling-point is about 290°.
The phosphorus of commerce is usually preserved under water in
the form of waxy, semi-transparent sticks; if exposed to the air white
fumes are given off, luminous in the dark, with a peculiar onion-like
odour. On heating phosphorus it readily inflames, burning with a very
white flame. - -
At 0° phosphorus is brittle ; the same quality may be imparted to
it by a mere trace of sulphur. Phosphorus may be obtained in dodeca-
hedral crystals by slowly cooling large melted masses. It may also be
obtained crystalline by evaporating a solution in bisulphide of carbon, or
hot naphtha in a current of carbon dioxide. It is but little soluble in
water. Julius Hartmann * found in some experiments that 100 grms. of
water digested with phosphorus for sixty-four hours at 38°5’ dissolved
-000127 grn. He also investigated the solvent action of bile, and
* Zur acutem. Phosphor- Vergiftung, Dorpat, 1866.
§ 273.] PHOSPHORUS. 225
found that 100 grms. of bile under the same conditions dissolved
'02424 grm., and that the solubility of phosphorus rose both in water
and bile when the temperature was increased. Phosphorus is somewhat
soluble in alcohol and ether, and also, to some extent, in fatty and
ethereal oils; but the best solvent is carbon disulphide.
The following is the order of solubility in certain menstrua, the
figures representing the number of parts by weight of the solvent
required to dissolve one part of phosphorus:—
Carbon Disulphide, º e - - e 4
Almond Oil, g º g e - º 100
Concentrated Acetic Acid,” º e -> g 100
Ether, e te º º - - to 250
Alcohol, specific gravity ‘822, • - - - 400
Glycerin, . g 588
Phosphorus exists in, or can be converted into, several allotropic
modifications, of which the red or amorphous phosphorus is the most
important. This is effected by heating it for some time, in the absence
of air, from 230° to 235°. It is not poisonous.f Commercial red
phosphorus does, however, contain very small quantities of unchanged
or ordinary phosphorus—according to Fresenius, from 6 per cent. down-
wards; it also contains phosphorous acid, and about 4.6 per cent. of
other impurities, among which is graphite f and often arsenic.
§ 273. Phosphuretted Hydrogen.—Phosphine (PHA), mol. weight
34, specific gravity 1-178, percentage composition, phosphorus 91:18,
hydrogen 8-82 by weight. The absolutely pure gas is not spontaneously
inflammable, but that made by the ordinary process is so. It is a
colourless, highly poisonous gas, which does not support combustion,
but is itself combustible, burning to phosphoric acid (PH3+2O3= P0, Ha).
Extremely dangerous explosive mixtures may be made by combining
phosphine and air or oxygen. Phosphine, when quite dry, burns with
a white flame, but if mixed with aqueous vapour, it is green; hence a
hydrogen flame containing a mixture of PH, possesses a green colour.
If sulphur is heated in a stream of phosphine, hydric sulphide and
sulphur phosphide are the products. Oxides of the metals, heated with
phosphine, yield phosphides with formation of water. Iodine, warmed
in phosphine, gives white crystals of iodine phosphonium, and biniodide
of phosphorus, 51 +4PHs=3PIH, + PIs. Chlorine inflames the gas,
the final result being hydric chloride and chloride of phosphorus, PH2 +
8Cl = 30l.H + PCls. One of the most important decompositions for
* Phosphorus is very little soluble in cold acetic acid, and the solubility given
is only correct when the boiling acid acts for some time on the phosphorus,
+ A hound took 200 grims, of red phosphorus in twelve days, and remained
healthy.—Sonnenschein.
† Schrotter, Chem. Wews, vol. xxxvi. p. 198.
I 5
226 POISONS: THEIR EFFECTS AND DETECTION. [$274,275.
our purpose is the action of phosphine on a solution of nitrate of
silver; there is a separation of metallic silver, and mitric and phosphoric
acids are found in solution, thus — 8AgNO3 + PHs +4OH,-8Ag+
8HNO3 + PO, Hs. This is, however, rather the end reaction; for, at
first, there is a separation of a black precipitate composed of phosphor-
silver. The excess of silver can be separated by hydric chloride, and
the phosphoric acid made evident by the addition of molybdic acid in
€XCéSS.
§ 274. The medicinal preparations of phosphorus are not numerous;
it is usually prescribed in the form of pills, made by manufacturers of
coated pills on a large scale. The pills are composed of phosphorus,
balsam of Tolu, yellow wax, and curd soap, and 3 grains equal so grain
of phosphorus. There is also a phosphorated oil, containing about 1
part of phosphorus in 100; that of the French Pharmacopoeia is made
with 1 part of dried phosphorus dissolved in 50 parts of warm almond
oil; that of the German has 1 part in 80; the strength of the former
is therefore 2 per cent., of the latter 125 per cent. The medicinal
dose of phosphorus is from T}o to a grain.
§ 275. Matches and Vermin Pastes.—An acquaintance with the
percentage of phosphorus in the different pastes and matches of com-
merce will be found useful. Most of the vermin-destroying pastes
contain from 1 to 2 per cent. of phosphorus.
A phosphorus paste that was fatal to a child,” and gave rise to
serious symptoms in others, was composed as follows:–
- Per cent.
Phosphorus, . º e ſº o tº © ſº . . 1 “4
Flowers of sulphur, . e g e e & e º 42*2
Flour, . º - * e - e º º g 42°2
Sugar, . g - e e º e o & º 14 °2
100'00
Three common receipts give the following proportions:—
Per cent.
Phosphorus, . o e e • º e º e 1 ‘5
Lard, . tº © o o º g º s º 18°4
Sugar, . º tº e e & s & . . . 18°4
Flour, . & - e º º e - tº º 61 °7
100'00
- Per cent.
Phosphorus, . o e º e tº º s ſº 1-2
Warm water, . º º & tº * e * ge 26.7
Rye flour, . - . . . . . . . 26'7
Melted butter, e º º o e - º º 26-7
Sugar, , • e º 0 º s º e º 18.7
100 :00
* Casper's 204th case.
§ 275.] PHOSPHORUS. - 227
Per cent.
Phosphorus, . º gº º e º e º e e 1 *6
Nut oil, . • . * s e - º & - 15-7
Warm water, . º º * º e e & e 31'5
Flour, . º e & º * º ſº & º 31'5
Sugar, . o * e º e º º * º 19.7
100'00
A very common phosphorus paste, to be bought everywhere in
England, is sold in little pots; the whole amount of phosphorus con-
tained in these varies from 324 to 388 grm. (5 to 6 grains), the active
constituent being a little over 4 per cent. Matches differ much in
composition. Six matchheads, which had been placed in an apple for
criminal purposes, and were submitted to Tardieu, were found to con-
tain 20 mgrms. of phosphorus—i.e. 33 grm. in 100. Mayet found
in 100 matches 55 mgrms. of phosphorus. Gonning * analysed ten
different kinds of phosphorus matches with the following result:-
Three English samples contained in 100 matches 34, 33, and 32 mgrms.
of phosphorus; a Belgian sample, 38 mgrms. ; and 5 others of unknown
origin, 12, 17, 28, 32, and 41 mgrms. respectively. Some of the pub-
lished formularies are as follows:—
(1.) Glue, 6 parts.
Phosphorus, 4 , , or 14'4 per cent.
Nitre, 10 5 3
Red ochre, 5 , ,
Q
Blue smalts,
(2.) Phosphorus,
*/ } }
9 parts, or 16'3 per cent.
Gum 3. 16 3 5
Nitre, 14 ,
Smalts, 16 , ,
(3.) Phosphorus, 4 parts, or 14.4 per cent.
Glue, 6 3 ×
Nitre, 10 , ,
Red lead, . 5 , ,
Smalts, 2 2 3
(4.) Phosphorus,
17 parts, or 17 per cent.
Glue, 21 5 3
Nitre, 38 , ,
Red lead, . 24 , ,
Phosphorus poisoning by matches is, however, becoming rare, for
those containing the ordinary variety of phosphorus are being superseded
by matches of excellent quality, which contain no phosphorus whatever,
or by matches which are manufactured with phosphorus sesquisulphide,
P,S, ; for example, the matches made in France in the national factories
* Nederlandsch Tijdschr, voor Geneesk., Afdl. i., 1866.
228 POISONS : THEIR EFFECTS AND DETECTION. [$ 276.
contain only the sesquisulphide, which has not the injurious qualities
of the ordinary phosphorus. º
§ 276. Statistics.-The deaths for ten years ending 1903 from
phosphorus poisoning in England and Wales amount to 148; of these,
67 (29 males, 38 females) were due to accident, and 81 (21 males and
60 females) were suicidal.
Phosphorus as a cause of death occupies the eleventh place among
poisons; as a cause of suicide it occupies the seventh.
A far greater number of cases of poisoning by phosphorus occur yearly
in France and Germany than in England. Phosphorus may be considered
as the favourite poison which the common people on the Continent em-
ploy for the purpose of self-destruction. It is an agent which, before the
change of manufacture, was within the reach of anyone who had two sous
in his pocket wherewith to buy a box of matches; but to the educated and
those who know the horrible and prolonged torture ensuing from a toxic
dose of phosphorus, such a means of exit from life will never be favoured.
Otto Schraube * has collected 92 cases from Meischner's work,i and
added 16 which had come under his own observation, giving in all 108
cases. Seventy-one (or 65 per cent.) of these were suicidal—of the
suicides 24 were males, 47 females (12 of the latter being prostitutes);
21 of the cases were those of murder, 11 were accidental, and in 3 the
cause was not ascertained. The number of cases in successive years, and
the kind of poison used, is given as follows:–
Phosphorus in Phosphorus
Number of Cases. In the Years Substance, Matches.
Or as Paste.
15 tº º º 1798–1850 e tº 13 to g tº 2
36 g e & 1851–1860 tº ſº tº 15 tº g tº 21
41 tº ſº q 1861–1864 tº e Q 6 . . . . 35
I 6 tº º º 1865–1867 & a tº 5 tº t tº 11
Of the 108 cases, 18 persons recovered and 90 (or 83.3 per cent.) died.
Falck also has collected 76 cases of poisoning from various sources
during eleven years; 55 were suicidal, 5 homicidal f (murders), and
the rest accidental. Of the latter, 2 were caused by the use of phos-
phorus as a medicine, 13 by accidents due to phosphorus being in the
house; in 1 case phosphorus was taken intentionally to try the effects
of an antidote.S. With regard to the form in which the poison was
* Schmidt's Jahrbuch der ger. Med., Bd, clxxxvi. S. 209–248, 1867.
† Die acute Phosphorose und einige Refleasionen über die acute gelbe Leberatrophie,
etc., Inaug. Diss., Leipzig, 1864.
† Dr. Dannenberg has shown by direct experiment that a poisonous dose of
phosphorus may be introduced into spirits or coffee, and the mixture have but little
odour or taste of phosphorus.-Schuchardt in Maschka's Handbuch.
§ Géry, “Ueber Terpentinessenz als Gegenmittel gegen Phosphor,” in Gaz.
Hebd. de Med., 2 ser., x. 2, 1873.
§ 277–279.] PHOSPHORUS. 229
taken, 2 of the 76, as already mentioned, took it as prescribed by
physicians, the remaining 74 were divided between poisonings by phos-
phorus paste (22) and matches (52) = 70 per cent. Of the 76 cases, 6
were children, 43 adult males, 13 adult females, and 14 adults, sex not
given. Of the 76 cases, 42, or 55.3 per cent, died—a much smaller
rate of mortality than that shown by Schraube's collection.
§ 277. Fatal Dose.—The smallest dose on record is that mentioned
by Lobenstein Lobel, of Jena, where a lunatic died from taking 7-5
mgrms. (‘l 16 grain). There are other cases clearly indicating that this
small quantity may produce dangerous symptoms in a healthy adult.
§ 278. Effects of Phosphorus.-Phosphorus is excessively poisonous,
and will destroy life, provided only that it enters the body in a fine state
of division, but if taken in coarse pieces no symptoms may follow, for
it has been proved that single lumps of phosphorus will go the whole
length of a dog's intestinal canal without causing appreciable loss of
weight, and without destroying life.* Magendie injected oleum phos-
phoratum into the veins, and although the animals experimented on
exhaled white fumes, and not a few died asphyxiated, yet no symptoms
of phosphorus poisoning resulted—an observation confirmed by others—
the reason being that the phosphorus particles in a comparatively coarse
state of division were arrested in the capillaries of the lung, and may be
said to have been, as it were, outside the body. On the other hand,
A. Brunner, f working in L. Hermann's laboratory, having injected into
the veins phosphorus in such a fine emulsion that the phosphorus could
pass the lung capillaries, found that there were no exhalations of white
fumes, but that the ordinary symptoms of phosphorus poisoning soon
manifested themselves. Phosphorus paste, by the method of manu-
facture, is in a state of extreme subdivision, and hence all the
phosphorus pastes are extremely poisonous.
§ 279. In a few poisons there is a difference, more or less marked,
between the general symptoms produced on man, and those noticeable
in the different classes of animals; but with phosphorus, the effects on
animals appear to agree fairly with those witnessed most frequently in
man. Tardieu (who has written perhaps the best and most complete
clinical record of phosphorus poisoning extant) divides the cases under
three classes, and to use his own words:—“I think it useful to establish
that poisoning by phosphorus in its course, sometimes rapid, sometimes
slow, exhibits in its symptoms three distinct forms—a common form, a
nervous form, and a haemorrhagic form. I recognise that, in certain
cases, these three forms may succeed each other, and may only constitute
periods of poisoning; but it is incontestable that each of them may show
* Reveil, Amm. d’Hygiène Publ. (3), xii. p. 370.
t Arch. J. d. Ges. Physiologie, iii. p. 1.
23O POISONS : THEIR EFFECTS AND DETECTION. [$ 280.
itself alone, and occupy the whole course of the illness produced by the
poison.” Premising that the common form is a blending of irritant,
nervous, and hamorrhagic symptoms, we adopt here in part Tardieu's
division. The name of “haemorrhagic form * may be given to that in
which hamorrhage is the predominant feature, and the “nervous” to
that in which the brain and spinal cord are from the first affected.
There yet remain, however, a few cases which have an entirely
anomalous course, and do not fall under any of the three classes.
From a study of 121 recorded cases of phosphorus poisoning,
the relative frequency of the different forms appears to be as follows:–
The common form 83 per cent., haemorrhagic 10 per cent, nervous 6
per cent, anomalous 1 per cent. The “anomalous” are probably
over-estimated, for the reason that cases presenting ordinary features
are not necessarily published, but others are nearly always chronicled
in detail.
§ 280. Common Form.—At the moment of swallowing, a disagree-
able taste and smell are generally experienced, and there may be
immediate and intense pain in the throat, gullet, and stomach, and
almost immediate retching and vomiting. The throat and tongue also
may become swollen and painful; but in a considerable number of cases
the symptoms are not at once apparent, but are delayed from one to six
hours—rarely longer. The person's breath may be phosphorescent
before he feels in any way affected, and he may go about his business
and perform a number of acts requiring both time and mental integrity.
Pain in the stomach (which, in some of the cases, takes the form of
violent cramp and vomiting) succeeds; the matters vomited may shine
in the dark, and are often tinged with blood. Diarrhoea is sometimes
present, sometimes absent ; sleeplessness for the first night or two is
very common. The pulse is variable, sometimes frequent, sometimes
slow ; the temperature in the morning is usually from 36'0" to 36'5", in
the evening 37° to 38°.
The next symptom is jaundice, as was observed in the following
23 cases:–In 1 within twenty-four hours, in 3 within thirty-six
hours, in 3 within two days, in 11 within three days, in 1 within four
days, in 1 within five days, in 1 within nine days, in 1 within eighteen
days, and in 1 within twenty-seven days; so that in about 78 per
cent. jaundice occurred before the end of the third day. Out of 26
cases, in which the patients lived long enough for the occurrence
of jaundice, in 3 (or 11 per cent.) it was entirely absent. In 132 cases
recorded by Lewin, Meischner, and Heisler, jaundice occurred in 65,
or about 49 per cent, but it must be remembered that in many
of these cases the individual died before it had time to develop. The
* Etude Médico-Legale et Clinique sur l'Empoisonnement, Paris, 1875, p. 483.
§ 281, 282.] PHOSPHORUS. 23 I
jaundice having thoroughly pronounced itself, the system may be con-
sidered as not only under the influence of the toxic action of phosphorus,
but as suffering in addition from all the accidents incidental to the
retention of the biliary secretion in the blood ; nor is there from this
point any special difference between phosphorus poisoning and certain
affections of the liver—such, for example, as acute yellow atrophy. There
is retention of urine, sleeplessness, headache, frequent vomiting, painful
and often involuntary evacuations from the bowels, and occasionally skin
affections, such as urticaria or erythema. The case terminates either by
acute delirium with fever, followed by fatal coma, or, in a few instances,
coma comes on, and the patient passes to death in sleep without delirium.
In this common form there is in a few cases, at the end of from twenty-
four to thirty hours, a remission of the symptoms, and a non-medical
observer might imagine that the patient was about to recover without
further discomfort; but then jaundice supervenes, and the course is as
described. Infants often do not live long enough for the jaundiced
stage to develop, but die within twenty-four hours, the chief symptoms
being vomiting and convulsions.
§ 281. Haºmorrhagic Form.—The symptoms set in as just detailed,
and jaundice appears, but accompanied by a new and terrible train of
events—viz., great effusion of blood. In some cases the blood has been
poured out simultaneously from the nose, mouth, bladder, kidneys, and
bowels. Among women there is excessive haemorrhagia. The liver is
found to be swollen and painful; the bodily weakness is great. Such
cases are usually of long duration, and a person may die months after
taking the poison from weakness, anaemia, and general cachexia. In
many of its phases the hamorrhagic form resembles scurvy, and, as in
Scurvy, there are spots of purpura all over the body.
§ 282. The nervous form is less common than the two forms
just described. From the beginning, there are strange creeping
sensations about the limbs, followed by painful cramps, repeated
faintings, and great somnolence. Jaundice, as usual, sets in, erythe-
matous spots appear on the skin, and, about the fifth day, delirium
of an acute character breaks out, and lockjaw and convulsions close
the scene.
The following are one or two brief abstracts of anomalous cases in
which symptoms were either wanting, or ran a course entirely different
from any of the three forms described:—
A woman, aged 20, took about 3 grains of phosphorus in the form
of rat-paste. She took the poison at 6 in the evening, behaved accord-
ing to her wont, and sat down and wrote a letter to the king. During
the night she vomited once, and died the next morning at 6 o'clock,
exactly twelve hours after taking the poison. There appear to have
232 POISONS: THEIR EFFECTS AND DETECTION. [$ 283—286.
been no symptoms whatever, save the single vomiting, to which may be
added that in the course of the evening her breath had a phosphorus
odour and was luminous.*
A girl swallowed a quantity of phosphorus paste, but there were no
marked symptoms until the fifth day, on which there was sickness and
purging. She died on the seventh day. A remarkable blueness of the
finger nails was observed a little before death, and was noticeable after-
wards, f
§ 283. Sequelae.—In several cases in which the patients have
recovered from phosphorus poisoning, there have been observed para-
lytic affections.# O. Bollinger has recorded a case in which paralysis
of the foot followed; $ in another, published by Bettelheim, there were
peculiar cerebral and spinal symptoms. Most of these cases are to be
explained as disturbance or loss of function from small haemorrhages in
the nervous substance.
§ 284. Period at which the first Symptoms commence,—The time
when the symptoms commence is occasionally of importance from a
forensic point of view. Out of 28 cases in which the commencement
of evident symptoms—i.e. pain, or vomiting, or illness—is precisely
recorded, in 8 the symptoms were described as either immediate or
within a few minutes after swallowing the poison; in 6 the symptoms
commenced within the hour ; in 3 within two hours; in other 3 within
four hours; and in 1 within six hours. One was delayed until the lapse
of twelve hours, 1 from sixteen to eighteen hours, 1 two, and another
five days. We may, therefore, expect that in half the cases which may
occur, the symptoms will commence within the hour, and more than 80
per cent. Within six hours.
$ 285. Period of Death. –In 129 cases death took place as follows:—
In 17 within twenty-four hours, in 30 within two days, in 103 within
seven days. Three patients lived eight days, 6 nine days, 13 ten days,
1 eleven days, 1 sixteen days, 1 seventeen days, and 1 survived eight
months. It hence follows that 79.8 per cent, of the fatal cases die
within the week.
§ 286. Phosphorus Vapour.—There are one or two cases on record of
acute poisoning by phosphorus in the form of vapour. The symptoms
are somewhat different from the effects produced by the finely-divided
solid, and in general terms it may be said that phosphorus vapour is
more apt to produce the rarer “nervous” form of poisoning than the
solid phosphorus.
* Casper's 205th case. + Taylor on Poisons, p. 277.
# See Gallavardin, Les Paralyses Phosphoriques, Paris, 1865.
§ Deutsches Archiv f. klin. Med., Bd. vi. Hft. 1, S. 94, 1869.
| Wiener Med. Presse, 1868, No. 41.
§ 286.] PHOSPHORUS. 233
Bouchardat " mentions the case of a druggist who, while preparing a
large quantity of rat-poison in a close room, inhaled phosphorus vapour.
He fainted repeatedly, fell into a complete state of prostration, and died
within a week.
The following interesting case came under the observation of
Professor Magnus Huss —A man, 39 years old, married, was ad-
mitted into the Seraphin-Lazareth, Stockholm, on the 2nd of February
1842. He had been occupied three years in the manufacture of
phosphorus matches, and inhabited the room in which the materials
were preserved. He had always been well-conducted in every way, and
in good health, until a year previously, when a large quantity of the
material for the manufacture of the matches accidentally caught fire and
exploded. In his endeavours to extinguish the flames, he breathed a
large quantity of the vapour, and he fell for a time unconscious. The
spine afterwards became so weak that he could not hold himself up, and
he lost, in a great measure, power over his legs and arms. On admission,
his condition was as follows:–He could make a few uncertain and
staggering steps, his knees trembled, his arms shook, and if he attempted
to grasp anything when he lay in bed, there were involuntary twitchings
of groups of muscles. There was no pain; the sensibility of the skin
was unchanged ; he had formication in the left arm ; the spine was
neither sensitive to pressure, nor unusually sensitive to heat (as, e.g., to
the application of a hot sponge); the organs of special sense were not
affected, but his speech was somewhat thick. He lived to 1845 in the
same condition, but the paralysis became worse. There does not seem
to have been any autopsy.
The effects of phosphorus vapour may be still further elucidated by
one of Eulenberg's f experiments on a rabbit. The vapour of burning
phosphorus, mixed with much air, was admitted into a wooden hutch in
which a strong rabbit sat. After 5 mgrms, of phosphorus had been in
this manner consumed, the only symptoms in half an hour were
salivation, and quickened and somewhat laboured respiration. After
twenty-four hours had elapsed there was sudden indisposition, the
animal fell as if lifeless, with the hind extremities stretched out, and
intestinal movements were visible ; there was also expulsion of the urine.
These epileptiform seizures seem to have continued more or less for
twelve days, and them ceased. After fourteen days the experiment was
repeated on the same rabbit. The animal remained exposed to the
vapour for three-quarters of an hour, when the epilepsy showed itself as
before, and, indeed, almost regularly after feeding. Between the
* Amnuaire de Thérap., 1874, p. 109; Schuchardt in Maschka's Handbuch; also
Schmidt's Jahrbuch, Bd. li. S. 101, 1846.
† Gewerbe Hygiene, p. 255.
234 POISONS: THEIR EFFECTS AND DETECTION. [$ 287, 288.
attacks the respiration was slowed. Eight weeks afterwards there was
an intense icterus, which disappeared at the end of ten weeks.
§ 287. Chronic phosphorus poisoning has frequently been noticed in
persons engaged either in the manufacture of phosphorus or in its
technical application. Some have held that the symptoms are due to
an oxidation product of phosphorus rather than to phosphorus itself;
but in one of Eulenberg's experiments, in which a dove was killed by
breathing phosphorus fumes evolved by phosphorus oil, phosphorus was
chemically recognised in the free state in the lungs. The most constant
and peculiar effect of breathing small quantities of phosphorus vapour
is a necrosis of the lower jaw. There is first inflammation of the
periosteum of the jaw, which proceeds to suppuration and necrosis of a
greater or smaller portion. The effects may develop with great sudden-
ness, and end fatally. Thus Fournier and Olliver * relate the case
of a girl, 14 years old, who, after working four years in a phosphorus
manufactory, was suddenly affected with periostitis of the upper jaw,
and with intense anaemia. An eruption of purpuric spots ensued, and
she died comatose. There is now little doubt that minute doses of
phosphorus have a specific action on the bones generally, and more
especially on the bones of the jaw. Wegner f administered small daily
doses to young animals, both in the state of vapour, and as a finely-
divided solid. The condition of the bones was found to be more compact
than normal, the medullary canals being smaller than in healthy bone,
the Ossification was quickened. The formation of callus in fractured
limbs was also increased.
§ 288. Changes in the Urinary Secretion.—It has been before stated
that, at a certain period of the illness, the renal secretion is scantier
than in health, the urine diminishing, according to Lebert and Wyss's i
researches, to one-half on the third, fourth, or fifth day. It frequently
contains albumen, blood, and casts. When jaundice is present, the urine
has then all the characters noticed in icterus; leucin and tyrosin, always
present in acute yellow atrophy of the liver, have been found in small
quantity in jaundice through phosphorus; lactic acid is also present.
The urea is much diminished, and, according to Schultzen and Riess, $
may be towards death entirely absent. Lastly, it is said that there is
an exhalation of either phosphorus vapour or phosphine from such urine.
In some cases the urine is normal, e.g. in a case recorded by E. H.
Starling, M.D., and F. G. Hopkins, B.Sc. (Guy's Hospital Report, 1890),
in which a girl, aged 18, died on the fifth day after taking phosphorus
* Gaz. held. de Méd., xxix. p. 461, 1868.
f Virchow's Arch. f. path. Amat., lv. 11.
# Archiv Générale de Méd., 6 Sér., Tom. xii., 1868, p. 709.
§ Annalen der Charité, Berlin.
§ 289–291.] PHOSPHORUS. 235
paste, the liver was fatty, and there was jaundice; but the urine con-
tained neither leucin nor tyrosin, and was stated to be generally normal.
§ 289. Changes in the blood during life have been several times
observed. In a case attended by M. Romellaere of Brussels,” in which
a man took the paste from 300 matches, and under treatment by
turpentine recovered, the blood was frequently examined, and the
leucocytes found much increased in number. There is a curious conflict
of evidence as to whether phosphorus prevents coagulation of the blood
or not. Nasse asserted that phosphorated oil given to a dog fully
prevented coagulation; P. I. Liebreck f also, in a series of researches,
found the blood dark, fluid, and in perfect solution. These observations
were also supported by W. Bibra and Schuchardt. I Nevertheless,
Lebert and Wyss found the blood, whether in the veins or in extravasa-
tions, in a normal condition. Phosphorus increases the fatty contents of
the blood. Ritter found that phosphorus mixed with starch, and given
to a dog, raised the fatty content from the normal 2 per 1000 up to
3:41 and 3:47 per 1000. Eug. Menard Ś saw in the blood from the
jugular and portal veins, as well as in extravasations, microscopic fat
globules and fine needle-shaped crystals soluble in ether.
§ 290. Antidote—Treatment.—After emptying the stomach by
means of emetics or by the stomach-pump, oil of turpentine in full
medicinal doses, say 2.5 c.c. (about 40 min.), frequently administered,
seems to act as a true antidote, and a large percentage of cases treated
early in this way recover.
§ 291. Poisonous Effects of Phosphine (phosphuretted hydrogen).
—Experiments on pigeons, on rats, and other animals, and a few very
rare cases among men, have shown that phosphine has an exciting action
on the respiratory mucous membranes, and a secondary action on
the nervous system. Eulenberg || exposed a pigeon to an atmosphere
containing 1-68 per cent. of phosphine. There was immediate unrest ;
at the end of three minutes, quickened and laboured breathing (100 a
minute); after seven minutes, the bird lay prostrate, with shivering of
the body and wide-open beak; after eight minutes, there was vomiting ;
after nine minutes, slow breathing (34 per minute); after twelve
minutes, convulsive movements of the wings; and after thirteen minutes,
general convulsions and death.
* Tardieu, op. cit., Case 31.
t Diss. de Venefico Phosphoreo Acuto, Upsal, 1845.
† W. Bibra u. Geist, Die Kramkheiten der Arbeiter in den Phosphorzundhol:
Fabriken, 1847, S. 59, etc.; Henle u. v. Pfeuffer's Zeitschr. f. ration. Med., N. F.,
Bd, vii., Hft, 3, 1857.
§ Etude Expérimentale sur quelques lesions de l'Empoisonnement aigu par le
Phosphore (Thèse), Strasbourg, 1869.
| Gewerbe Hygiene, p. 273.
236 POISONS: THEIR EFFECTS AND DETECTION. [$ 292.
The membranes of the brain were found strongly injected, and there
were extravasations. In the mucous membrane of the crop there was
also an extravasation. The lungs externally and throughout were of a
dirty brown-red colour; the entire heart was filled with coagulated
blood, which was weakly acid in reaction.
In a second experiment with another pigeon, there was no striking
symptom save that of increased frequency of respiration and loss of
appetite; at the end of four days it was found dead. There was much
congestion of the cerebral veins and vessels, the mucous membrane of
the trachea and bronchi were weakly injected, and the first showed a
thin, plastic, diphtheritic-like exudation.
Dr. Henderson's + researches on rats may also be noticed here. He
found that an atmosphere consisting entirely of phosphine killed rats
within ten minutes, an atmosphere with 1 per cent. in half an hour.
The symptoms observed were almost exactly similar to those noticed in
the first experiment on the pigeon quoted above, and the post-mortem
appearances were not dissimilar. With smaller quantities of the gas, the
first symptom was increased frequency of the respiration ; then the
animals showed signs of suffering intense irritation of the skin, scratching
and biting at it incessantly; afterwards they became drowsy, and assumed
a very peculiar attitude, sitting down on all-fours, with the back bent
forward, and the nose pushed backwards between the forepaws, so as to
bring the forehead against the floor of the cage. When in this position,
the rat presented the appearance of a curled-up hedgehog. Phosphine,
when injected into the rectum, is also fatal; the animals exhale some of
the gas from the lungs, and the breath, therefore, reduces solutions of
silver nitrate,f
Brenner i has recorded the case of a man 28 years old, a phar-
maceutist, who is supposed to have suffered from illness caused by
repeated inhalations of minute quantities of phosphine. He was
engaged for two and a half years in the preparation of hypophosphites;
his illness commenced with spots before the eyes, and inability to fix the
attention. His teeth became very brittle, and healthy as well as carious
broke off from very slight causes. Finally, a weakness of the arms and
limbs developed in the course of nine months into complete locomotor
ataxy. -
§ 292. Blood takes up far more phosphine than water does. Dybs-
kowsky found that putting the coefficient of solubility of phosphine in
pure water at 1122 at 15°, the coefficient for venous blood was 13, and
* Journ. Anat, and Physiol., vol. xiii. p. 19.
f Dybskowsky, Med. Chem. Untersuchungen aus Hoppe-Seyler's Labor. in
Tübingen, p. 57.
# St. Petersburg Med. Zeitschr., 4 Hft., 1865.
§ 293.] Phosphorus. . 237
for arterial 26-73; hence the richer the blood is in oxygen the more
phosphine is absorbed. It seems probable that the poisonous gas reacts
on the oxyhaemoglobin of the blood, and phosphorous acid is formed.
This is supported by the fact that a watery extract of such blood re-
duces silver nitrate, and has been also found feebly acid. The dark
blood obtained from animals poisoned by phosphine, when examined
spectroscopically, has been found to exhibit a band in the violet.
§ 293. Post-mortem Appearances.—There are a few perfectly well
authenticated cases showing that phosphorus may cause death, and yet
no lesion be discovered afterwards. Thus, Tardieu º cites a case in
which a woman, aged 45, poisoned herself with phosphorus, and died
suddenly the seventh day afterwards. Dr. Mascarel examined the
viscera with the greatest care, but could discover absolutely no
abnormal conditions; the only symptoms during life were vomiting, and
afterwards a little indigestion. It may, however, be remarked that the
microscope does not seem to have been employed, and that probably a
close examination of the heart would have revealed some alteration of
its ultimate structure. The case quoted by Taylor f may also be
mentioned, in which a child was caught in the act of sucking phosphorus
matches, and died ten days afterwards in convulsions. None of the
ordinary post-mortem signs of poisoning by phosphorus were met with,
but the intestines were reddened throughout, and there were no less
than ten invaginations; but the case is altogether a doubtful one, and
no phosphorus may actually have been taken. It is very difficult to
give in a limited space anything like a full picture of the different
lesions found after death from phosphorus, for they vary according as to
whether the death is speedy or prolonged, whether the phosphorus has
been taken as a finely-divided solid, or in the form of vapour, etc. It
may, however, be shortly said, that the most common changes are fatty
infiltration of the liver and kidneys, fatty degeneration of the heart,
enlargement of the liver, ecchymoses in the serous membranes, in the
muscular, in the fatty, and in the mucous tissues. When death occurs
before jaundice supervenes, there may be little in the aspect of the
corpse to raise a suspicion of poison ; but if intense jaundice has existed
during life, the yellow staining of the skin, and, it may be, spots of
purpura, will suggest to the experienced pathologist the possibility of
phosphorus poisoning. In the mouth and throat there will seldom be
anything abnormal. In one or two cases of rapid death among infants,
some traces of the matches which had been sucked were found clinging
to the gums. The stomach may be healthy, but the most common
appearance is a swelling of the mucous membrane and superficial
* L'Empoisonmement, p. 520.
f Poisons, 3rd ed., p. 276.
238 POISONS : THEIR EFFECTS AND DETECTION. [$ 293.
erosions. Virchow,” who was the first to call attention to this peculiar
grey swelling of the intestinal mucous membrane under the name of
gastritis glandularis or gastrademitis, shows that it is due to a fatty
degeneration of the epithelial cells, and that it is by no means peculiar
to phosphorus poisoning. The swelling may be seen in properly-
prepared sections to have its essential seat in the glands of the mucous
membrane; the glands are enlarged, their openings filled with large
cells, and each single cell is finely granular. Little centres of haemor-
rhage, often microscopically small, are seen, and may be the centres of
small inflammations; their usual situation is on the summit of the
rugae. Very similar changes are witnessed after death from septicaemia,
pyamia, diphtheria, and other diseases. The softening of the stomach,
gangrene, and deep erosions, recorded by the earlier authors, have not
been observed of late years, and probably were due to post-mortem
changes, and not to processes during life. The same changes are to be
seen in the intestines, and there are numerous extravasations in the
peritoneum.
The liver shows of all the organs the most characteristic signs; a
more or less advanced fatty infiltration of its structure takes place
which was first described as caused by phosphorus by Hauff in 1860.f
It is the most constant pathological evidence both in man and animal,
and seems to occur at a very early period, Munk and Leyden having
found a fatty degeneration in the liver far advanced in twenty-four
hours i after poisoning. In rats and mice poisoned with paste, this
may be seen by the naked eye twelve hours after the fatal dose.
The liver is mostly large, but in a case $ recorded in the Lancet,
* Virchow's Archiv. f. path. Amat., Bd. xxxi. Hft. 3, 399.
+ Hauff collected 12 cases, and found a fatty liver in 11. – Würtemb. Med.
Corresp. Bl., 1860, No. 34.
+ Die acute Phosphor-Vergiftung, Berlin, 1865.
§ This case, from the similarity of the pathological appearances to those pro-
duced by yellow atrophy, deserves fuller notice —“Frances A. Cowley, aged 20, on
her own admission, took some rat-paste on Tuesday, June 19th. Death ensued
eleven days later. The initial symptoms were not very marked. Nausea and
vomiting continued with moderate severity for a few days and then ceased.
There ensued a feeling of depression. Towards the end insensibility, icterus, and
somewhat profuse metrorrhagia supervened. At the necropsy the skin and con-
junctive were observed of a bright yellow colour. There was no organic disease save
of a recent nature, and entirely attributable to the action of the poison ingested.
The stomach contained about three-quarters of a pint of dark claret-coloured fluid,
consisting largely of blood derived from capillary hamorrhage from the mucous
membrane. There was no solution of continuity of the mucous membrane, which
showed traces of recent irritation. The whole surface presented a yellow icteric
tint, except the summits of some of the ruge, which were of a bright pink colour.
There was also faint wrinkling of the mucous membrane. The upper part of the
small intestine was affected in much the same manner as the stomach. The
large intestine contained a quantity of almost colourless feces. The liver was
§ 293.] * PHOSPHORUS. 239
July 14, 1888, the liver was shrunken; it has a pale yellow (or some-
times an intense yellow) colour; on section the cut surface presents a
mottled appearance; the serous envelopes, especially along the course of
the vessels, exhibit extravasations of blood. The liver itself is more
deficient in blood than in the normal condition, and the more bloodless
it is, the greater the fatty infiltration.
In the museum of the Royal College of Surgeons there is a prepara-
tion (No. 2737) of the section of a liver derived from a case of phosphorus
poisoning.
. A girl aged 18, after two days' illness, was admitted into Guy's
Hospital. She confessed to having eaten a piece of bread coated with
phosphorus paste. She had great abdominal pain, and died on the
seventh day after taking the phosphorus. A few hours before her death
she was profoundly and suddenly collapsed. The liver weighed 66 ozs.
The outlines of the hepatic lobules were very distinct, each central vein
being surrounded by an opaque yellowish zone; when fresh the hue was
more uniform, and the section was yellowish-white in colour. A micro-
scopical examination of the hepatic cells showed them laden with fat
globules, especially in the central parts of the liver.
The microscopic appearances are also characteristic. In a case of
suicidal poisoning by phosphorus, in which death took place on the
seventh day, the liver was very carefully examined by Dr. G. F. Goodart,
who reported as follows:–
“Under a low power the structure of the liver is still readily recognisable, and in
this the specimen differs from slides of three cases of acute yellow atrophy that I
have in my possession. The hepatic cells are present in large numbers, and have
their natural trabecular arrangement. The columns are abnormally separated by
dilated blood or lymph-spaces, and the individual cells are cloudy and ill-defined.
The portal channels are everywhere characterised by a crowd of small nuclei which
stain with logwood deeply. The epithelium of the smaller ducts is cloudy, and
blocks the tubes in many cases. Under a high power (one-fifth) it is seen that the
hepatic cells are exceedingly ill-defined in outline, and full of granules and even
drops of oil. But in many parts, even where the cells themselves are hazy, the
shrunken, weighing only 26 ozs., and both on its outer and sectional surface
exactly resembled the appearances produced by acute yellow atrophy, except that
there were greater congestion and interstitial haemorrhage in patches. The lobules
of the liver were in many places unrecognisable ; in others they stood in bold
relief as brilliant canary-yellow patches, standing in strong contrast to the deep
dark red areas of congestion and extravasation. The gall-bladder contained about
2 drachms of thin greyish fluid, apparently all but devoid of bile. The urinary
bladder was empty; the kidneys were enlarged ; the cortex was very pale and bile-
"stained, of greater depth than natural, and of softer consistence. The spleen was
not enlarged, nor was it in the least degree softened. In addition to the bleeding
from the uterus noticed during life, there was capillary hamorrhage into the right
lung and pleura, into the pericardium, and, as already mentioned, into the stomach.
The brain was healthy.”
24O POISONS : THEIR EFFECTS AND DETECTION. [$ 294.
nucleus is still fairly visible. It appears to me that, in opposition to what others
have described, the nuclei of the cells have in great measure resisted the degenera-
tive process. The change in the cells is uniform throughout each lobule, but some
lobules are rather more affected than others. The blood-spaces between the cells are
empty, and the liver appears to be very bloodless. The portal canals are uniformly
studded with small round nuclei or cells, which are in part, and might be said in
great part, due to increase of the connective tissue or to a cirrhotic process. But I
am more disposed to favour the view that they are due to migration from the blood-
Vessels, because they are so uniform in size, and the hepatic cells and connective
tissue in their neighbourhood are undergoing no changes in the way of growth what-
ever. I cannot detect any fatty changes in the vessels, but some of the smaller
biliary ducts contain some cloudy albuminous material, and their nucleation is not
distinct. No retained biliary pigment is visible.””
Oscar Wyss, f in the case of a woman 23 years old, who died
on the fifth day after taking phosphorus, describes, in addition to the
fatty appearance of the cells, a new formation of cells lying between
the lobules and in part surrounding the gall-ducts and the branches of
the portal vein and hepatic artery.
Salkowsky j found in animals, which he killed a few hours after
administering to them toxic doses of phosphorus, notable hyperamia
of the throat, intestine, liver, and kidneys—both the latter organs being
larger than usual. The liver cells were swollen, and the nuclei very
evident, but they contained no fat, fatty drops being formed afterwards.
§ 294. The kidneys exhibit alterations very similar and analogous to
those of the liver. They are mostly enlarged, congested, and flabby,
with extravasations under the capsule, and show microscopic changes
essentially consisting in a fatty degeneration of the epithelium. In
cases attended with haemorrhage, the tubuli may be here and there
filled with blood. The fatty epithelium is especially seen in the con-
torted tubes, and the walls of the vessels, both of the capsule and
of the malpighian bodies, also undergo the same fatty change. In cases
in which death has occurred rapidly, the kidneys have been found almost
healthy, or a little congested only. The pancreas has also been found
with its structure in part replaced by fatty elements.
Of great significance are also the fatty changes in the general muscular
system, and more especially in the heart. The muscular fibres of the
heart quickly lose their transverse striae, which are replaced by drops of
fat. Probably this change is the cause of the sudden death not un-
frequently met with in phosphorus poisoning.
In the lungs, when the phosphorus is taken in substance, there is
little “naked-eye” change, but Perls,S by manometric researches, has
* “A Recent Case of Suicide,” by Herbert J. Capon, M.D.—Lancet, March 18,
{
* Virchow's Archiv f. path. Amat., Bd. xxxiii. Hft. 3, S. 432, 1865. a
f Ibid., Bd. xxxiv. Hft. I u. 2, S. 73, 1865.
§ Deutsch. Archiv f. klin. Med., vi. Hft. 1, S. 1, 1869.
§ 295, 296.] PHOSPHORUS. 24 I
shown that the elasticity is always decreased. According to experiments
on animals, when the vapour is breathed, the mucous membrane is red,
congested, swollen, and has an acid reaction.
In the nervous system no change has been remarked, save occasion-
ally hamorrhagic points and extravasations.
§ 295. Diagnostic Differences between Acute Yellow Atrophy of
the Liver and Fatty Liver produced by Phosphorus.-O. Schultzen
and O. L. Riess have collected and compared ten cases of fatty liver from
phosphorus poisoning, and four cases of acute yellow atrophy of the liver,
and, according to them, the chief points of distinction are as follows:–
In phosphorus poisoning the liver is large, doughy, equally yellow, and
with the acini well marked ; while in acute yellow atrophy the liver is
diminished in size, tough, leathery, and of a dirty yellow hue, the acini
not being well mapped out. The “phosphorus” liver, again, presents
the cells filled with large fat drops, or entirely replaced by them ; but in
the “atrophy” liver, the cells are replaced by a finely-nucleated detritus
and through newly-formed cellular tissue. Yellow atrophy seems to be
essentially an inflammation of the intralobular connective tissue, while in
phosphorus poisoning the cells become gorged by an infiltration of fat,
which presses upon the vessels and lessens the blood supply, and the
liver, in consequence, may, after a time, waste.
There is also a clinical distinction during life, not only in the lessening
bulk of the liver in yellow atrophy, in opposition to the increase of size
in the large phosphorus liver, but also in the composition of the renal
secretion. In yellow atrophy the urine contains so much leucine and
tyrosin, that the simple addition of acetic acid causes at once a precipitate.
Schultzen and Riess also found in the urine, in cases of yellow atrophy,
oxymandelic acid (CsPIs(),), but in cases of phosphorus poisoning a mitro-
genised acid, fusing at 184° to 185°.
According to Maschka, grey-white, knotty, faecal masses are found in
the intestines in yellow atrophy, but never in cases of phosphorus poison-
ing. In the latter, it is more common to find a slight intestinal catarrh
and fluid excreta.
§ 296. The Detection of Phosphorus.-The following are the chief
methods in use for the separation and detection of phosphorus : *—
1. Mitscherlich's Process.-The essential feature of this process is
simply distillation of free phosphorus, and observation of its luminous
properties as the vapour condenses in the condensing tube. The condi-
* It has been recommended to dissolve the phosphorus out from organic matters.
by carbon disulphide. On evaporation of the latter the phosphorus is recognised
by its physical properties. Such a method is of but limited application, although
it may sometimes be found useful. The senior author has successfully employed it
in the extraction of phosphorus from the crop of a fowl; but on this occasion it
happened to be present in large quantity. 6
I
242 POISONS : THEIR EFFECTS AND DETECTION. [$ 296.
tions necessary for success are—(1) that the apparatus should be in total
darkness; * and (2) that there should be no substance present, such
as alcohol or ammonia, f which, distilling over with the phosphorus
vapour, could destroy its luminosity. A convenient apparatus, and one
certain to be in all laboratories, is an ordinary Florence flask, containing
the liquid to be tested, fitted to a glass Liebig's condenser, supported on
an iron sand-bath (which may, or may not, have a thin layer of sand), and
heated by a Fletcher's low temperature burner. The distillate is received
into a flask. This apparatus, if in darkness, works well; but should the
observer wish to work in daylight, the condenser must be enclosed in
a box perfectly impervious to light, and having a hole through which
the luminosity of the tube may be seen, the head of the operator and the
box being covered with a cloth. If there be a stream of water passing
continuously through the condenser, a beautiful luminous ring of light
appears in the upper part of the tube, where it remains fixed for some
time. Should, however, the refrigeration be imperfect, the luminosity
travels slowly down the tube into the receiver. In any case, the deli-
cacy of the test is extraordinary. If the organic liquid is alkaline, or
even neutral, there will certainly be some evolution of ammonia, which
will distil over before the phosphorus, and retard (or, if in sufficient
quantity, destroy) the luminosity. In such a case it is well, as a precau-
tion, to add enough sulphuric acid to fix the ammonia, omitting such
addition if the liquid to be operated upon is acid.
2. The Production of Phosphine (PHA).-Any method which pro-
duces phosphine (phosphuretted hydrogen), enabling that gas to be
passed through nitrate of silver solution, may be used for the detection
of phosphorus. Thus, Sonnenschein states that he has found phos-
phorus in extraordinary small amount, mixed with various substances,
by heating with potash in a flask, and passing the phosphine into silver
nitrate, separating the excess of silver, and recognising the phosphoric
acid by the addition of molybdate of ammonia. §
The usual way is, however, to produce phosphine by means of the
action on free phosphorus of nascent hydrogen evolved on dissolving
metallic zinc in dilute sulphuric acid. Phosphine is formed by the
* Any considerable amount of phosphorescence can, however, be observed in
twilight.
+ Many volatile substances destroy the luminous appearance of phosphorus
vapour, e.g. chlorine, hydric sulphide, sulphur dioxide, carbon disulphide, ether,
alcohol, petroleum, turpentine, creasote, and most essential oils. On the other hand,
-bromine, hydrochloric acid, camphor, and carbonate of ammonia do not seem to inter-
fere much with the phosphorescence.
† Fresenius states that he and Neubauer, with 1 mgrm. of phosphorus in 200,000,
recognised the light, which lasted for half an hour. —Zeitschr. f. anal. Chem., i.
p. 336.
§ Sonnenschein, Handbuch der gerichtlichen Chemie, Berlin, 1869,
§ 296.] PHOSPHORUS. 243
action of nascent hydrogen on Solid phosphorus, phosphorous acid, and
hypophosphorous acid; but no phosphine can be formed in this way by
the action of hydrogen on phosphoric acid.
Since it may happen that no free phosphorus is present, but yet the
first product (phosphorous acid) of its oxidation, the production of phos-
phine becomes a necessary test to make on failure of Mitscherlich's
test ; if no result follows the proper application of the two processes,
the probability is that phosphorus has not been taken.
Blondlot and Dusart evolve hydrogen from zinc and dilute sulphuric
acid, and pass the gas into silver nitrate; if the gas is pure, there is
of course no reduction: the liquid to be tested is then added to the
hydrogen-generating liquid, and if phosphorous or hypophosphorous acids
be present, a black precipitate of phosphor-silver will be produced. To
prove that this black precipitate is neither that produced by SH2, nor
by antimony nor arsenic, the precipitate is collected and placed in the
apparatus to be presently described, and the spectroscopic appearances of
the phosphine flame observed.
3. Tests dependent on the Combustion of Phosphine (PH,)—A
hydrogen flame, containing only a minute trace of phosphorus, or of the
lower product of its oxidation, acquires a beautiful green tint, and
possesses a characteristic spectrum. In order to obtain the latter in its
best form, the amount of phosphine must not be too large, or the flame
will become whitish and livid, and the bands lose their defined character,
rendering the spectrum continuous. Again, the orifice of the tube
whence the gas escapes must not be too small ; and the best result is
obtained when the flame is cooled.
M. Salet has proposed two excellent methods for the observation of
phosphine by the spectroscope —
(1) He projects the phosphorus flame on a plane vertical surface,
maintained constantly cold by means of a thin layer of running water;
the green colour is especially produced in the neighbourhood of the
cool surface. -
(2) At the level of the base of the flame there is an annular space,
through which a stream of cold air is continually blown upwards. Thus
cooled, the light is very pronounced, and the band 8, which is almost
invisible in the ordinary method of examination, is plainly seen.”
An apparatus (devised by Blondlot, and improved by Fresenius) for
the production of the phosphine flame in medico-legal research, is repre-
sented in the diagram on the following page:–
Several of the details of this apparatus may be modified at the com-
* Consult Spectres Luminewa, par M. Lecoq de Boisbaudran, Paris, 1874. See
also Christofle and Beilstrom’s “Abhandlung,” in Fresenius' Zeitschr. f. anal. Chem.,
B. ii. p. 465, and B. iii. p. 147.
244 POISONS : THEIR EFFECTS AND DETECTION. [$297.
venience of the operator. A is a vessel containing sulphuric acid ; B is
partly filled with granulated zinc, and hydrogen may be developed at
pleasure; c contains a solution of nitrate of silver; d is a tube at which
the gas can be lit ; e, a flask containing the fluid to be tested, and pro-
vided with a tube f at which also the gas issuing can be ignited. The
orifice should be provided with a platinum nozzle. When the hydrogen
has displaced the air, both tubes are lit, and the two flames, being side
by side, can be compared. Should any phosphorus come over from the
zinc (a possibility which the interposed silver nitrate ought to guard
against), it is detected ; the last flask is now gently warmed, and if
the flame is green, or, indeed, in any case, it should be examined by
the spectroscope.*
º
<=l |||||||||||||||ſium
ÉÉ:
$297. The spectrum, when fully developed, shows one band in the
orange and yellow between C and D, but very close to D, and several
bands in the green. But the bands 8, y, a, and 3 are the most
characteristic. The band 8 has its centre about the wave-length 599'4;
it is easily distinguished when the slit of the spectroscope is a little
wide, but may be invisible if the slit is too narrow. It is best seen by
M. Salet's second process, and, when cooled by a brisk current of air, it
broadens, and may extend closer to D. The band y has a somewhat
decided border towards E, while it is nebulous towards D, and it is,
therefore, very difficult to say where it begins or where it ends; its
centre may, however, be put at very near 109 of Boisbaudran's scale,
corresponding to W. L. 560-5, if the flame is free. This band is more
* F. Selmi has proposed the simple dipping of a platinum loop into a liquid con-
taining phosphoric acid, and then inserting it into the tip of a hydrogen flame.

§ 298.] PHOSPHORUS. 245
distinct than 8, but with a strong current of air the reverse is the case.
The middle of the important band a is nearly marked by Fraunhofer's
line E. Boisbaudran gives it as coinciding with 122 of his scale W. L.
526'3. In ordinary conditions (that is, with a free uncooled flame) this
is the brightest and most marked of all the bands. The approximate
middle of the band 8 is W. L. 510-6 (Boisbaudran's scale 129:00).
Lipowitz's Sulphur Test.—Sulphur has the peculiar property of
condensing phosphorus on its surface, and of this Lipowitz proposed to
take advantage. Pieces of sulphur are digested some time with the
liquid under research, subsequently removed, and slightly dried. When
examined in the dark, should phosphorus be present, they gleam strongly
if rubbed with the finger, and develop a phosphorus odour. The test is
wanting in delicacy, nor can it well be made quantitative; it has, how-
ever, an advantage in certain cases, e.g. the detection of phosphorus in
an alcoholic liquid.
Scherer's test, as modified by Hager,” is a very delicate and almost
decisive test. The substances to be examined are placed in a flask with
a little lead acetate (to prevent the possibility of any hydric sulphide
being evolved), some ether added, and a strip of filter-paper soaked in a
solution of silver nitrate is then suspended in the flask; this is con-
veniently done by making a slit in the bottom of the cork, and in the
slit securing the paper. The closed flask is placed in the dark, and if
phosphorus is present, in a few minutes there is a black stain. It may
be objected that arsine will cause a similar staining, but then arsine
could hardly be developed under the circumstances given. It is
scarcely necessary to observe that the paper must be wet.
§ 298. Chemical Examination of the Urine.—It may be desirable,
in any case of suspected phosphorus poisoning, to examine the renal
secretion for leucin and tyrosin, etc. Leucin may be found as a deposit
in the urine. Its general appearance is that of little oval or round discs,
looking like drops of fat. It can be recognised by taking up one or more
of these little bodies and placing them in the author's subliming cell (see
p. 259). By careful heating it will sublime wholly on to the upper cover.
On now adding a little nitric acid to the sublimed leucin, and drying,
and then to the dried residue adding a droplet of a solution of sodium
hydrate, leucin forms an oily drop. Tyrosin also may occur as a sediment
of little heaps of fine needles. The best test for tyrosin is to dissolve in
hot water, and then add a drop of a solution of mercuric nitrate and
mercurous nitrate, when a rose colour is at once developed, if the tyrosin
is in very minute quantity; but if in more than traces, there is a distinct
crimson precipitate. To separate leucin and tyrosin from the urine, the
best process is as follows:—The urine is filtered from any deposit,
- * Pharm. Central-halle, xx. 353.
246 POISONS : THEIR EFFECTS AND DETECTION, [$299.
evaporated to a thin syrup, and decanted from the second deposit that
forms. The two deposits are mixed together and treated with dilute
ammonia, which will dissolve out any tyrosin and leave it in needles, if
the ammonia is spontaneously evaporated on a watch-glass. The urine
is then diluted and treated with neutral and basic acetates of lead, filtered,
and the lead thrown out of the filtrate by hydric sulphide. The filtrate
is evaporated to a syrup, and it then deposits leucin mixed with some
tyrosin. If, however, the syrup refuses to crystallise, it is treated with
cold absolute alcohol, and filtered; the residue is then boiled up with
spirit of wine, which extracts leucin, and deposits it on cooling in a
crystalline form. To obtain oxymandelic acid, the mother-liquor, from
which leucin and tyrosin have been extracted, is precipitated with
absolute alcohol, filtered, and then the alcoholic solution evaporated to a
syrup. This syrup is acidified by sulphuric acid, and extracted with
ether; the ether is filtered off and evaporated to dryness; the dry residue
will be in the form of oily drops and crystals. The crystals are collected,
dissolved in water, and the solution precipitated by lead acetate to remove
colouring matters; after filtration it is finally precipitated by basic acetate.
On decomposition of the basic acetate, by suspending in water and
saturating with hydric sulphide, the ultimate filtrate on evaporation
deposits colourless, flexible needles of oxymandelic acid. The nitro-
genised acid which Schultzen and Riess obtained from urine in a case of
phosphorus poisoning, was found in an alcohol and ether extract—warts
of rhombic scales separating out of the syrupy residue. These scales gave
no precipitate with basic acetate, but formed a compound with silver
nitrate. The silver compound was in the form of shining white needles,
and contained 33.9 per cent. of silver; the acid was decomposed by heat,
and with lime yielded aniline. Its melting-point is given at from 184°
to 185°. The occurrence of some volatile substance in phosphorus
urine, which blackens mitrate of silver, and which is probably phosphine,
was first noticed by Selmi.* Pesci and Stroppa have confirmed Selmi's
researches. It is even given off in the cold.
§ 299. The quantitative estimation of phosphorus is best carried
out by oxidising it into phosphoric acid, and estimating as ammon.
magnesian phosphate. To effect this, the substances are distilled in an
atmosphere of CO2 into a flask with water, to which a tube containing
silver nitrate is attached; the latter retains all phosphine, the former
solid phosphorus. If necessary, the distillate may be again distilled into
AgNO, ; and in any case the contents of the U-tube and flask are mixed,
oxidised with nitromuriatic acid, filtered from silver chloride, and the
phosphoric acid determined in the usual way.
In the case of a child poisoned by lucifer matches, Sonnenschein
* Giornwale Internaz, della Scienza Med., 1879. Nro. 5, p. 645.
§ 3OO.] PHOSPHORUS. 247
estimated the free phosphorus in the following way:—The contents of
the stomach were diluted with water, a measured part filtered, and
the phosphoric acid estimated. The other portion was then oxidised
by HCl and potassic chlorate, and the phosphoric acid estimated—the
difference being calculated as free phosphorus.
§ 300. How long can Phosphorus be recognised after Death?–One
of the most important matters for consideration is the time after death in
which free phosphorus, or free phosphoric acids, can be detected. Any
phosphorus changed into ammon. mag. phosphate, or into any other salt,
is for medico-legal purposes entirely lost, since the expert can only take
cognisance of the substance either in a free state, as phosphine, or as a
free acid.
The question, again, may be asked in court—Does the decomposition
of animal substances rich in phosphorus develop phosphine? The answer
to this is, that no such reaction has been observed.
A case is related * in which phosphorus was recognised, although the
body had been buried for several weeks and then exhumed.
The expert of pharmacy of the Provincial Government Board of
Breslau has also made some experiments in this direction, which are
worthy of note –Four guinea-pigs were poisoned, each by 0.023 grn.
of phosphorus; they died in a few hours, and were buried in sandy-loam
soil, 0.5 metre deep. Exhumation of the first took place four weeks after.
The putrefying organs—heart, liver, spleen, stomach, and all the intes-
tines—tested by Mitscherlich's method of distillation, showed charac-
teristic phosphorescence for nearly one hour.
The second animal was exhumed after eight weeks in a highly putres-
cent state. Its entrails, on distillation, showed the phosphorescent
appearance for thiry-five minutes.
The third animal was taken from the earth after twelve weeks, but no
free phosphorus could be detected, although there was evidence of the
lower form of oxidation (POs) by Blondlot's method.
The fourth animal was exhumed after fifteen weeks, but neither free
phosphorus nor POs could be detected.t
A man, as well as a cat, was poisoned by phosphorus. On analysis,
twenty-nine days after death, negative results were alone obtained.—
(Sonnenschein.)
It will thus be evident that there is no constant rule, and that, even
when decomposition is much advanced, an examination may be
successful.
* Pharm. Zeitsch. f. Russl., Jahrg. 2, p. 87.
+ Vierteljahrsschrift für gerichtliche Medicin, Jan. 7, 1876; see also Zeitschr, f.
anal. Chemie, 1872.
PART VI. —ALKALOIDS AND POISONOUS VEGETABLE PRIN-
CIPLES SEPARATED FOR THE MOST PART BY ALCO-
HOLIC SOLVENTS.
DIVISION I.- VEGETABLE ALKALOIDS.
I.—General Methods of Testing and Extracting Alkaloids.
§ 301. General Tests for Alkaloids.-In order to ascertain whether
an alkaloid is present or not, a method of extraction must be pursued
which, while disposing of fatty matters, salts, etc., shall dissolve as little
as possible of foreign substances—such a method, e.g., as the original
process of Stas, or one of its modern modifications.
If to the acid aqueous solution finally obtained by this method a
dilute solution of soda be added, drop by drop, until it is rendered
feebly alkaline, and no precipitate appear, whatever other poisonous
plant-constituents may be present, all ordinary alkaloids” are absent.
In addition to this negative test, there are also a number of sub-
stances which give well-marked crystalline or amorphous precipitates
with alkaloids.
§ 302. These may be called “group reagents.” The chief members
of the group reagents are—iodine dissolved in hydriodic acid, iodine
dissolved in potassic iodide solution, bromine dissolved in potassic
bromide solution, hydrargo-potassic iodide, bismuth-potassic iodide,
cadmic potassic iodide ; the chlorides of gold, of platinum, and mercury;
picric acid, gallic acid, tannin, chromate of potash, bichromate of potash,
phospho-molybdic acid, phospho-tungstic acid, silico-tungstic acid, and
Fröhde's reagent. It will be useful to make a few general remarks on
some of these reagents. -
Iodine in hydriodic acid gives either crystalline or amorphous pre-
cipitates with nearly all alkaloids; the compound with morphine, for
* In the case of morphine tartrate, this test will not answer. See the article on
Morphine.
248
§ 3O3.] WEGETABLE ALKALOIDS. 249
example, is in very definite needles; with dilute solutions of atropine,
the precipitate is in the form of minute dots, but the majority of the
precipitates are amorphous, and all are more or less coloured. -
Iodine dissolved in a solution of potassic iodide gives with alkaloids
a reddish or red-brown precipitate, and this in perhaps a greater dilu-
tion than almost any reagent. Since the testing solution may be also
used for ascertaining the weight of the alkaloid, it is convenient to make
it a decinormal one, that is, 12.7 grms. I and 60 grnms. KI, dissolved in
a litre of water. When added to an aqueous solution, the precipitates
are amorphous, but if added to an alcoholic solution, certain alkaloids
then form crystalline precipitates; this, for example, is the case with
berberine and narceine. The aqueous solution should be either neutral
or feebly acid. The alkaloid may be recovered by the process detailed
on page 253. A solution of bromine in potassic bromide solution also
gives similar precipitates to the above, but it forms insoluble compounds
with phenol, orcin, and other substances.
Mercuric potassic iodide is prepared by decomposing mercuric
chloride with potassic iodide in excess. The proportions are 13:546
grms. of mercuric chloride and 49.8 of potassic iodide, and water
sufficient to measure, when dissolved, 1 litre. The precipitates from
this reagent are white and flocculent ; many of them become, on
standing, crystalline.
Bismuthic potassic iodide in solution precipitates alkaloids, and the
compounds formed are of great insolubility, but it also forms compounds
with the various albuminoid bodies.
Iodised parethoxyphenyl succinimide is another reagent which
precipitates alkaloids, and is said to be even more sensitive than iodine
in pot, iodide.
Chloride of gold forms with the alkaloids compounds, many of which
are crystalline, and most admit of utilisation for quantitative determina-
tions. Chloride of gold does not precipitate amides or ammonium com-
pounds, and on this account its value is great. The precipitates are
yellow, and after a while are partly decomposed, when the colour is of a
reddish-brown.
Platinic chloride also forms precipitates with most of the alkaloids,
but since it also precipitates ammonia and potassic salts, it is inferior to
gold chloride in utility.
§ 303. (1) Phosphomolybdic Acid as a Reagent for Alkaloids.
Preparation : Molybdate of ammonia is precipitated by phosphate of
soda ; and the well-washed yellow precipitate is suspended in water and
warmed with carbonate of soda, until it is entirely dissolved. This solu-
tion is evaporated to dryness, and the ammonia fully expelled by heat-
ing. If the molybdic acid is fairly reduced by this means, it is to be
25O POISONS : THEIR EFFECTS AND DETECTION. [$ 3O3,
moistened by nitric acid, and the heating repeated. The now dry residue
is warmed with water, nitric acid added to strong acid reaction, and the
mixture diluted with water, so that 10 parts of the solution contain 1 of
the dry salt. The precipitates of the alkaloids are as follows:—
Aniline, . tº e o e Bright yellow, flocculent.
Morphine, 3 3 2 3
Narcotine, e e º & Brownish-yellow, , ,
Quinine, . o º º e Whitish-yellow, , ,
Cinchonine, 3 3 } }
Codeine, . t º e e Brownish-yellow, voluminous.
Strychnine, . º - e White-yellow, 3 j
Brucine, . º º º º Yelk-yellow, flocculent.
Weratrine, e º © tº Bright yellow, 2 3
Jervine, 2 3 } }
Aconitine, 3 3 2 3
Emetime, . 3 x 2 3
Theine, . e s - g Bright yellow, voluminous.
Theobromine, 5 2 5 5
Solanine, . g & º º Citron-yellow, pulverulent.
Atropine, º e - e Bright yellow, flocculent.
Hyoscyamine, . 5 5 5 5
Colchicine, o e e & Orange-yellow, } %
Delphinine, . . e e Grey-yellow, voluminous.
Berberine, & e º e Dirty yellow, flocculent.
Coniine, . & * . Bright yellow, voluminous.
Nicotine, .
5 3 5 5
Piperine, . e Brownish-yellow, flocculent.
(2) Silico-Tungstic Acid as a Reagent for Alkaloids.-Sodium tung-
state is boiled with freshly precipitated gelatinous silica. To the solution
is added mercurous nitrate, which precipitates the yellow mercurous
silico-tungstate. This is filtered, well washed, and decomposed by an
equivalent quantity of hydrochloric acid; silico-tungstic acid then goes
into solution, and mercurous chloride (calomel) remains behind. The
clear filtrate is evaporated to drive off the excess of hydrochloric acid,
and furnishes, on spontaneous evaporation, large, shining, colourless
octahedra of silico-tungstic acid, which effloresce in the air, melt at 36°,
and are easily soluble in water or alcohol. - -
This agent produces no insoluble precipitate with any metallic salt.
Caesium and rubidium salts, even in dilute solutions, are precipitated by
it ; neutral solutions of ammonium chloride give with it a white precipi-
tate, soluble with difficulty in large quantities of water. It precipitates
solutions of the salts of quinine, cinchonine, morphine, atropine, etc.; if
in extremely dilute solution, an opalescence only is produced: for in-
stance, it has been observed that cinchonine hydrochlorate in gooºooo,
quinia hydrochlorate in goºd, morphia hydrochlorate in Tºss dilution,
all gave a distinct opalescence.—Archiv der Pharm, Nov., Dr. Richard
Godeffroy.
§ 3O4–306.] WEGETABLE ALKALOIDS. 25 I
According to Gabriel Bertrand (Compt. Rend., cyxviii. 742), the salts
possess the general formula 12WoO,SiO, Alk+ n}{20, the morphine salt
has the formula of 12WoOº.SiO,2H,04C, Hiſ MOs 4-9H,0; dried at
120°, it still contains 2 molecules of water; the strychnine salt is
similar, but retains only 1 mol. of water on drying. These compounds
are insoluble in acids or cold water; for the most part they do not
interfere with colour tests, and on treatment with dilute alkalies,
silicium and tungsten pass into solution and the alkaloid can either be
filtered off or shaken out with appropriate solvents.
(3) Scheibler's Method for Alkaloids: Phospho-Tungstic Acid.—
Ordinary commercial sodium tungstate is digested with half its weight
of phosphoric acid, specific gravity 1-13, and the whole allowed to stand
for some days, when the acid separates in crystals. A solution of these
crystals will give a distinct precipitate with the most minute quantities
of alkaloids, gooºowd of strychnine, and Toºwo of quinine. The alkaloid
is liberated by digestion with barium hydrate (or calcium hydrate); and
if volatile, may be distilled off; if fixed, dissolved out by chloroform.
In complex mixtures, colouring matter may be removed by plumbic
acetate, the lead thrown out by SH, and concentrated, so as to remove
the excess of SH3. -
§ 304. Schulze's reagent is phospho-antimonic acid. It is prepared
by dropping a strong solution of antimony trichloride into a saturated
solution of sodic phosphate. The precipitation of the alkaloids is
effected by this reagent in a sulphuric acid solution.
§ 305. Dragendorff's reagent is a solution of potass-bismuth iodide ;
it is prepared by dissolving bismuth iodide in a hot solution of
potassium iodide, and then diluting with an equal volume of iodide of
potassium solution. On the addition of an acid solution of an alkaloid,
a kermes-red precipitate falls down, which is in many cases crystalline.
Marmé's reagent is a solution of potass-cadmium iodide. It is made
on similar principles.
Potass-zinc iodide in solution is also made similarly. The pre-
cipitates produced in solutions of narceine and codeine are crystalline
and very characteristic. *
§ 306. Colour Tests.-Fröhde's reagent is made by dissolving 1
part of sodic molybdate in 10 parts of strong sulphuric acid; it strikes
distinctive colours with many alkaloids.
Mandelin's reagent is a solution of meta-vanadate of ammonia in
mono- or dihydrated sulphuric acid. The strength should be 1 part of
the salt to 200 of the acid. This reagent strikes a colour with many
alkaloids, and aids to their identification. It is specially useful to
supplement and correct other tests. (See p. 58 for the spectroscopic
appearances of certain of the colour tests.)
252 POISONS : THEIR EFFECTS AND DETECTION. [Š 3O7.
METHODS OF SEPARATION.
$307. General processes for the Separation of Alkaloidal Substances
from Organic Matters.-The processes in use are the Stas-Otto process,
the process of Kippenberger, and that of Dragendorff. The Hilger-
Kuster method, in which gypsum is used, apparently leads to poor
results, and will therefore not be described.
The three processes are seldom used singly, but more or less in com-
bination. The Stas-Otto process consists in exhausting the organic
matters with strong alcohol. With every kilogramme of such sub-
stances as liver or other internal organs, rather more than a litre of
alcohol of 92 to 95 per cent. strength is required. The more finely
divided the organ is the better. For this purpose it is often advisable
to pass the matters through a mincing machine. The flask containing
the substances and the alcohol is placed in a water-bath and the cork
connected with a reflux condenser. The water in the bath is kept at a
boiling temperature from one to two hours. In the original Stas-Otto
process an acid, such as tartaric acid, was usually added ; but if the
substance itself, as is usually the case, has an acid reaction, and at the
end of the operation the alcohol is found acid, it is preferable not to add
acid. The alcoholic solution is filtered through a piece of muslin and
the organic matter pressed in a filter press, so as to squeeze the solution
out of the mass. It is best now to distil off the alcohol, and then to
extract the watery fluid in a separating funnel by petroleum ether two
or three times, otherwise there will be much difficulty in filtration.
The petroleum ether extract contains all the fatty matter and, it may
be, some of the alkaloid dissolved in the fat. To recover this the
petroleum is distilled off, a little paraffin wax added to the fatty matter
left behind, and the fatty matters washed in a separating funnel with
hot water made slightly acid by means of hydrochloric acid.
The original liquid, free from fat, is then filtered. The clear liquid
to which the washings of the fat are added is now evaporated to dryness
and treated with absolute alcohol. The absolute alcoholic extract is
filtered and evaporated to dryness. This contains all the alkaloid in an
impure state. It is, however, important to note that even when no
alkaloidal poison is present, the extract invariably contains residues
which give decided reactions with the group-alkaloidal reagents, such
as iodine and potassic iodide, phospho-tungstic acid, and so forth.
Kippenberger's Process.-In Kippenberger's process the reaction
of the final product with general alkaloidal reagents in operating
on alkaloidal free substances is much less than in the Stas-Otto
process.
Kippenberger extracts the organic substances with glycerin holding
§ 308.] WEGETABLE ALKALOIDS, 253
tannin in solution. To 500 grms. of glycerin should be added about
100 grms. of tannin.
The extraction may be conducted at a gentle heat, and should be
continued for several hours. The glycerin solution is filtered, a process
which is facilitated by diluting the glycerin; with this extract, as with
the Stas-Otto process, it is advisable to extract the fat by petroleum
ether before filtration.
It is best in practice to combine the Stas-Otto process with Kippen-
berger's, that is to say, to apply Kippenberger's process to the ultimate
alcoholic extract derived from the Stas-Otto process in order to get rid
of impurities.
In either case the final aqueous, slightly acid solution may be
treated with either the general alkaloidal reagents or it may be very
carefully alkalised by a solution of potash; if no turbidity or precipitate
occurs, then no ordinary alkaloid is present. Should a cloud or precipitate
occur the liquid can be made acid, so as to dissolve the precipitate,
and be submitted to Dragendorff's process.
Most alkaloids can also be purified by Kippenberger's* iodine method,
which is as follows:—The supposed alkaloid is dissolved in a little acid
water, which is then just made neutral by soda solution; it is then pre-
cipitated by a solution of iodine and potassic iodide (12.7 grms. I and 60
grims. KI to the litre), the precipitate is filtered through an asbestos
filter and washed with cold water, it is then dissolved in acetone, to
the acetone is added NaOH solution to saturate free iodine, the alkaline
solution is next acidified and mixed with water. The scarcely coloured
final solution contains the alkaloid as an acid salt. The solution is now
gently warmed in the water-bath to evaporate off the acetone, and while
still warm a few drops of d.m. solution of thio-sulphate added. The acid
is now over-saturated with sodic carbonate and the alkaloids shaken out
by means of an appropriate volatile solvent. A silico-tungstate of the
alkaloid may also be made, or a picrate ; in either case on alkalising the
alkaloid is set free, and may be separated by amyl-alcohol, chloroform,
ether, according to its solubility.
§ 308. Selmi's Process for Separating Alkaloids.-A method of
separating alkaloids from an ethereal solution has been proposed by
Selmi.f. The alcoholic extract of the viscera, acidified and filtered, is
evaporated at 65°; the residue taken up with water, filtered, and
decolorised by basic acetate of lead. The lead is thrown out by
sulphuretted hydrogen; the solution, after concentration, repeatedly
extracted with ether ; and the ethereal solution saturated with dry
CO, which generally precipitates some of the alkaloids. The ethereal
* Zeit. f. analytische Chemie, 1896, 414.
f Selmi, Gazett. Chim, Ital., vi. 153–166, and Journ. Chem. Soc., i., 1877, 93.
254 POISONS : THEIR EFFECTS AND DETECTION, [$ 309.
solution is then poured into clean vessels, and mixed with about half
its volume of water, through which a current of CO2 is passed for twenty
minutes; this may cause the precipitation of other alkaloids not thrown
down by dry CO2. If the whole of the alkaloids are not obtained by
these means, the solution is dehydrated by agitation with barium oxide,
and a solution of tartaric acid in ether is added (care being taken to
avoid excess); this throws down any alkaloid still present. The detec-
tion of any yet remaining in the viscera is effected by mixing with
barium hydrate and a little water, and agitating with purified amylic
alcohol; from the alcohol the alkaloids may be subsequently extracted
by agitation with very dilute sulphuric acid.
Another ingenious method (also the suggestion of Selmi) is to treat
the organic substance with alcohol, to which a little sulphuric acid has
been added, to filter, digest with alcohol, and refilter. The filtrates are
united, evaporated down to a smaller bulk, filtered, concentrated to a
syrup, alkalised by barium hydrate, and, after the addition of freshly
ignited barium oxide and some powdered glass, exhausted with dry
ether; the ether filtered, the filtrate digested with lead hydrate; the
ethereal solution filtered, evaporated to dryness, and finally again taken
up with ether, which, this time, should leave on evaporation the alkaloid
almost pure.
§ 309. Dragendorff's Process.--To Dragendorff we owe an elaborate
general method of separation, since it is applicable not only to alkaloids,
but to glucosides, and other active principles derived from plants. His
process is essentially a combination of those already known, and its dis-
tinctive features are the shaking up—(1) of the acid fluid with the
solvent, thus removing colouring matters and certain non-alkaloidal
principles; and (2) of the same fluid made alkaline.
I. The substance, in as finely-divided form as possible, is digested for
a few hours in water acidified with sulphuric acid, at a temperature of
40° to 50°, and this operation is repeated two or three times, with
filtering and pressing of the substances; later, the extracts are united.
This treatment (if the temperature mentioned is not exceeded) does not
decompose the majority of alkaloids or other active substances; but there
are a few (e.g. solanine and colchicine) which would be altered by it;
and, if such are suspected, maceration at the common temperature is
necessary, with substitution of acetic for sulphuric acid.*.
II. The extract is next evaporated until it begins to be of a syrupy
consistence; the residue mixed with three to four times its volume of
alcohol, macerated for twenty-four hours at about 34", allowed to become
* When blood is to be examined, it is better to dry it, and then powder and
extract with water acidified with dilute sulphuric acid. However, if the so-called
volatile alkaloids are suspected, this modification is to be omitted.
§ 309.] DRAGENDORFF'S PROCESS. 255
quite cool, and filtered from the foreign matters which have separated.
The residue is washed with alcohol of 70 per cent.
III. The filtrateisfreed from alcohol by distillation, the watery residue
poured into a capacious flask, diluted (if necessary) with water, and
filtered. Acid as it is, it is extracted at the common temperature, with
frequent shaking, by freshly-rectified petroleum ether; and, after the
fluids have again separated, the petroleum ether is removed, carrying
with it certain impurities (colouring matter, etc.), which are in this way
advantageously displaced. By this operation ethereal oils, carbolic acid,
picric acid, etc., which have not been distilled, besides piperin, may also
be separated. The shaking up with petroleum ether is repeated several
times (as long as anything remains to be dissolved), and the products are
evaporated on several watch-glasses.
The fluid is next successively shaken up with benzene and chloroform,
the solvents being removed and evaporated as before, the last traces of
chloroform are removed by petroleum ether, and the liquid alkalised by
ammonia is shaken up successively with petroleum ether, benzene,
chloroform, and lastly amyl alcohol.
The original process was based upon the supposed fact that volatile
solvents, such as ether, petroleum ether, acetic acid, tetrachloride of
carbon, extracted from acid solutions, fats, glucosides, and various non-
alkaloidal substances, while the same solution alkalised gave up to an
appropriate solvent alkaloidal substances—the said alkaloidal substances
being, with a few exceptions, almost insoluble in the volatile solvent
acting on acid solutions. This has now been shown to be only true to a
certain extent. For example, Kippenberger has shown that 200 mgrms.
of strychnine dissolved in 70 c.c. of water, acidified by 2 c.c. of HCl, and
the whole shaken up with 50 c.c. of chloroform, is taken up by the
solvent to the extent of 43 to 49 per cent. ; 200 mgrms. of papaverine
dissolved with 1 c.c. of HCl in 70 c.c. of water can, by repeated shaking
with chloroform, be entirely extracted; and, according to the dilution
and the kind and strength of acid, a great number of the alkaloids may
be to a considerable extent shaken out of acid solutions. The reason
of this is that dissociation of the alkaloidal salt takes place under
certain conditions of dilution and acidity; then the alkaloidal base is
soluble in the volatile solvent, the hydrochlorides being more easily
dissociated than the sulphates, and, therefore, sulphuric acid being the
more suitable to use ; the solutions must not be too dilute.
Dragendorff's process, or modifications thereof, is seldom employed
now for the direct extraction of poisons, but is useful for the investi-
gation of the extracts obtained by the Stas-Otto process.
Kippenberger's modification of Dragendorff's process is as follows:*
* Zeit. f. analytische Chemie, 1900, 290.
256 POISONS : THEIR EFFECTS AND DETECTION. [$ 3 IO.
—The fluid, which should be as free from mineral salts as possible, is
acidified with sulphuric acid until it contains at least 1 per cent. free
sulphuric acid; it is warmed to 30° C., allowed to cool, and then shaken
up twice with petroleum ether (b.p. 30°–50°) in a separating funnel.
The petroleum ether extracts fat, fatty acids, veratroidin, jervin-
xanthin bases, and other matters.
The petroleum ether remaining in the fluid is completely got rid of
by evaporation in the water-bath, cooled, and shaken up with chloroform ;
this removes from the acid solution colchicin, digitalin, picrotoxin,
cantharidin, papaverin, aconitine, narcein, jervin, geisospermin, caffein ;
it also extracts some delphinin, brucine, emetime, and thebaine, and
mere traces of narceine, strychnine, veratrine, and cocaine.
The acid liquid may now be alkalised with weak soda solution, and
shaken with chloroform. The chloroform extracts sparteine, coniine,
nicotine, atropine, codeine, emetime, brucine, Strychnine, Veratrine,
delphinine, pilocarpine, apomorphine, hyoscyamine, daturine, scopola-
mine, and alkaloids generally soluble in chloroform ; it must be
noted that in the alkaline liquid there may remain morphine, narcotine,
papaverine, aconitine, and caffein. To the alkaline fluid is now added a
concentrated solution of sodic bicarbonate and common salt, the latter
in the proportion of 15 grns. per cent, and the liquid again heated
with chloroform to which 10 per cent. alcohol has been added; this
dissolves out morphine, narceine, and strophantine.
If the shaking out process of Dragendorff is applied to quite small
quantities of fluid, say up to 50 c.c., derived from an alcoholic extract,
there is seldom any practical difficulty in its execution; if, on the other
hand, solutions containing mucus, peptones, albumoses, and carbohydrates
are treated by the volatile solvents, emulsions are obtained, difficult to
separate. Some partial success in separation is possible by warming the
mixture, and also by whirling the separating funnel and its contents in
a centrifugal apparatus; but unless meat, well-defined separations occur,
the process should not be used.
§ 310. Scheibler's Process.-This is to precipitate the phosphotungstate of the
alkaloid, and then to liberate the latter by digesting the precipitate with either
hydrate of barium or hydrate of calcium, dissolving it out by chloroform, or, if
volatile, by simple distillation. The details of Scheibler's process are as follows:—
The organic mixture is repeatedly extracted by water strongly acidified with
sulphuric acid; the extract is evaporated at 30° to the consistence of a thin syrup;
then diluted with water, and after several hours' standing, filtered in a cool place.
To the filtered fluid phosphotungstic acid is added in excess, the precipitate filtered,
washed with water to which some phosphotungstic acid solution has been added,
and, while still moist, rinsed into a flask. Caustic baryta or carbonate of potash is
added to alkaline reaction, and after the flask has been connected with bulbs con-
taining HCl, it is heated at first slowly, then more strongly. Ammonia and any
volatile alkaloids are driven over into the acid, and are there fixed, and can be
§ 31 I-313.] IDENTIFICATION OF THE ALKALOIDS. 257
examined later by suitable methods. The residue in the flask is carefully evaporated
to dryness (the excess of baryta having been precipitated by CO2), and then extracted
by strong alcohol. On evaporation of the alcohol, the alkaloid is generally sufficiently
pure to be examined, or, if not so, it may be obtained pure by re-solution, etc.
Scheibler's process cannot be used with advantage directly on watery-
acid extracts of the organs, for it not only precipitates alkaloids, but
also invariably gives voluminous precipitates with ordinary flesh ex-
tracts, so that a preliminary purification from albuminous matters by
alcohol or glycerin tannin is necessary.
§ 311. Grandval and Lajoux's Method.”—The alkaloids are precipitated from a
solution slightly acidified by hydrochloric or sulphuric acid by a solution of hydrarg-
potassium iodide. The precipitate is collected on a filter, washed and then trans
ferred to a flask; drop by drop, a solution of sodium sulphide is added ; after each
addition the suspended precipitate is shaken and allowed to stand for a few minutes,
and a drop of the liquid taken out and tested with lead acetate; directly a slight
brown colour appears, sufficient sodic sulphide has been added. The liquid is now left
for half an hour, with occasional shaking. Then sulphuric acid is added until it is
just acid, and the liquid is filtered and the mercury sulphide well washed. In the
filtrate will be the sulphate of any alkaloid in solution ; this liquid is now made
alkaline with soda carbonate and shaken up, as in Dragendorff's process, with
appropriate solvents; such, for example, as ether, or chloroform, or acetone, or amylic
alcohol, according to the particular alkaloid the analyst is searching for, and the
solvent finally separated and allowed to evaporate, when the alkaloid is found in the
residue.
§ 312. Identification of the Alkaloids.-Having obtained, in one way or other,
a crystalline or amorphous substance, supposed to be an alkaloid, or, at all events, an
active vegetable principle, the next step is to identify it.
In medico-legal researches there is seldom any considerable quantity of the
material to work upon. Hence the greatest care must be taken from the commence-
ment not to waste the substance in useless tests, but to study well at the outset what
—by the method of extraction used, the microscopic appearance, the reaction to
litmus-paper, and the solubility in different menstrua—it is likely to be. However
minute the quantity may be, it is essential to divide it into different parts, in order
to apply a variety of tests; but as any attempt to do this on the solid substance will
probably entail loss, the best way is to dissolve it in a watch-glass in half a c.c. of
alcohol, ether, or other suitable solvent. Droplets of this solution are then placed
on watch-glasses or slips of microscopic glass, and to these drops, by the aid of a
glass rod, different reagents can be applied, and the changes watched under the
microscope as the drops slowly evaporate. -
§ 313. Behrens’ Method of Identification of the Alkaloids.-The micro-chemi-
cal methods of Behrems, aided by a few special tests, are useful for the identification of
certain of the alkaloids. The results are trustworthy, provided similar tests are
applied to pure samples of the particular alkaloid believed to be present.
Behrenst divides the alkaloids as follows:—
1. Alkaloids which are capable of being distilled from an aqueous solution.
2. Alkaloids soluble in water, but which cannot be distilled.
3. Difficultly soluble bases precipitable by sodium carbonate soluble in soda, but
* “Dosage des alcaloides à l'aide de l’iodure double de mercure et de potassium,”
par MM. A. Grandvalet Henri Lajoux, Journ. de Pharmacie, 5 ser, t. xxviii. 152–156.
+ Zeit. f. anal. Chemie, 1904, 333.
17
258 POISONS: THEIR EFFECTS AND DETECTION. [$ 314.
precipitable from the alkaline solution by sodium bicarbonate or ammonium carbonate,
such as morphine, apomorphine, and cupreine.
4. The rarer opium bases precipitable by sodic carbonate insoluble in caustic
soda solution, such as narcein, narcotine, papaverine, and thebaine.
5. Bases precipitable by sodium carbonate, but not precipitable by sodium
bicarbonate ; strychnine, brucine, veratrine.
6. Quinine bases precipitable by sodium carbonate, also by sodium bicarbonate
if not in too dilute solution.
7. The rare quinine bases.
The individual members of the group are then identified by their behaviour to
potassic ferrocyanide, cobalt thiocyanide, platin chloride, and other reagents described
in this work under the particular alkaloid.
§ 314. Sublimation of the Alkaloids.-A very beautiful and elegant
aid to the identification of alkaloids, and vegetable principles generally,
is their behaviour towards heat.
Alkaloids, glucosides, the organic acids, etc., when carefully heated,
either—(1) sublime wholly without decomposition (like theine, cytisin,
and others); or (2) partially sublime with decomposition ; or (3) are
changed into new bodies (as, for example, gallic acid); or (4) melt and
then char; or (5) simply char and burn away.
Many of these phenomena are striking and characteristic, taking place
at different temperatures, subliming in characteristic forms, or leaving
characteristic residues.
One of the first to employ sublimation systematically, as a means of
recognition of the alkaloids, etc., was Helwig.” His method was to place
a small quantity (from # to Tºro of a mgrim.) in a depression on
platinum foil, cover it with a slip of glass, and then carefully heat by a
small flame. After Helwig, Dr. Guy f greatly improved the process by
using porcelain discs, and more especially by the adoption of a convenient
apparatus, which may be termed “the subliming cell.” It is essentially
composed of a ring of glass from # to 3 of an inch in thickness, such as
may be obtained by sections of tubing, the cut surfaces being ground
perfectly smooth. This circle was converted into a closed cell by resting
on it one of the ordinary thin discs of glass used as a covering for micro-
scopic purposes, and supporting a similar disc. The cell was placed on
a brass plate, provided with a nipple, which carried a thermometer, and
was heated by a small flame applied midway between the thermometer
and the cell; the heat was raised very gradually, and the temperature at
which any change took place was noted. In this way Dr. Guy made
determinations of the subliming points of a large number of substances,
and the microscopic appearances of the sublimates were described with
the greatest fidelity and accuracy. On repeating with care Dr. Guy's
* Das Mikroscop in der Toxicologie.
+ Pharm. Journ. Trans. (2), viij. 719 ; ix. 10, 58. Forensic Medicine, London,
1875.
§ 314.] SUBLIMATION OF THE ALKALOIDS. 259
determinations, however, the senior author could in no single instance
agree with his subliming points, nor with the apparatus he figures
and describes could two consecutive observations exactly coincide.
Further, on examining the various subliming temperatures of substances,
as stated by different authors, the widest discrepancies were found—
differences of 2 or even 3 degrees might be referred to errors of
observation, a want of exact coincidence in the thermometers employed,
and the like; but to what, for example, can we ascribe the irrecon-
cilable statements which have been made with regard to theine !
According to Strauch, this substance sublimes at 177° ; according to
Mulder, at 1847". But that both of these observations deviate more
than 70° from the truth may be proved by any one who cares to place a
few mgrms. of theine, enclosed between two watch-glasses, over the
water-bath; in a few minutes a distinct sublimate will condense on
the upper glass, and, in point of fact, theine will be found to sublime
several degrees below 100°.
Since this great divergency of opinion is not found either in the
specific gravity, or the boiling-points, or any of the like determinations
of the physical properties of a substance, it is self-evident that the
processes hitherto used for the determination of subliming points are
faulty. The sources of error are chiefly—
(1) Defects in the apparatus employed—the temperature read being
rather that of the metallic surface in the immediate vicinity of the
thermometer than of the substance itself.
(2) The want of agreement among observers as to what should be
called a sublimate—one considering a sublimate only that which is
evident to the naked eye, another taking cognisance of the earliest
microscopic film.
(3) No two persons employing the same process.
With regard to the apparatus employed, the senior author adopts
Dr. Guy's subliming cell; but the cell, instead of resting on a metallic
solid, floats on a metallic fluid. For any temperature a little above
100° this fluid is mercury, but for higher temperatures fusible metal is
preferable. -
The exact procedure is as follows:—A porcelain crucible (a in fig.),
about 3 inches in diameter, is nearly filled with mercury or fusible
metal, as the case may be ; a minute speck (or two or three crystals of
the substance to be examined) is placed on a thin disc of microscopic
covering glass, floated on the liquid, and the cell is completed by the
glass ring and upper disc. The porcelain crucible is supported on a
brass plate (b), fixed to a retort-stand in the usual way, and protected
from the unequal cooling effects of currents of air by being covered by a
flask (c), from which the bottom has been removed. The neck of the
26O POISONS : THEIR EFFECTS AND DETECTION, [š 314.
flask conveniently supports a thermometer, which passes through a cork,
and the bulb of the thermometer is immersed in the bath of liquid metal.
In the first examination of a substance the temperature is raised some-
what rapidly, taking off the upper disc with a forceps at every 10° and
exchanging it for a fresh disc, until the substance is destroyed. The
second examination is conducted much more slowly, and the discs
exchanged at every 4” or 5", whilst the final determination is effected by
raising the temperature with great caution, and exchanging the discs at
about the points of change (already partially determined) at every half
degree. All the discs are examined microscopically. The most con-
venient definition of a sublimate is this—the most minute films, dots, or
crystals, which can be observed by 3-inch
power, and which are obtained by keeping
the subliming cell at a definite temperature
for 60 seconds. The commencement of many
sublimates assumes the shape of dots of
extraordinary minuteness, quite invisible to
the unaided eye; and, on the other hand,
since the practical value of sublimation is
mainly as an aid to other methods for the
recognition of substances, if we go beyond
short intervals of time, the operation, other-
wise simple and speedy, becomes cumber-
some, and loses its general applicability.
There is also considerable discrepancy of
statement with regard to the melting-point
of alkaloidal bodies; in many instances a
viscous state intervenes before the final com-
plete resolution into fluid, and one observer
will consider the viscous state, the other complete fluidity, as the
melting-point.
In the melting-points given below, the same apparatus was used, but
the substance was simply placed on a thin disc of glass floating on the
metallic bath before described (the cell not being completed), and
examined from time to time microscopically, for by this means alone
can the first drops formed by the most minute and closely-adherent
crystals to the glass be discovered.
Cocaine melts at 93*, and gives a faint sublimate at 98°; if put
between two watch-glasses on the water-bath, in fifteen minutes there
is a good cloud on the upper glass.
Aconitine turns brown, and melts at 179° C. ; it gives no character-
istic sublimate up to 190°.
Morphine, at 150°, clouds the upper disc with nebulae; the nebulae

§ 314.] SUBLIMATION OF THE ALKALOIDS. 26 I
are resolved by high magnifying powers into minute dots; these dots
gradually become coarser, and are generally converted into crystals at
188”; the alkaloid browns at or about 200°.
Thebaine sublimes in theine-like crystals at 135°; at higher tempera-
tures (160° to 200°), needles, cubes, and prisms are observed. The
residue on the lower disc, if examined before carbonisation, is fawn-
coloured with non-characteristic spots.
Narcotine gives no sublimate; it melts at 155° into a yellow liquid,
which, on raising the temperature, ever becomes browner to final black-
ness. On examining the residue before carbonisation, it is a rich brown
amorphous substance ; but if narcotine be heated two or three degrees
above its melting-point, and then cooled slowly, the residue is crystalline
—long, fine needles radiating from centres being common.
Narceine gives no sublimate ; it melts at 134° into a colourless
liquid, which undergoes at higher temperatures the usual transition of
brown colours. The substance, heated a few degrees above its melting-
point, and then allowed to cool slowly, shows a straw-coloured residue,
divided into lobes or drops containing feathery crystals.
Papaverine gives no sublimate ; it melts at 130°. The residue, heated
a little above its melting-point, and then slowly cooled, is amorphous,
of a light brown colour, and in no way characteristic.
Hyoscyamine gives no crystalline sublimate ; it melts at 89°, and
appears to volatilise in great part without decomposition. It melts into
an almost colourless fluid, which, when solid, may exhibit a network
not unlike vegetable parenchyma ; on moistening the network with
water, interlacing crystals immediately appear. If, however, hyoscya-
mine be kept at 94° to 95° for a few minutes, and then slowly cooled,
the edges of the spots are arborescent, and the spots themselves
crystalline,
Atropine (daturine) melts at 97° ; at 123° a faint mist appears on
the upper disc. Crystals cannot be obtained ; the residue is not
characteristic.
Solanine,—The upper disc is dimmed with nebulae at 190°, which
are coarser and more distinct at higher temperatures; at 200” it begins
to brown, and then melts; the residue consists of amber-brown non-
characteristic drops.
Strychnine gives a minute sublimate of fine needles, often disposed
in lines, at 169"; about 2.21° it melts; the residue (at that temperature)
is resinous.
Brucine melts at 151° into a pale yellow liquid, at higher tempera-
tures becoming deep brown. If the lower disc, after melting, be
examined, no crystals are observed, the residue being quite transparent,
with branching lines like the twigs of a leafless tree; light mists, pro-
262 POISONS : THEIR EFFECTS AND DETECTION. [$ 3 I 5.
duced rather by decomposition than by true sublimation, condense on
the upper disc at 185° and above.
Saponin neither melts nor sublimes; it begins to brown about 145°,
is almost black at 185°, and quite so at 190°.
Delphinine begins to brown about 102° ; it becomes amber at 119°,
and melts, and bubbles appear. There is no crystalline sublimate;
residue not characteristic.
Pilocarpine gives a distinct crystalline sublimate at 153”; but thin
mists, consisting of fine dots, may be observed as low as 140°. Pilo-
carpine melts at 159° ; the sublimates at 160° to 170° are in light
yellow drops. If these drops are treated with water, and the water
evaporated, feathery crystals are obtained ; the residue is resinous.
Theine wholly sublimes; the first sublimate is minute dots, at 79° ;
at half a degree above that very small crystals may be obtained; and
at such a temperature as 120°, the crystals are often long and silky.
Theobromine likewise wholly sublimes; nebulae at 134°, crystals
at 170° and above.
Salicin melts at 170° ; it gives no crystalline sublimate. The melted
mass remains up to 180° almost perfectly colourless; above that tem-
perature browning is evident. The residue is not characteristic.
Picrotoxin gives no crystalline sublimate. The lowest temperature
at which it sublimes is 128°; the usual nebulae then make their appear-
ance; between 165° and 170° there is slight browning ; at 170° it melts.
The residue, slowly cooled, is not characteristic.
Cantharidin sublimes very scantily between 82° and 83°; at 85° the
sublimate is copious.
The active principles of plants may, in regard to their behaviour to
heat, be classed for practical purposes into—
1. Those which give a decided crystalline sublimate :
(a) Below 100", e.g. cocaine, theime, thebaine, cantharidin.
(b) Between 100° and 150°, e.g. quinetum.
(c) Between 150° and 200", e.g. strychnine, morphine,
pilocarpine.
2. Those which melt, but give no crystalline sublimate :
(a) Below 100°, e.g. hyoscyamine, atropime.
(b) Between 100° and 150', e.g. papaverine.
(c) Between 150° and 200", e.g. salicin.
(d) Above 200°, e.g. solanine.
3. Those which neither melt nor give a crystalline sublimate, e.g.
saponin.
§ 315. Melting-point.—The method of sublimation just given also
determines the melting-point ; such a determination will, however,
§ 316.] MELTING-POINT—IDENTIFICATION. 263
seldom compare with the melting-points of the various alkaloids as
given in text-books, because the latter melting-points are not determined
in the same way. The usual method of determining melting-points is
to place a very small quantity in a thin glass tube closed at one end; the
tube should be almost capillary. The tube is fastened to a thermometer
by means of platinum wire, and then the bulb of the thermometer,
with its attached tube, is immersed in strong sulphuric acid or paraffin,
contained in a flask. The thermometer should be suspended midway
in the liquid and heat carefully applied, so as to raise the temperature
gradually and equably. It will be found that rapidly raising the heat
gives a different melting-point to that which is obtained by slowly
raising the heat. During the process careful watching is necessary :
most substances change in hue before they actually melt. A constant
melting-point, however often a substance is purified by recrystallisation,
is a sign of purity.
§ 316. Identification by Organic Analysis.-In a few cases (and in
a few only) the analyst may have sufficient material at hand to make
an organic analysis, either as a means of identification or to confirm
other tests. By the vacuum process described in “Foods,” in which
carbon and nitrogen are determined by measuring the gases evolved
by burning the organic substance in as complete a vacuum as can be
obtained, very minute quantities of a substance can be dealt with, and
the carbon and nitrogen determined with fair accuracy. It is found
in practice that the carbon determinations appear more reliable than
those of the nitrogen, and there are obvious reasons why this should
be so.
Theoretically, with the improved gas-measuring appliances, it is
possible to measure a c.c. of gas; but few chemists would care to create
a formula on less than 10 c.c. of CO3. Now, since 10 c.c. of CO2 is equal
to 6:33 mgrms. of carbon, and alkaloids average at least half their
weight of carbon, it follows that 12 mgrms. of alkaloid represent about
the smallest quantity with which a reliable single combustion can
be made.
The following determinations may also be of service occasionally in
identifying the alkaloids.
Oxygen.—The majority of the alkaloids contain oxygen, but there
is no oxygen in coniine, methylconiine, y-comiceine, nicotine, nicotinine,
nicoteine, nicotelline, sparteine, lupinidine, curarine, comessine, aribine,
adenine, and hymenodictime.
Methoayl groups may be determined by Zeisel's method, which
consists in boiling from 0-2 to 0.3 gramme of the substance with
10 c.c. of hydriodic acid of sp. gr. 1.68, and passing the methyl iodide
formed into a solution of silver nitrate. From the weight of silver
264 POISONS : THEIR EFFECTS AND DETECTION. [Š 317.
iodide formed, the number of methoxyl groups may be calculated,
one molecule of silver iodide = one methoxyl group. There is one
methoxyl group in quinine and codeine, two in hydrastine and
brucine, three in narcotine, four in papaverine and aconitine, and six
in pseudaconitine.
Nitrogen.—By a modification of Zeisel's method the methyl groups
attached to nitrogen may be determined, methyl being the only
alcoholic radical which occurs attached to the nitrogen of alkaloids,
Herzig and Meyer have shown that when the hydriodic acid salt
of the base is subjected to dry distillation, the methyl groups are
eliminated as methyl iodide, and may be determined by means of
silver nitrate. Thus it has been found that chrysanthemine and
caffeine contain one methyl group; cusohygrine, narcelne, and theo-
bromine contain two; trigonelline, arecoline, methyl coniine, nicotine,
hygrine, pseudopelleturine, atropine, cocaine, morphine, codeine, nar-
cotine, and eserine contain one; and lupinine, lupanine, cinchonine,
and harmaline mone.
§ 317. Quantitative Estimation of the Alkaloids.-For medico-
legal purposes the alkaloid obtained is usually weighed directly, but
for technical purposes other processes are used. One of the most
convenient of these is titration with d.l. acid, using a suitable
indicator.
Rippenberger * has shown, in a special research, that the choice of
an indicator is not indifferent, some indicators giving to titration values
for the alkaloids entirely erroneous; he gives the following list of
suitable indicators; those in brackets may be used, but are not as
suitable as the others.
ATROPINE.—Iodeosin (methyl-orange), azolithmin, haematoxylin, lacmoid, cochi-
neal, uranine.
MORPHINE. –(Iodeosin), cochineal, lacmoid.
ACONITINE. —Iodeosin, azolithmin, haematoxylin, cochineal.
VERATRINE. – Iodeosin, haematoxylin, cochineal, lacmoid.
THEBAINE.--Iodeosin, uranine (haematoxylin), cochineal, lacmoid.
CODEINE,-Iodeosin (azolithmin), uranine, haematoxylin, cochineal, lacmoid.
CoCAINE.—Lacmoid, uranine, cochineal, haematoxylin,
STRYCHNINE. –Iodeosin, azolithmin (uranine), haematoxylin, cochineal, lacmoid.
BRUCINE.—Iodeosin, azolithmin (uranine), haematoxylin, cochineal (lacmoid).
NICOTINE. –(Iodeosin, uranine, cochineal), lacmoid. -
CONIINE,-Iodeosin (methyl-orange, azolithmin), haematoxylin, alkannin, cochi-
neal, lacmoid, Congo-red.
SPARTEINE. –Azolithmin (uranine), haematoxylin, phenolphthalein, alkannin.
PAPAVERINE. —Lacmoid.
A reagent of general application is found in the so-called Mayer's
reagent, which consists of 13:546 grms, of mercuric chloride, and 49.8
* Zeit. f. amal. Chemie, 1900, 301.
§ 3.17.] ESTIMATION OF THE ALKALOIDS. 265
grms. of iodide of potassium in a litre of water. Each c.c. of such
solution precipitates—
Of Strychnine, t & s º - . .0167 grm.
,, Brucine, . g t * e - . .0233 ,,
,, Quinine, . g º e e. - . '0108 , ,
,, Cinchonine, 4. e e - - . .0102 , ,
,, Quinidine, e e . . - . ‘0128 , ,
,, Atropine, . * - º e - . ‘0145 , ,
,, Aconitine, . º & e ſº - . .0268 , ,
,, Veratrine, . º o º º - . .0269 , ,
,, Morphine, . g º o e - . .0200 , ,
,, Narcotine, . e - º • - . .0206 , ,
,, Nicotine, . e - º s - . .00405 , ,
,, Coniine, . º - º & -> . .00416 ,,
The final reaction is found by filtering, from time to time, a drop on
to a glass plate, resting on a blackened surface, and adding the test
until no precipitate appears. The results are only accurate when the
strength of the solution of the alkaloid is about 1:200, and when the
solutions are pure; so that it is absolutely necessary first to ascertain
approximatively the amount present, and then to dilute or concentrate,
as the case may be, until the proportion mentioned is obtained.
Similarly, the iodine solution described on p. 253 may be used volu-
metrically by precipitating the alkaloid by the solution, filtering, and
then ascertaining by means of thiosulphate solution the amount of free
iodine in the filtrate; if the iodine solution is standardised by approxi-
mately equal weights of the particular alkaloid under investigation, the
process is capable of giving fair results, although more adapted for
technical use than for forensic cases, as the precipitates, both with
iodine and Meyer's reagent, have not always a definite composition,
being influenced by solubility, concentration, and the presence of other
bodies.
It is useful for quantitative purposes to combine an alkaloid with
gold or platinum, by treating the solution with the chlorides of either
of those metals—the rule as to selection being to give that metal the
preference which yields the most insoluble and the most crystallisable
compound. -
The following table gives the percentage of gold or platinum left on
ignition of the double salt:—
Rold. Platinum.
Atropine, . ſº e • * º 31.57
Aconitine, . e º º - e 20-0
Amanitine, . - º - - * 44 ° 23 tº e º
Berberime, . - º - - º 29' 16 18-11
Brucine, e - º o e * - - - 16 °52
Cinchonine, • tº © - * * * * 27-36
Cinchonidine, - • . º - - - - 27 '87
266 POISONS: THEIR EFFECTS AND DETECTION. [$318, 319.
- Gold. Platinum.
Codeine, * e g * * g tº tº º 19 11
Coniine, * & g g - º & © tº 29'38
Curarine, . & e - - g * * * 32°65
Delphinine, & * & g º 26-7 * † tº º
Delphinoidine, . * tº º º 29'0 15 °8
Emetime, tº . e. e e g e e tº e 29-7
Hyoscyamine, © * e tº g 34°6 ° tº tº &
Morphine, . * * , & - e tº º q 19 °52
Muscarine, . * & g & e 43'01 s & t
Narcotine, . * & tº & . 15-7 15°9
Narceine, . © * , g * * to ſº º 14°52
Nicotine, . t e e * * tº tº ſº 34°25
Papaverine, . . . . . . # tº gº 17.82
Pilocarpine, . tº ſº * ſº * 35°5 23°6 to 25°2
Piperine, ſº {} ig & º & tº ſº 12.7
Quinine, º * e g & tº 40 °0 26 °26
Strychnine, . e e e * & 29 "15 18°16
Thebaine, . & * & t tº º ſº 18-71
Theine, o & * tº g e 37:02 24 °58
Theobromine, e g º te tº º ſº 25 °55
Weratrine, . o & ſº g © 21 °01
II.-Liquid Wolatile Alkaloids.
THE ALKALOIDS OF HEMLOCK–NICOTINE–PITURIE--SPARTEINE.
1. THE ALKALOIDS OF HEMLOCK (CONIUM).
§ 318. The Conium maculatum, or spotted hemlock, is a rather
common umbelliferous plant, growing in waste places, and flowering
from about the beginning of June to August. The stem is from three
to five feet high, smooth, branched, and spotted with purple; the
leaflets of the partial involucres are unilateral, ovate, lanceolate, with
an attenuate point shorter than the umbels; the seeds are destitute of
vittae, and have five prominent crenate wavy ridges. The whole plant
is foetid and poisonous. Conium owes its active properties to the
liquid-alkaloids Coniine and y-Coniceine, with a crystalline alkaloid,
Conhydrine. Small quantities of Pseudoconhydrine and Methylconiine
also occur in the plant. The alkaloids are in the plant combined with
malic and caffeic acid. -
§ 319. Coniine (conia, conicine), (CºHº,N)—specific gravity 0-862
at 0°, 0.845 at 20° ; melting-point, — 2-5°; boiling-point, 166.6°. Pure
coniine has been prepared synthetically by Ladenburg, and found to
be a-propyl-piperidine, C.H16NCAH, but the synthetically-prepared
piperidine has no action on polarised light. By uniting it with dextro-
tartaric acid, and evaporating, it is possible to separate the substance
§ 319.] HEMLOCK. 267
into dextro-a-propyl-piperidine and lavo-a-propyl-piperidine. The former
is in every respect identical with coniine from hemlock; it is a clear,
oily fluid, possessing a peculiarly unpleasant, mousy odour. One part
is soluble in 150 parts of water,” in 6 parts of ether, and in almost all
proportions of amyl alcohol, chloroform, and benzene. It readily
volatilises, and, provided air is excluded, may be distilled unchanged.
It ignites easily, and burns with a smoky flame. It acts as a strong
base, precipitating the oxides of metals and alkaline earths from their
solutions, and it coagulates albumen. Coniine forms salts with hydro-
chloric acid (CsIIIs N.HCl), phosphoric acid, iodic acid, and oxalic acid,
which are in well-marked crystals. The sulphate, nitrate, acetate,
and tartrate are, on the other hand, non-crystalline.
If coniine is oxidised with nitric acid, or bichromate of potash, and
diluted sulphuric acid, butyric acid is formed ; and since the latter has
an unmistakable odour, and other characteristic properties, it has been
proposed as a test for coniine. This may be conveniently performed
thus:–A crystal of potassic bichromate is put at the bottom of a test
tube, and some diluted sulphuric acid with a drop of the supposed
coniine added. On heating, the butyric acid reveals itself by its odour,
and can be distilled into baryta water, the butyrate of baryta being
subsequently separated in the usual way, and decomposed by sulphuric
acid, etc.
Another test for coniine is the following:—If dropped into a solution
of alloxan, the latter is coloured after a few minutes an intense purple-
red, and white needle-shaped crystals are separated, which dissolve in
cold potash-lye into a beautiful purple-blue, and emit an odour of the
base.f. Dry hydrochloric acid gives a purple-red, then an indigo-blue
colour, with coniine ; but if the acid is not dry, there is formed a bluish-
green crystalline mass. This test, however, is of little value to the
toxicologist, the pure substance alone responding with any definite result.
The ordinary precipitating agents, according to Dragendorff, act as
follows:—
Potass, bismuth iodide.
1: 2000, a strong orange precipitate.
1 : 3000. The drop of the reagent is surrounded with a muddy border.
1:4000. The drop of thereagent is surrounded with a muddy border.
1 : 5000, still perceptible.
1:6000. The last limit of the reaction.
Phosphomolybdic acid gives a strong yellow precipitate ; limit,
1 : 5000. -
* The saturated watery solution of coniine at 15° becomes cloudy if gently
warmed, and clears again on cooling.
t Schwarzenbach, Vierteljahrsschr. f. prakt. Pharm., viij. 170.
268 POISONS : THEIR EFFECTS AND DETECTION. [$ 32O.
Potass, mercuric iodide gives a cheesy precipitate; limit, 1 : 1000 in
neutral, 1 :800 in acid, solutions.
Potass, cadmic iodide gives an amorphous precipitate, 1:300. The
precipitate is soluble in excess of the precipitant. (Nicotine, under
similar circumstances, gives a crystalline precipitate.)
Flückiger recommends the following reaction: *—“Add to 10 drops
of ether in a shallow glass crystallising dish 2 drops of coniine, and cover
with filter-paper. Set upon the paper a common-sized watch-glass
containing bromine water, and invert a beaker over the whole arrange-
ment. Needle-shaped crystals of coniine hydro-bromine soon form in
the dish as well as in the watch-glass.” Hydrochloric acid, used in the
same way, instead of bromine water, forms with coniine microscopic
needles of coniine hydrochlorate; both the hydro-bromide and the
hydrochlorate doubly refract light. Nicotine does not respond to
this reaction.
Coniine forms with carbon disulphide a thiosulphate and a sulphite.
If carbon disulphide, therefore, be shaken with an aqueous solution of
coniine, the watery solution gives a brown precipitate with copper sul-
phate, colours ferric chloride solution dark brown-red, and gives a milky
opalescence with dilute acids. If coniine itself is added to carbon
disulphide, there is evolution of heat, separation of sulphur, and forma-
tion of thiosulphate. Nicotine does not respond to this reaction.
§ 320. The Constitution of the Coniine Bases.—Coniine is the
dextromodification of a-propylpiperidine,
CH,
H2C /N C H2
H2C U CH-CH2 – CH2 – CH,
N
H
Comiime.
If the hydrochloride is distilled with zinc dust comyrine or a-propyl-pyri-
dine is formed,
U C4Hz
N
Conyrine.
The conicelines are a-propylpiperidines. Five isomers have been
prepared, of which a-comiceine and y-coniceine are more poisonous
than coniine.
* Reactions, by F. A. Flückiger, Detroit, 1893.
$ 32 I.] HEMLOCK. . 269
a-coniceine is a liquid which boils at 158°. y-coniceine occurs in
Conium maculatum and also in commercial coniine ; it is a liquid
boiling at 171°–172”, optically inactive, and reduced by tin and HCl or
sodium and alcohol to inactive coniine,
CH,
H2C CH
H2C J C – C3H7
N
H
ºy-coniceine.
Conhydrine is found in Conium maculatum. Crystallises from ether
in colourless leaflets. Melts at 118°. Distils at 225°–226°. Soluble in
alcohol and in ether. Polarises to the right. It is an hydroxylated
coniine, and may be provisionally represented thus—
H 92 OH
H.C (NCH,
H2C U -- CH • * C3Hz
N
H
Pseudocomhydrine is isomeric with conhydrine and has similar
properties. It is a crystalline deliquescent powder, soluble in water,
alcohol, and ether. Melts at 101°–102°, boils at 229°–231°. Polarises
to the right. Is probably a stereoisomer of conhydrine.
Methylconiine is a colourless liquid. Sp. gr. 0.8318 at 24°. Boils
at 173°–174°. Polarises to the left.
CH,
H2C ^ CH,
|
NZ
N
|
CHs
Methylconiime.
§ 321. Pharmaceutical Preparations.—The percentage of coniine in
the plant itself, and in pharmaceutical preparations, can be approxi-
mately determined by distilling the coniine over, in a partial vacuum,”
* This is easily effected by uniting a flask containing the alkaloidal fluid, air-
tight, with a Liebig's condenser and a receiver, the latter being connected with
Bunsen's water-pump, or one of the numerous exhausting apparatus now in use in
every laboratory. -
27O POISONS: THEIR EFFECTS AND DETECTION. [$ 322, 323.
and titrating the distillate with Meyer's reagent, each c.c. = -00416 grm.
of coniine. It appears to be necessary to add powdered potassic chloride
and a small quantity of diluted sulphuric acid before titrating, or the
precipitate does not separate. In any case, the end of the reaction is
difficult to observe.*
The fresh plant is said to contain from about :04 to '09 per cent.,
and the fruit about 0.7 per cent. of coniine.
The officinal preparations are—the leaves, the fruit, a tincture of
the fruit, an extract of the leaves, the juice of the leaves (Succus conii),
a compound hemlock pill (composed of extract of hemlock, ipecacuanha,
and treacle), an inhalation of coniine (Vapor conii), and a poultice
(Cataplasma conii) made with the leaves.
§ 322. Statistics of Coniine Poisoning.—F. A. Falck f has been
able to collect 17 cases of death recorded in medical literature, up to
the year 1880, from either coniine or hemlock. Two of these cases
were criminal (murders), 1 suicidal, 2 cases in which coniine had been
used medicinally (in one instance the extract had been applied to a
cancerous breast ; in the other, death was produced from the injection
of an infusion of hemlock leaves). The remaining 12 were cases in
which the root, leaves, or other portions of the plant had been
ignorantly or accidentally eaten.
§ 323. Effects on Animals.-It destroys all forms of animal life. The
senior author made Some years ago an investigation as to its action on
the common blow-fly. Droplets of coniine were applied to various parts
of blow-flies, which were then placed under glass shades. The symptoms
began within a minute by signs of external irritation: there were rapid
motions of the wings, and quick and aimless movements of the legs.
Torpor set in speedily, the buzz soon ceased, and the insects lay on
their sides, motionless, but for occasional twitching of the legs. The
wings, as a rule, became completely paralysed before the legs, and
death occurred at a rather variable time, from ten minutes to two
hours. If placed in a current of air in the sun, a fly completely
under the influence of coniine may recover. Coniine causes in frogs,
similar to curarine, peripheral paralysis of the motor nerves, combined
with a transitory stimulation, and afterwards a paralysis of the motor
centres; in frogs the paralysis is not preceded by convulsions. Dragendorff
experimented on the action of coniine when given to five cats,
the quantities used being '05 to 5 grn. The symptoms came on .
almost immediately, but with the smaller dose given to a large
cat, no effect was witnessed until twenty-five minutes afterwards;
* Dragendorff, Die chemische Werthbestimmung einiger starkwirkender Droguen,
St. Petersb., 1874.
+ Prakt. Toacicologie, p. 273.
§ 324-326.] HEMLOCK. 271
this was the longest interval. One of the earliest phenomena
was dilatation of the pupil, followed by weakness of the limbs passing
into paralysis, the hinder legs being affected prior to the fore. The
respiration became troubled, and the frequency of the breathing dim-
inished; the heart in each case acted irregularly, and the sensation
generally was blunted; death was preceded by convulsions. In the
cases in which the larger dose of '4 to 5 grim. was administered, death
took place within the hour, one animal dying in eight minutes, a second
in eighteen minutes, a third in twenty minutes, and a fourth in fifty-
eight minutes. With the smaller dose of -051 grnm. given to a large cat,
death did not take place until eight hours and forty-seven minutes after
administration.
§ 324. Effects on Man,—In a case recorded by Bennet,” and quoted
in most works on forensic medicine, the symptoms were those of general
muscular weakness deepening into paralysis. The patient had eaten
hemlock in mistake for parsley; in about twenty minutes he experienced
weakness in the lower extremities, and staggered in walking like a
drunken man; within two hours there was perfect paralysis of both
upper and lower extremities, and he died in three and a quarter hours.
In another case, related by Taylor, the symptoms were also mainly those
of paralysis, and in other instances stupor, coma, and slight convulsions
have been noted.
§ 325. Physiological Action.—It is generally agreed that coniine
paralyses, first the ends of the motor nerves, afterwards their trunks,
and lastly, the motor centre itself. At a later period the sensory nerves
participate. In the earlier stage the respiration is quickened, the pupils
contracted, and the blood-pressure increased ; but on the development of
paralysis the breathing becomes slowed, the capillaries relaxed, and the
blood-pressure sinks. Death takes place from cessation of the respir-
ation, and not primarily from the heart, the heart beating after the
breathing has stopped. Coniine is eliminated by the urine, and is also
in part separated by the lungs, while a portion is, perhaps, decomposed
in the body.
§ 326. Post-mortem. Appearances.—There is nothing characteristic
in the appearances after death.
Fatal Dose.—The fatal dose of coniine is not accurately known ;
it is about 150 mgrms. (2-3 grains). In the case of Louise Berger, 10
to 15 drops appear to have caused death in a few minutes. The auto-
experiments of Dworzak, Heinrich, and Dillaberger would indicate that
one drop may cause unpleasant symptoms. Albers, in the treatment of
a woman suffering from cancer of the breast, witnessed convulsions and
loss of consciousness from the third dose of 4 mgrms. ('06 grain); and
* Edin. Med, and Surg. Journ., July 1845, p. 169.
272 POISONs: THEIR EFFECTS AND DETECTION, [$ 327, 328.
Eulenberg, its full marcotic effects on a child after subcutaneous in-
jection of 1 mgrm. (.015 grain).
§ 327. Separation of Coniine from Organic Matters or Tissues.—
The substances are digested with water, acidulated with H2SO4, at a
temperature not exceeding 40°, and then filtered. If the filtrate should
be excessive, it must be concentrated; alcohol is then added, the liquid
refiltered, and from the filtrate the alcohol separated by distillation.
On cooling, the acid fluid is agitated with benzene, and the latter
separated in the usual way. The fluid is now alkalised with ammonia,
and shaken up once or twice with its own volume of petroleum ether ; ,
the latter is separated and washed with distilled water, and the alkaloid
is obtained almost pure. If the petroleum ether leaves no residue, it is
certain that the alkaloid was not present in the contents of the stomach
or intestine. f
The affinity of coniine with ether or chloroform is such, that its solu-
tion in either of these fluids, passed through a dry filter, scarcely
retains a drop of water. In this way it may be conveniently purified,
the impurities dissolved by water remaining behind. \-, -
In searching for coniine, the stomach, intestines, blood, urine, liver,
and lungs are the parts which should be examined. According to
Dragendorff, it has been discovered in the body of a cat six weeks after
death.
Great care must be exercised in identifying any volatile alkaloid as
coniine, for the sources of error seem to be numerous. In one case * a
volatile coniine-like ptomaine was separated from a corpse, and thought
to be coniine ; but Otto found that in its behaviour to platinic chloride,
it differed from coniine; it was very poisonous—:07 was fatal to a frog,
'44 to a pigeon, in a few minutes. In the seeds of Lupinus luteus there
is a series of coniine-like substances,t but they do not give the character-
istic crystals with hydrochloric acid.
2. TOBACCO-NICOTINE.
§ 328. The different forms of tobacco are furnished by three species
of the tobacco plant, viz., Nicotianum tabacum, N. rustica, and N.
persica.
Havana, French, Dutch, and the American tobaccos are in the main
derived from N. tabacum; Turkish, Syrian, and the Latakia tobaccos
are the produce of N. rustica. There seems at present to be little of
N. persica in commerce. The following alkaloids have been isolated
from the aqueous extract from tobacco —Nicotine, C10H14N2; Nicotin-
ine, Clo H, N, ; Nicoteine, Ciołłign, ; and Nicotelline, CiołIsM2,
* Otto, Anleitung z. Ausmittlung d. Gifte, 1875. .
+ Sievert, Zeitschrift für Naturwissenschaften, 1869.
$ 329.] -- NICOTINE. 273
The general composition of the whole plant may be gathered from
the following table:–
TABLE SHOWING THE COMPOSITION OF FRESH LEAVES OF TOBACCO
(POSSELT AND REINMANN).
Nicotine and other alkaloids, g g † g Q te 0-060
Concrete volatile oil, . g g º & g * * 0 °010
Bitter extractive, . * g s & ſº g * g 2.870
Gum with malate of lime, . e e g g e & I '740
Chlorophyll, & g s º º * & g * 0.267
Albumen and gluten, . {º} * * * * & e 1°308
Malic acid, . 0 °510
Lignine and a trace of starch, . tº tº g & * 4'969
Salts (sulphite, nitrate, and malate of potash, chloride of -
potassium, phosphate and malate of lime, and *} 0.734s
of ammonia), \ S.
Silica, . e g * tº * , & e g e § 0'088
Water, e e e * º * g º As . 88°280
100°836
§ 329. Quantitative Estimation of Nicotine in Tobacco.—Keller's
process (J.C.S., Abs., 1899, ii. 193) gives fair results, and is as follows:
–6 grms, of tobacco dried over quick-lime are powdered and treated
with 60 grms, of ether, 60 of petroleum ether, after the addition of 10
c.c. of 20 per cent. KOH solution ; after digesting 3–4 hours, 100 grims.
of the ethereal liquid are placed in a 200 c.c. flask, and a strong current
of air passed over to expel ammonia; 10 c.c. of water, 10 c.c. of alcohol,
and a drop of a 10 per cent, solution of iodeosin are added and the
whole shaken; this causes the nicotine and iodeosin to pass into the
aqueous liquid. D.n. HCl, acid is now added until the liquid is colour-
less; the slight excess of acid is titrated back with d.n. ammonia. One
c.c. of the acid equals 16.2 mgrms. of nicotine.
M. Popoirci “ has proposed a method based on Kissling's process of
extraction, but the estimation is a polarimetric one ; in this way the
difficulty of separating nicotine from ammonia is obviated. From 20
to 40 grims. of dry tobacco are treated with 10 c.c. of alcoholic soda
solution (6 per cent. NaOH in 100 c.c. of 57 per cent. alcohol) and
extracted with ether in a Soxhlet apparatus. The ether extract is
treated with 10 c.c. of a tolerably concentrated Solution of phospho-
molybdic acid in nitric acid and shaken ; the phosphomolybdate of
nicotine (with ammonia) is precipitated, the ether is separated, and the
precipitate treated with water to bring up the volume to 50 c.c.; lastly,
8 grms, of BaOH are added; the yellow solution after standing for
some hours is filtered and polarised.
* Ztschr. f. physiol. Chem., 1889, 445.
I 8
274 POISONS: THEIR EFFECTS AND DETECTION. [$ 329.
The following table is used —
Grms. of Nicotine in Totation in 2 drin. tube One minute of a degree
50 c.c. solution. (minutes). corresponds to grim. Nicotine.
2 : 00 337 0 °00594 - .
1.75 298 0 °00588
1'50 258 0 °00582
1:25 217 0.00576
1°00 175 0.00572
0-75 133 . 0 °00564
0 °50 89 0 °00562
0.25 45 0-00556 ºr
Mr. Cox * has determined the amount of nicotine in a number of
tobaccos as follows:—
Twenty-five grammes (or more or less, according to the amount of the
sample at disposal) of the dried and powdered tobacco were intimately
mixed with slaked lime, and distilled in a current of steam until the con-
densed steam was no longer alkaline; the distillate was slightly acidu-
lated with dilute H2SO4, and evaporated to a conveniently small bulk.
This was made alkaline with soda, and agitated repeatedly with successive
portions of ether. The separated batches of ethereal solution of nicotine
were then mixed and exposed to the air in a cool place. This exposure
to the air carries away ammonia, if any be present, as well as ether.
Water was added to the ethereal residue, and the amount of nicotine
present determined by decinormal H2SO4, using methyl-orange as an
indicator. One c.c. of decinormal H2SO, represents 0.0162 gramme of
nicotine (CoH14N2).
TABLE OF RESULTS, ARRANGED ACCORDING TO PER CENT.
OF NICOTINE.
Variety examined. Nicotine per cent.
1. Syrian leaves (a), . º g * § * g '612
2. American chewing, . º g g * e ſº ‘935
3. Syrian leaves (b), . # g * g g º 1 °093
4. Chinese leaves, ſo e * g s & & 1902
5. Turkish (coarse cut), & º * s g g 2-500
6. Golden Virginia (whole strips), & s e º 2'501
7. Gold Flake (Virginia), . e s e * & 2°501
8. “Navy-cut” (light coloured), s * & - 2°530
9. Light returns (Kentucky), * * 9. e s 2.733
10. “Navy-cut” (dark “all tobacco”), tº g º 3 *640
11. Best “Bird’s-eye,” . º e e tº e * 3 ‘931
12. Cut Cavendish (a), . e s ſº g * e 4'212
13. “Best Shag” (a), . & . . . g g g 4 '907
14. “Cut Cavendish ’” (b), . & º * g g 4°970
15. “Best Shag” (b), . & g tº * e ſº 5'000
16. French tobacco, e & . . . p . . . . 8-711
17. Algerian tobacco (a), * . . . * . º 8 °813
18. Algerian tobacco (b), & tº * & . . 8'900
f Pharm. Journ., Jan. 20, 1894.
$ 33O.] NICOTINE. 275
It is therefore obvious that the strength of tobacco in nicotine
varies between wide limits.
§ 330. Nicotine is methyl-pyridyl-pyrrolidine
CH2. CH,
|
. CH CH,
/N |
U.S.
N. CH,
- N
and has been recently synthetised by Pictet and Rotschy;” the suc-
cessive steps of the synthesis are as follows: £-amino-pyridine-mucate
is distilled and N./3. pyridyl-pyrrole obtained; the vapour of this is
passed through a red-hot tube, when it isomerises to a £-pyridyl-
pyrrole; on acting on this last product with methyl-iodide, methiodide
of nicotyrine is formed, the same as on carefully oxidising natural
nicotine ; nicotyrine can be obtained from the methiodide by distillation
with lime. By acting on nicotyrine with iodine and NaOH, an iodine
substitution compound is obtained, which is reduced by zinc and
hydrochloric acid to dihydro-nicotyrine; this substance is transformed
into the perbromide, and on reduction of this, inactive nicotine is
obtained. By fractional crystallisation of the tartrates the inactive
nicotine is divided into laevo- and dextro-rotatory nicotines, the former
being identical with the natural product.
B. p. at Bar. p. D 10°/4° D 20°/4” [a]”
Natural nicotine, l. | L) o
rotatory, . . 246"1 – 246 2 730.5 1 018 1'0097 – 166°39
l. Nicotine from the e
synthetised base, 246 – 246'5 734 - 5 1-0177 1-0092 — 160 '93
d. Nicotine from the - *
synthetised base, 245'5 – 246'5 729 1.0171 1-0094 + 163' 17
The dextro-artificial nicotine has apparently a slighter and some-
what different physiological action to ordinary nicotine. The odour of
nicotine, especially on warming, is strong and unpleasantly like tobacco,
and it has a sharp, caustic taste. It absorbs water when exposed to the
air, and dissolves in water in all proportions, partly separating from
such solution on the addition of a caustic alkali. The aqueous solution
acts in many respects like ammonia, saturating acids fully, and may
therefore be in certain cases estimated with accuracy by titration, 49
parts of H2SO, corresponding to 162 of nicotine. -
Alcohol and ether dissolve nicotine in every proportion; if such
solutions are distilled, nicotine goes over first. The salts which it forms
with hydrochloric, nitric, and phosphoric acids crystallise with difficulty;
tartario and oxalic acid form white crystalline salts, and the latter,
oxalate of nicotine, is soluble in alcohol, a property which distinguishes it
* Ber., 1904, 1225.
276 POISONS: THEIR EFFECTS AND DETECTION. [$ 330,
from the oxalate of ammonia. The best salts are the oxalate and the acid
tartrate of nicotine, from which to regenerate nicotine in a pure state.
Hydrochloride of nicotine is more easily volatilised than the pure
base. Nicotine is precipitated by alkalies, also by many oxyhydrates,
lead, copper, etc. It is also precipitated by tannin and gallic acids; an
alcoholic solution of tannin completely precipitates an alcoholic solution
of nicotine. By the action of light, it is soon coloured yellow and brown
and becomes thick, in which state it leaves, on evaporation, a brown
resinous substance, only partly soluble in petroleum ether.
A very excellent test for nicotine, as confirmatory of others, is the
beautiful, long, needle-like crystals obtained by adding to an ethereal
solution of nicotine a solution of iodine in ether. The crystals require a
few hours to form. The various iodides, partly intramolecular and partly
additive, and the conditions under which they form, have been studied
by Kippenberger.”
Chlorine gas colours nicotine blood-red or brown; the product is
soluble in alcohol, and separates on evaporation in crystals.
Cyanogen also colours nicotine brown ; the product out of alcohol is
not crystalline. Platin chloride throws down a reddish crystalline pre-
cipitate, soluble on warming. A drop of nicotine poured on dry chromic
acid blazes up, and gives out an odour of tobacco camphor; if the ignition
does not occur in the cold, it is produced by a gentle heat. A solution
of nicotine in chloroform on the addition of iodine forms fine red crystals
(Roussin's crystals), Clo H.N., HI, I, + æ CHCls: the best proportions
seem to be the reaction of 2 atoms iodine on 1 molecule of nicotine.
It is scarcely possible to confound nicotine with ammonia, by reason
of its odour; and, moreover, ammonia may always be excluded by
converting the base into the oxalate, and dissolving in absolute alcohol.
On the other hand, a confusion between coniine and nicotine is apt
to occur when small quantities only are dealt with. It may, however,
be guarded against by the following tests:–
(1) If coniine be converted into oxalate, the oxalate dissolved in
alcohol, and coniine regenerated by distillation (best in vacuo) with
caustic lye, and then hydrochloric acid added, a crystalline hydrochlorate
of coniine is formed, which doubly refracts light, and is in needle-shaped
or columnar crystals, or dendritic, moss-like forms. The columns after-
wards become torn, and little rows of cubical, octahedral, and tetrahedral
crystals (often cross or dagger-shaped) grow out of yellow amorphous
masses. Crystalline forms of this kind are rare, save in the case of
dilute solutions of chloride of ammonium (the presence of the latter is,
of course, rendered by the treatment impossible); and nicotine does
not give anything similar to this reaction. -
* Zeit, anal. Chemie, 1903, 232.
$ 33 I.] NICOTINE. 277
(2) Coniine coagulates albumen; nicotine does not.
(3) Nicotine yields a characteristic crystalline precipitate with an
aqueous solution of mercuric chloride ; the similar precipitate of coniine
is amorphous.
(4) An alcoholic solution of coniine mixed with carbon disulphide
is coloured yellow—nicotine is not ; on adding to the solution a few drops
of a dilute solution of copper sulphate (1:200) or ferric chloride, coniine
precipitates yellow or brown—nicotine does not precipitate. On dissolv-
ing nicotine, even in traces, in epi-chlor-hydrin and heating to boiling, a
deep red colour is produced ; coniine gives no colour. * -
§ 331. Effects on Animals.-Nicotine is rapidly fatal to all animal
life—from the lowest to the highest forms. Very minute quantities in
water kill infusoria. Fish of 30 grms. weight die in a few minutes
from a milligramme of nicotine ; the symptoms observed are rapid move-
ments, then shivering and speedy paralysis, with decreased motion of
the gills, and death. With frogs, if doses not too large are employed,
there is first great restlessness, then strong tetanic convulsions, and a
very peculiar position of the limbs; the respiration after fatal doses
Soon ceases, but the heart beats even after death. Birds also show
tetanic convulsions followed by paralysis and speedy death. The
symptoms witnessed in mammals poisoned by nicotine are not essentially
dissimilar. With large doses the effect is similar to that of prussic
acid—viz., a cry, one or two shuddering convulsions, and death. If the
dose is not too large, there is trembling of the limbs, excretion of faeces
and urine, a peculiar condition of stupor, a staggering gait, and then
the animal falls on its side. The respiration, at first quickened, is
afterwards slowed, and becomes deeper than natural; the pulse, also,
with moderate doses, is first slowed, then rises in frequency, and finally,
, again falls. Tetanic convulsions soon develop ; during the tetanus the
pupils have been noticed to be contracted, but afterwards dilated; the
tongue and mouth are livid, and the vessels of the ear dilated. Very
characteristic of nicotine poisoning as witnessed in the cat, the rabbit,
and the dog, is its peculiarly violent action, for after the administration
of from one to two drops, the whole course from the commencement of
symptoms to the death may take place in five minutes. F. Was has
drawn the smoke of tobacco from an immense pipe, and condensed the
products; he finds the well-washed tarry products without physiological
action, but the soluble liquid affected the health of rabbits, they lost
weight, the number of the blood corpuscles was decreased, and the
haemoglobin of the blood diminished.t
The larger animals, such as the horse, are affected similarly to the
* H. Meltzer, Zeit, unal. Chem., 1898, 345–358.
† Archiv. f. Baper. Pathol, w, Pharm., Bd. xxxiii.
278 POISONS : THEIR EFFECTS AND DETECTION. [$ 332.
smaller domestic animals. A veterinary surgeon, Mr. John Howard, of
Woolwich,” has recorded a case in which a horse suffered from the most
violent symptoms of nicotine-poisoning, after an application to his skin
of a strong decoction of tobacco. The symptoms were trembling,
particularly at the posterior part of the shoulders, as well as at the
flanks, and both fore and hind extremities; the superficial muscles were
generally relaxed and felt flabby, and the pupils were widely dilated.
There was also violent dyspnoea, the respirations being quick and short,
pulse 32 per minute, and extremely feeble, fluttering, and indistinct.
When made to walk, the animal appeared to have partly lost the use of
his hind limbs, the posterior quarter rolling from side to side in an
unsteady manner, the legs crossing each other, knuckling over, and
appearing to be seriously threatened with paralysis. The anus was very
prominent, the bowels extremely irritable, and tenesmus was present.
He passed much flatus, and at intervals of three or four minutes, small
quantities of faeces in balls, partly in the liquid state, and coated with
slimy mucus. There was a staring, giddy, intoxicated appearance
about the head and eyes, the visible mucous membrane being of a
dark red colour. A great tendency to collapse was evident, but by
treatment with cold douches and exposure to the open air, the horse
recovered.
In a case occurring in 1863, in which six horses ate oats which had
been kept in a granary with tobacco, the symptoms were mainly those
of narcosis, and the animals died..i
§ 332. Effects on Man.—Poisoning by the pure alkaloid nicotine is
so rare that, up to the present, a few cases only are on record. One of
these, viz., the poisoning of M. Fougnies by Count Bocarmé and his
wife, is ever memorable in the history of toxicology, being the first
instance in which a pure alkaloid had been criminally used. The
detection of the poison exercised the attention of the celebrated chemist
Stas, For the unabridged narrative of this interesting case the reader
may consult Tardieu's Étude Médico-Légale sur l'Empoisonnement.
Bocarmé actually studied chemistry in order to prepare the alkaloid
himself, and, after having succeeded in enticing his victim to the chateau
of Bitremont, administered the poison forcibly. It acted immediately,
and death took place in five minutes. Bocarmé now attempted to hide
all traces of the nicotine by pouring strong acetic acid into the mouth
and over the body of the deceased. The wickedness and cruelty of the
crime were only equalled by the clumsy and unskilful manner of its
perpetration. The quantity of nicotine actually used in this case must
have been enormous, for Stas separated no less than 4 grim, from the
stomach of the victim. tº -
* Veter, Jowrmal, vol. iii. + Annales Vétérinaires, Bruxelles, 1868.
§ 333.] NICOTINE. - 279
Another known case of nicotine-poisoning was that of a man who
took it for the purpose of suicide. The case is related by Taylor. It
occurred in June 1863. The gentleman drank an unknown quantity
from a bottle ; he stared wildly, fell to the floor, heaving a deep sigh,
and died quietly without convulsion. A third case happened at
Cherbourg,” where an officer committed suicide by taking nicotine,
but how much had been swallowed, and what were the symptoms, are
equally unknown, for no one saw him during life after he had taken
the poison.
Poisoning by nicotine, pure and simple, then is rare. Tobacco.
poisoning is very common, and has probably been experienced in a
mild degree by every smoker in first acquiring the habit. Nearly all
the fatal cases are to be ascribed to accident ; but criminal cases are
not unknown. Christison relates an instance in which tobacco in
the form of snuff was put into whisky for the purpose of robbery.
In 1854 a man was accused of attempting to poison his wife by
putting snuff into her ale, but acquitted. In another case, the father
of a child, 10 weeks old, killed the infant by putting tobacco into its
mout *He defended himself by saying that it was applied to make
the child sleep.
In October 1855, a drunken sailor swallowed (perhaps for the
purposé of suicide) his quid of tobacco, containing from about half an
ounce to an ounce. He had it some time in his mouth, and in half an
- . . . suffered from frightful tetanic convulsions. There was also
boea; the pupils were dilated widely; the heart's action became
ir $gular; and towards the end the pupils again contracted. He died
cases of two girls, 18 years of age, who suffered from severe symptoms
“sº-
Öbacco-poisoning after drinking some coffee. They recovered; and
was found that tobacco had been mixed with the coffee-berries, and
hground up together.
§ºaccidents have occurred from children playing with old pipes. In
*18 7s a child, aged 3, used for an hour an old tobacco-pipe, and blew
º jap bubbles with it. Symptoms of poisoning soon showed themselves,
and the child died in three days. -
º Tobacco-juice, as expressed or distilled by the heat developed in the
tisual method of smoking, is very poisonous. Sommenschein relates the
ase of a drumken student, who was given a dram to drink, into which
his fellows had poured the juice from their pipes. The result was fatal.
# -
| * Ann. d’Hygiène, x. p. 404, 1861. † Edin. Med. Journ., 1855.
ji + Barkhausen, P. Ver. Z'g., xvii. p. 83, 1838.
§ Pharm. Jowrm., 1877, p. 377.












28O POISONS : THEIR EFFECTS AND DETECTION. [$ 333.
Death from smoking is not unknown.” Helwig saw death follow in the
case of two brothers, who smoked seventeen and eighteen German
pipefuls of tobacco. Marshall Halli records the case of a young
man, 19 years of age, who, after learning to smoke for two days,
attempted two consecutive pipes. He suffered from very serious
symptoms, and did not completely recover for several days. Gordon has
also recorded severe poisoning from the consecutive smoking of nine
cigars. The extermal application of the leaf may, as already shown in
the case of the horse, produce all the effects of the internal adminis-
tration of nicotine. The old instance, related by Hildebrand, of the
illness of a whole squadron of hussars who attempted to smuggle
* The question as to whether there is much nicotine in tobacco-smoke cannot be
considered settled ; but it is probable that most of the poisomous symptoms produced
are referable to the pyridene bases of the general formula (CnH2n-gn), and some
at least of its germicidal value is due to the presence of formic aldehyde. Wohl and
Eulenberg (Arch. Pharmac., 2, Cxlvi. p. 130) made some very careful experiments
on the smoke of strong tobacco, burnt both in pipes and also in cigars. The method
adopted was to draw the Smoke first through potash, and then through dilute
sulphuric acid. The potash absorbed prussic acid, hydric sulphide, fo 1 *
propionic, butyric, valeric, and carbolic acids; while in the acid the
fixed, and these were found to consist of the whole series of pyridene E
pyridene (C5H5N), boil.-point 117°, picoline (C6H.N.), boil.-point 133;
(C.H.,N), boil-point 154°, upwards. When smoked in pipes, the chief
pyrideme ; when in cigars, collidine (CsIIIN); and in general, pipe-sm
found to produce a greater number of volatile bases. The action of these b
been investigated by several observers. They all have a special action on
ism, and all show an increase in physiological activity as the series is ascende he
lowest produce merely excitement from irritation of the encephalic nervous centres,
and the highest, paralysis of those centres. Death proceeds from gradual fail
the respiratory movements, leading to asphyxia—(Kendrick and Dewar, Proc
seems to be a hydrate of picoline—(Compt. Remd., t. cxv. pp. 992, 993)
derivatives of the pyridene series are also active. The methiodides strongly:
the brain and paralyse the extremities. A similar but more energetic ad º
exerted by the ethyl and allyl derivatives ; the iod-allyl derivatives are:
poisons. Methylic pyridene carboxylate is almost inactive, but the corresp
ammonium salt gives rise to symptoms resembling epilepsy—(Ramsay, Phº.”
[5] iv. p. 241, 1877). One member of the pyridene series 3 lutidine has bee
investigated by C. Greville Williams and W. H. Waters—(Proc. Roy. Soc
xxxii. p. 162, 1881). They conclude that it affects the heart profoundly, ca.
an increase in its tonicity, but the action is almost confined to the ventricles. The
auricles are but little affected, and continue to beat after the ventricles h
stopped. The rate of the heart's beat is slowed, and the inhibitory power of thes.
vagus arrested. By its action on the nervous cells of the spinal cord, it in the ‘.
first place lengthens the time of reflex action, and then arrests that function.
Finally, they point out that it is antagonistic to strychnine, and may be successfully
employed to arrest the action of strychnine on the spinal cord. - -
+ Edºm. Med, and Surg. Jowr., xii., 1816.
















§ 334.] NICOTINE. 281
tobacco by concealing the leaf next to their skin, is well known, and is
supported by several similar cases. The common practice of the
peasantry, in many parts of England, of applying tobacco to stop
the bleeding of wounds, and also as a sort of poultice to local swellings,
has certainly its dangers. The symptoms—whether nicotine has been
taken by absorption through the broken or unbroken skin, by the
bowel, by absorption through smoking, or by the expressed juice, or
the consumption of the leaf itself—show no very great difference, save
in the question of time. Pure nicotine acts with as great a rapidity
as prussic acid ; while if, so to speak, it is entangled in tobacco, it takes
more time to be separated and absorbed; besides which, nicotine, taken
in the concentrated condition, is a strong enough base to have slight
caustic effects, and thus leaves some local evidences of its presence. In
order to investigate the effects of pure nicotine, Dworzak and Heinrich
made auto-experiments, beginning with 1 mgrm. This small dose pro-
duced unpleasant sensations in the mouth and throat, salivation, and a
peculiar feeling spreading from the region of the stomach to the fingers
and toes. With 2 mgrms, there was headache, giddiness, numbness,
disturbances of vision, torpor, dulness of hearing, and quickened respira-
tions. With 3 to 4 mgrms., in about forty minutes there was a great
feeling of faintness, intense depression, weakness, with pallid face and
cold extremities, sickness, and purging. One experimenter had shivering
of the extremities and cramps of the muscles of the back, with difficult
breathing. The second suffered from muscular weakness, fainting, fits of
shivering, and creeping sensations about the arms. In two or three
hours the severer effects passed away, but recovery was not complete
for two or three days. It is therefore evident, from these experiments
and from other cases, that excessive muscular prostration, difficult
breathing, tetanic cramps, diarrhoea, and vomiting, with irregular pulse,
represent both tobacco and nicotine poisoning. The rapidly-fatal result
of pure nicotine has been already mentioned; but with tobacco-
poisoning the case may terminate lethally in eighteen minutes. This
rapid termination is unusual; with children it is commonly about an
hour and a half although in the case previously mentioned, death did
not take place for two days. -
§ 334. Physiological Action.—Nicotine is absorbed into the blood
and excreted unchanged, in part by the kidneys and in part by the -
saliva (Dragendorff). According to the researches of Rosenthal and
Krocker,” nicotine acts energetically on the brain, at first exciting it,
and then lessening its activity; the spinal marrow is similarly affected.
The convulsions appear to have a cerebral origin; paralysis of the peri-
pheral nerves follows later than that of the nerve centres, whilst
* Ueber die Wirkwng des Nicotimes auf den thierischen Organismus, Berlin, 1868.
\
282 POISONS: THEIR EFFECTS AND DETECTION. [š 335–337.
muscular irritability is unaffected. The convulsions are not influenced
by artificial respiration, and are therefore to be considered as due to
the direct influence of the alkaloid on the nervous system. Nicotine
has a striking influence on the respiration, first quickening, then slowing,
and lastly arresting the respiratory movements: section of the vagus is
without influence on this action. The cause of death is evidently due
to the rapid benumbing and paralysis of the respiratory centre. Death
never follows from heart-paralysis, although nicotine powerfully influ-
ences the heart's action, small doses exciting the terminations of the
vagus in the heart, and causing a slowing of the beats. Large doses
paralyse both the controlling and exciting nerve-centres of the heart;
the heart then beats fast, irregularly, and weakly. The blood-vessels
are first narrowed, then dilated, and, as a consequence, the blood-
pressure first rises, then falls. Nicotine has a special action on the
intestimes. As O. Nasse * has shown, there is a strong contraction of
the whole tract, especially of the small intestine, the lumen of which
may be, through a continuous tetanus, rendered very small. This is
ascribed to the peripheral excitation of the intestinal nerves and the
ganglia. The uterus is also excited to strong contraction by nicotine;
the secretions of the bile and saliva are increased.
§ 335. Fatal Dose.—The fatal dose for dogs is from 3 to 2 drops;
for rabbits, a quarter of a drop ; for an adult not accustomed to tobacco
the lethal dose is probably 6 mgrms.
$ 336. Post-mortem Appearances.—There seem to be no appearances
so distinctive as to be justly ascribed to nicotine or tobacco poisoning
and no other.
A more or less fluid condition of the blood, and, generally, the signs
of death by the lungs, are those most frequently found. In tobacco-
poisoning, when the leaves themselves have been swallowed, there may
be some inflammatory redness of the stomach and intestine.
§ 337. Separation of Nicotine from Organic Matters, etc.—The
process for the isolation of nicotine is precisely that used for coniine
(see p. 272). It appears that it is unaltered by putrefaction, and may
be separated and recognised by appropriate means a long time after
death. Orfila detected it in an animal two or three months after death;
Melsens discovered the alkaloid unmistakably in the tongues of two
dogs, which had been buried in a vessel filled with earth for seven
years; and it has been found, by several experiments, in animals buried
for shorter periods. Nicotine should always be looked for in the
tongue and mucous membrane of the mouth, as well as in the usual
viscera. The case may be much complicated if the person supposed
to be poisoned should have been a smoker ; for the defence would
* Beiträge zur Physiologie der Darmbewegung, Leipsic, 1866.
Af
$ 337A, 338.] PITURIE. 283
naturally be that there had been either excessive smoking or chewing,
or even swallowing accidentally a quid of tobacco.” A ptomaine has
been" discovered similar to nicotine. Wolckenhaar separated also an
alkaloid not unlike nicotine from the corpse of a woman addicted to
intemperate habits; but this base was not poisonous, nor did it give
any crystals when an ethereal solution was added to an ether solution
of iodine. It will be well always to support the chemical evidence by
tests on animal life, since the intensely poisonous action of nicotine
seems not to be shared by the nicotine-like ptomaines.
§ 337A. Antidote to Nicotine.—C. Zalackas,t in experiments on
animals with eserine and strychnine, finds that neither of these alkaloids
are antagonistic to any extent to nicotine ; he, however, obtained good
results from the expressed juice of Nasturtium officinale, two injections
of which completely counteracted the effect of a fatal dose of nicotine
(25 mgrms.) in a rabbit.
3. PITURIE. :
§ 338. Piturie (C6Hs N) is a liquid, nicotine-like alkaloid, obtained from the
Duboisia hopwoodvi, a small shrub or tree belonging to the natural order Solanaceae,
indigenous in Australia. The natives mix piturie leaves with ashes from some other
plant, and chew them. Piturie is obtained by extracting the plant with boiling
water acidified with sulphuric acid, concentrating the liquid by evaporation, and
then alkalising and distilling with caustic soda, and receiving the distillate in
hydrochloric acid. The solution of the hydrochlorate is afterwards alkalised and
shaken up with ether, which readily dissolves out the piturie. The ether solution of
piturie is evaporated to dryness in a current of hydrogen, and the crude piturie
purified by distillation in hydrogen, or by changing it into its salts, and again
recovering, etc. It is clear and colourless when pure and fresh, but becomes yellow
or brown when exposed to air and light. It boils and distils at 243° to 244°. It is
soluble in all proportions in alcohol, water, and ether ; its taste is acrid and
pungent; it is volatile at ordinary temperatures, causing white fumes with hydro-
chloric acid; it is very irritating to the mucous membranes, having a smell like
nicotine at first, and then, when it becomes browner, like pyridine. It forms salts
with acids, but the acetate, sulphate, and hydrochlorate are varnish-like films having
no trace of crystallisation ; the oxalate is a crystalline salt. Piturie gives precipi-
tates with mercuric chloride, cupric sulphate, gold chloride, mercur-potassic iodide,
tannin, and am alcoholic solution of iodine. If an ethereal solution of iodine is added
to an ethereal solution of piturie, a precipitate of yellowish-red needles, readily
soluble in alcohol, is deposited. The iodine compound melts at 110°, while the iodine
compound of nicotine melts at 100°. Piturie is distinguished from coniine by its
aqueous solution not becoming turbid either on heating or on the addition of chlorine
water; it differs from picoline in specific gravity, picoline being 96.13 specific gravity
at 0°, and piturie sinking in water ; it differs from aniline by not being coloured by
chlorinated lime. From nicotine it has several distinguishing marks, one of the best
* In an experiment of Dragendorff’s, nicotine is said to have been detected in
35 grims, of the saliva of a person who had half an hour previously smoked a cigar.
+ Compt. Rend., 1905.
# See “The Alkaloid from Piturie,” by Prof. Leversidge, Chem, News, March 18
and 25, 1881.
284 POIsoNs: THEIR EFFECTS AND DETECTION. [$ 339–34 I.
being that it does not change colour on warming with hydrochloric acid and the
addition to the mixture afterwards of a little nitric acid. The physiological action
seems to be but little different from that of nicotine. It is, of course, poisonous, but
as yet has no forensic importance.
4, SPARTEINE,
§ 339. In 1851 Stenhouse * separated a poisonous volatile alkaloid from Spartium.
scoparium, the common broom, to which he gave the name of sparteine. At the
same time a crystalline non-poisonous substance, Scoparin, was discovered.
Sparteine is separated from the plant by extraction with sulphuric acid holding
water, and then alkalising the acid solution and distilling : it has the formula
(C15H23N2), and belongs to the class of tertiary diamines. It is a clear, thick, oily
substance, scarcely soluble in water, to which it imparts a strong, alkaline reaction ;
it is soluble in alcohol, in ether, and chloroform ; insoluble in benzene and in petro-
leum ; it boils at 288°. Sparteine neutralises acids fully, but the oxalate is the only
one which can be readily obtained in crystals. It forms crystalline salts with platinic
chloride, with gold chloride, with mercuric chloride, and with zinc chloride. The
picrate is an especially beautiful salt, crystallising in long needles, which, when dried
and heated, explode. On sealing sparteine up in a tube with ethyl iodide and
alcohol, and heating to 100° for an hour, ethyl sparteine iodide separates in long,
necdle-like crystals, which are somewhat insoluble in cold alcohol.
Effect on Animals.-A single drop kills a rabbit ; the symptoms are similar to
those produced by nicotine, but the pupils are dilated. †
5. ANILINE.
§ 340. Properties.—Aniline or amido-benzol (C6H3NH2) is made by the reduction
of nitro-benzol. It is an oily fluid, colourless when quite pure, but gradually
assuming a yellow tinge on exposure to the air. It has a peculiar and distinctive
smell. It boils at 182°5°, and can be congealed by a cold of 8°. It is slightly soluble
in water, 100 parts of water at 16° retaining about 3 of aniline, and easily soluble in
alcohol, ether, and chloroform. It does not blue red litmus-paper, but nevertheless
acts as a weak alkali, for it precipitates iron from its salts. It forms a large number
of crystalline salts. The hydrochloride crystallises in white plates, and has a melting-
point of 192°. The platinum compound has the formula of (C6H3NH2.HCl), PtCl4, and
crystallises in yellow needles. *
§ 341. Symptoms and Effects.--Aniline, like picric acid, coagulates albumin.
Aniline is a blood poison ; it produces, even during life, in some obscure way,
methaemoglobin, and it disintegrates the red blood corpuscles; both these effects
lessen the power of the blood corpuscles to convey oxygen to the tissues, hence the
cyanosis observed so frequently in aniline poisoning is explained. Engelhardti has
found that aniline black is produced ; in every drop of blood there are fine black
granules, the total effect of which produces a pale blue or grey-blue colour of the skin.
Aniline has also an action on the central nervous system, at first stimulating, and
then paralysing. Schmiedeberg finds that para-amido-phenol-ether-sulphuric acid is
produced, and appears in the urine as an alkali salt ; a small quantity of fuchsine is
also produced, and has been found in the urine. Some aniline may be excreted
unchanged.
* Phil. Trams., 1851.
+ To the nicotine group, gelsemine (C2H9s W.O.) and oxalathylin (C8H16N2) also
belong, in a physiological sense, but gelsemine, like sparteine, dilates the pupil.
* Beiträge zur Tow. des Anilins. Imaug.-Diss., Dorpat, 1888.
§ 342–344.] OPIUM. 285
The symptoms are giddiness, weakness, cyanosis, blueness of the skin, sinking of
the temperature, and dilatation of the pupil. The pulse is small and frequent, the
skin moist and cold. The patient smells of aniline. Towards the end coma and con-
vulsions set in. The urine may be brown to brown-black, and may contain hyaline
cylinders. The blood shows the spectrum of methaemoglobin, and has the peculiarities
already mentioned. Should the patient recover, jaundice often follows. The out-
Ward application of aniline produces eczema.
Chronic poisoning by aniline is occasionally seen among workers in the manufac-
ture of aniline. Headache, loss of muscular power, diminished sensibility of the
skin, vomiting, loss of appetite, pallor, eruptions on the skin, and general malaise
are the chief symptoms. The perspiration has been noticed to have a reddish colour.
Cases of aniline poisoning are not common ; Dr. Fred. J. Smith has recorded one
in the Lancet of January 13, 1894.” The patient, a woman, 42 years of age, of
alcoholic tendencies, swallowed, 13th December 1893, at 1.40 P.M., about 3 ounces of
marking-ink, the greatest part of which consisted of aniline ; in a very little while
she became unconscious, and remained so until death. At 3 P.M. her lips were of a
dark purple, the general surface of the skin was deadly white, with a slight bluish
tinge ; the pupils were small and sluggish, the breathing stertorous, and the pulse
full and slow—60 per minute. The stomach was washed out, ether injected, and
Oxygen administered, but the patient died comatose almost exactly twelve hours after
the poison had been taken.
The post-mortem examination showed slight congestion of the lungs; the heart
was relaxed in all its chambers, and empty of blood—it had a peculiar green-blue
appearance. All the organs were healthy. The blood was not spectroscopically
examined. -
§ 342. Fatal Dose.—This is not known, but an adult would probably be killed
by a single dose of anything over 6 grims. Recovery under treatment has been known
after 10 grms. ; the fatal dose for rabbits is 1–1.5 grim., for dogs 3–5 grims.
§ 343. Detection of Aniline.—Aniline is easily separated and detected. Organic
fluids are alkalised by a solution of potash, and distilled. The organs, finely divided,
are extracted with water acidulated with sulphuric acid, the fluid filtered, and then
alkalised and distilled. The distillate is shaken up with ether, the ether separated
and allowed to evaporate spontaneously. Any aniline will be in the residue left after
evaporation of the ether, and may be identified by the following tests:–An aqueous
solution of aniline or its salts is coloured blue by a little chloride of lime or hypo-
chlorite of soda ; later on the mixture becomes red. The blue colour has an absorp-
tion band, when examined spectroscopically, extending from W.L. 656 to 560, and
therefore in the red and yellow from Fraunhofer's line C, and overlapping D.
Another test for aniline is the addition of kairine, hydrochloric acid, and sodium
nitrite, which strikes a blue colour. -
III.--The Opium Group of Alkaloids.
§ 344. General Composition.—Opium contains a larger number of
basic substances than any plant juice known. The list reaches at present
to some 21 nitrogenised bases, and almost each year there have been
additions. Opium is a gummy mass, consisting of the juice of the
imcised unripe fruit of the Papaver somniferum hardened in the air.
* See also a case reported by K. Dehio, in which a person drank 10 grims. and
recovered. Ber, klinis. Wochen., 1888, Nr. 1.
286 POISONS : THEIR EFFECTS AND DETECTION. [$ 344.
The following is a nearly complete list of the constituents which have
been found in opium :—
Alkaloids.-I. The Morphine Group. Very poisonous (except Pseudomorphine).
Morphine, Cly Big NO3. Pseudomorphine (C17HisNO3)2.
Codeine, CisB21NO3. Thebaine, CigH21NO3.
II. The Papaverine Group.
Papaverine, C20H21NO4. Cryptopine, Cal H23NO3.
Codamine, C20H2:NO4. Papaveramine, C2, Hsu NOg.
Laudanine, C20H25NO4. Narcotine, C22H23NOz.
Laudanidine, C20H25NO4. Gnoscopine, C22H23NO+.
Laudanosine, Coifſ;NOA. Oxynarcotine, C22H23NOs.
Tritopine (C21B2, NO3)2O. Narceine, C23H2, NOs.
Meconidine, C21H23NO!. Hydrocotarmine, C12H15 NO3.
Lanthopine, C23H25NO4. Xanthaline, Car PI36N2O9.
Protopine, C20H19NO5.
Other Constituents.
Lactic Acid. | Opianine.
Acetic Acid. | Fat.
Meconidine, C2, H23NO4. | Resin.
Mecomine, C10H16O4. | Caoutchouc.
Meconic acid, C, H2O7. Gummy matters—Vegetable mucus.
Thebolactic acid. Ash, containing the usual constituents.
The various opiums differ, the one from the other, in the percentages
of alkaloids, so that only a very general statement of the mean composi-
tion of opium can be made. The following statement may, however, be
accepted as fairly representative of these differences:—
Per cent,
Morphine, . e º º º - * º * . tº 6 to 23
Narcotine, - º - g - - - - º 4 to 8
Other alkaloids, º º tº - & o º º 5 to 2
Meconin, . e e - tº º wº º º e under 1
Meconic acid, e - e - e * º º 3 to 8
Peculiar resin and caoutchouc, . - e º - - 5 to 10
Fat, . s tº ſº o g & * º g t 1 to 4
Gum and soluble humoid acid matters, e & º . 40 to 50
Insoluble matters and mucus, . - e e e . 18 to 20
Ash, . º º s - e - º - º e 4 to 8
Water, º & * - g º º - º e 8 to 30
The general results of the analysis of 12 samples of Turkey opium,
purchased by Mr. Bott,” from leading druggists in London, Dublin, and
Edinburgh, are as follows:– -
Water.—Highest, 31-2; lowest, 1814; mean, 22.4 per cent.
Insoluble Residue.—Highest, 47.9; lowest, 25.45; mean, 32.48 per
Cent.
Aqueous Extract.—Highest, 56-15; lowest, 20.90; mean, 45.90 per
cent.
* Year Book of Pharmacy, 1876.
§ 345, 346.] OPIUM. 287
Crude Morphine (containing about fºr of pure morphine).-Highest,
12:30; lowest, 6-76; mean, 9.92 per cent., which equals 12.3 per cent.
of the dried drug.
Persian Opium, examined in the same way, varied in crude morphine
from 2:1 to 8.5 per cent. ; Malwa, from 5'88 to 7:30. In 18 samples of .
different kinds of opium, the mean percentage of crude morphine was
8.88 per cent. (11 per cent. of the dried opium). According to Guibourt,
Smyrna opium, dried at 100°, yields 11-7 to 21:46 per cent., the mean
being 12 to 14 per cent. ; Egyptian, from 5-8 to 12 per cent. ; Persian,
11:37 per cent. In East Indian Patna opium, for medical use, he found
7-72; in a sample used for smoking, 5.27 per cent. ; in Algerian opium,
12.1 per cent. ; in French opium, 14-8 to 22.9 per cent.
§ 345. Action of Solvents on Opium.—The action of various solvents
on opium has been more especially studied by several scientists who are
engaged in the extraction of the alkaloids.
Water dissolves nearly everything except resin, caoutchouc, and
woody fibre. Free morphine would be left insoluble; but it seems
always to be combined with meconic and acetic acids. The solubility
of free marcotine in water is extremely small.
Alcohol dissolves resin and caoutchouc, and all the alkaloids and
their combinations, with meconic acid, etc.
Amylic Alcohol dissolves all the alkaloids, if they are in a free state,
and it also takes up a little of the resin.
Ether, Benzene, and Carbon Sulphide do not dissolve the resin, and
only slightly morphine, if free; but they dissolve the other free alkaloids
as well as caoutchouc. -
Acids dissolve all the alkaloids and the resin.
Fixed Alkalies, in excess, dissolve in part resin; they also dissolve
morphine freely; narcotine remains insoluble. -
Lime Water dissolves morphine, but is a solvent for narcotine only
in presence of morphine. -
Ammonia dissolves only traces of morphine; but narceine and
codeine readily. It does not dissolve the other alkaloids, nor does it
dissolve the resin. -
§ 346. ASSay of Opium.—The following processes may be described :-
Process of Teschemacher and Smith.--This process, with a few
modifications, is as follows:–10 grims. of opium are as completely as
possible exhausted with proof spirit at a boiling temperature. The result-
ing alcoholic extract is treated with a few drops of ammonium oxalate
solution, and the solution is almost neutralised with ammonia. The
solution is concentrated to one-third, cooled, and filtered. The filtrate
is further concentrated to 5 c.c., and transferred to a small flask, or to
the extraction tube figured on p. 163; it is washed into this by 4 c.c.
288 POISONS : THEIR EFFECTS AND DETECTION. [$ 346.
of water and 3 c.c. of 90 per cent. alcohol; next 2 c.c. solution of
âmmonia (sp. gr. 0-960) and 25 c.c. of dry ether are added. The flask
is corked, shaken, and then allowed to rest over-night.
The ether is decanted, or drawn off, as completely as possible. Two
filter-papers are taken and counterpoised—that is to say, they are made
precisely the same weight. The filters are placed one inside the other,
and the precipitate collected on the inner one; the precipitate is washed
with morphinated water—that is to say, water in which morphine has been
digested for some days. The filter-papers with their contents are washed
with benzene and dried, the outer paper put on the pan of the balance
carrying the weights, and the inner filter with the precipitate weighed.
The precipitate is now digested with a known volume of decinormal acid,
and then the excess of acid ascertained by titration with decinormal
alkali, using either lacmoid or cochineal; each c.c. of decinormal acid
is equal to 30.3 mgrms, of morphine.*
Dott's Process.--Dott has proposed a new process, which he
states has given good results. The process is as follows:–10 grammes
of powdered opium are digested with 25 c.c. water; 18 grammes
barium chloride dissolved in about 12 c.c. water are then added, the solu-
tion made up to 50 c.c., well mixed, and after a short time filtered ;
22 c.c. (representing 5 grammes opium) are mixed with dilute sulphuric
acid in quantity just sufficient to precipitate the barium. About 1 c.c.
is required, and the solution should be warmed to cause the precipitate
to subside, and the solution to filter clear. To this filtered solution a
little dilute ammonia, about 0.5 c.c., is added to neutralise the free acid,
and the solution concentrated to 6 or 7 c.c., and allowed to cool. 1 c.c.
spirit and 1 c.c. ether are then added, and next ammonia in slight excess.
The ammonia should be added gradually until there is no further pre-
cipitation, and a perceptible odour of ammonia remains after well stirring
and breaking down any lumps with the stirring rod. After three hours
the precipitate is collected on counterpoised filters and washed. Before
filtering, it should be noted that the solution has a faint odour of
ammonia: if not, one or two drops of ammonia solution should be added.
The dried precipitate is washed with benzene or chloroform, dried, and
weighed. It is then titrated with n/10 acid, until the morphine is
neutralised, as indicated by the solution reddening litmus-paper, f
* Pharm. Journal, xix. 45, 82; xxii. 746. Wright and Farr, Chemist and
Druggist, 1893, i. 78.
+ Other methods of opium assay have been published : see A. B. Prescott's
method (Proceedings of Amer. Pharm. Assoc., 1878); Allen (Commercial Org.
Analysis, vol. ii. p. 473); E. R. Squibb's modification of Flückiger's method
(Pharm. Journ. (3), xii. p. 724); a rapid mode of opium assay, MM. Portes and
Lanjlois (Journ. de Pharm, et de Chim., Nov. 1881); Year Book of Pharmacy, 1882.
To the above may be added—(1) Schacht's Method.—5 to 10 grms, of dry, finely-
§ 346.] OPIUM. 289
Douzard Method.—Heat 8 grims. of the sample with 100 c.c. of
water in a closed flask for one hour, cool, add 3 grims of slaked lime,
shake during one hour, filter. Take 51-6 c.c. of the filtrate and place
in a corked flask with 5 c.c. of 90 per cent. alcohol and 30 c.c. of ether
and 2 grms, ammonium chloride. Shake during thirty minutes, and
allow to stand for twelve hours; filter; remove the ether from the filter
with a pipette; wash the flask and filter with morphinated water until
free from chlorides, then wash once with 10 c.c. of distilled water and
pour on to the filter 15 c.c. of ether which, after a few minutes, remove
with a pipette. Expose the filter to the air for thirty minutes, then place
in a beaker and gently heat with 20 c.c. of n/10 H,SO, ; cool and
titrate with n/10 NaOH, using methyl-orange as an indicator. 1 c.c.
n/10 H.S0, - 0:0283 grim. morphine; add '05 grim. to the weight
found.
If tincture of opium is to be estimated take 100 c.c. and evaporate
to 30 c.c., add 3 grims, of slaked lime and make up to 100 c.c., add
2 c.c. of water, shake during one hour, filter and treat 50 c.c. of this
filtrate as above.
powdered opium are digested with sufficient distilled water to make a thin pulp.
After twenty-four hours the whole is thrown on a weighed filter, and washed until
the washings are almost colourless and tasteless. The portion insoluble in water is
dried at 100° and weighed; in good opium this should not exceed 40 per cent. The
filtrate is evaporated until it is about one-fifth of the weight of the opium taken
originally; it is then cooled, filtered, and treated with pure animal charcoal, until the
dark brown colour is changed into a brownish-yellow. The liquid is then refiltered,
precipitated with a slight excess of ammonia, allowed to stand in an open vessel
until all odour of ammonia disappears, and at the same time frequently stirred, in
order that the precipitate may not become crystalline—a form which is always more
difficult to purify. The precipitate is now collected on a tared filter, washed, dried,
and weighed. With an opium containing 10 per cent. of morphine, its weight is
usually 14 per cent. A portion of the precipitate is then detached from the filter,
weighed, and exhausted, first with ether, and afterwards with boiling alcohol
(0-81 specific gravity). Being thus purified from narcotine, and containing a little
colouring matter only, it may now be dried and weighed, and the amount of mor-
phine calculated, on the whole, from the data obtained.
(2) Fleury has proposed a titration by oxalic acid as follows:–2 grims, of the
powdered opium are macerated a few hours with 8 c.c. of aqueous oxalate of
ammonia, brought on a filter, and washed with 5 c.c. of water. To the filtrate an
equal volume of 80 per cent. alcohol and ammonia to alkaline reaction is added;
and, after standing twenty-four hours in a closed flask, it is filtered, and the flask
rinsed out with some c.c. of 40 per cent, alcohol. The filter, with its contents,
after drying, is placed in the same flask (which should not be cleansed), a few
drops of alcoholic logwood solution are added, with an excess of oxalic acid solu-
tion of known strength, the whole being made up to 100 c.c. This is divided
into two parts, and the excess of acid titrated back with diluted soda-lye. If
the oxalic acid solution is of the strength of 4'42 grims. to the litre, every c.c. of
the oxalic acid solution which has become bound up with morphine, corresponds to
0.02 grm. of morphine.
I9
29O Poisons: THEIR EFFECTS AND DETECTION. [š 347.
§ 347. Medicinal and other Preparations of Opium,_The chief
mixtures, pills, and other forms, officinal and non-officinal, in which
opium may be met with, are as follows:—
(1) OFFICINAL.
Compound Tincture of Camphor, P. B. (Paregoric).-Opium, cam-
phor, benzoic acid, oil of anise, and proof spirit: the opium is in the
proportion of about 0°4 per cent., or 1 grain of opium in 240 minims.
Ammoniated Tincture of Opium (Scotch paregoric).-Strong solution
of ammonia, rectified spirit, opium, oil of anise, saffron, and benzoic
acid. Nearly 1 per cent, or 1 grain of opium in every 96 minims.
The Compound Powder of Kino, P. B.
Opium, . tº e o * * tº 5 per cent.
Cinnamom, e tº g tº ſº e 20 ,
Kino, º & t * e ſe gº 75 ,,
The Compound Powder of Opium, P. B.
Opium, . tº e & tº g . 10:00 per cent.
Black Pepper, . e tº ſº & . 13:33 ,
Ginger, . te wº * e e . 33.33 ,
Caraway Fruit, , gº e g s 40:00 ,,
Tragacanth, {- ſº e & tº . 3:33 ,
Pill of Lead and Opium, P. B.
Acetate of Lead, tº & e e . 75.0 per cent.
Opium, . ſº tº e © ſº . 12.5 } }
Confection of Roses, . gº e © . 12.5 35
Tincture of Opium (Laudanum).-Opium and proof spirit. One
grain of opium in 148 minims—that is, about 67 parts by weight in
100 by measure.
The amount of opium actually contained in laudanum has been
investigated by Mr. Woodland,” from fourteen samples purchased from
London and provincial chemists. The highest percentage of extract was
5:01, the lowest 3:21, the mean being 4-24; the highest percentage of
morphine was 70 per cent, the lowest '32, the mean being 51 per cent.
It is, therefore, clear that laudanum is a liquid of very uncertain
strength.
Aromatic Powder of Chalk and Opium.—Opium 2.5 per cent, the
rest of the constituents being cinnamon, nutmeg, saffron, cloves, carda-
moms, and sugar.
* Year Book of Pharmacy, 1882.
§ 347.] - OPIUM. 29 I
Compound Powder of Ipecacuanha (Dover's Powder).
Opium, º º e -> - º . 10 per cent.
Ipecacuanha, e -> º * º . 10 ,
Sulphate of Potash, . tº e . . 80 ,,
Confection of Opium (Confectio opii) is composed of syrup and
compound powder of opium; according to its formula, it contains 2.4 per
cent. of opium by weight.
Extract of Opium contains the solid constituents capable of extrac-
tion by water; it should contain 20 per cent. of morphine, and is therefore
about double the strength of dry powdered opium.
Liquid Extract of Opium has been also examined by Mr. Wood-
land:* ten samples yielded as a mean 395 per cent. of dry extract,
the highest, number being 4.92 per cent., the lowest 3-02. The mean
percentage of morphine was 28 per cent., the highest amount being 37,
and the lowest 19 per cent.
Liniment of Opium is composed of equal parts of laudanum and
soap liniment; it should contain about 0.0375 per cent. morphine.
The Compound Soap-pill is made of soap and opium, one part of
opium in every 5:5 of the mass—i.e. about 18 per cent.
Ipecacuanha and Morphine Lozenges, as the last, with the addition
of ipecacuanha; each lozenge contains ºr grain (18 mgrms.) morphine
hydrochlorate, ſº grain (5:4 mgrms.) ipecacuanha.
Morphia Suppositories are made with hydrochlorate of morphine,
benzoated lard, white wax, and oil of theobroma; each suppository
contains # grain (32°4 mgrms.) of morphine salt. -
Opium Lozenges are composed of opium extract, tincture of tolu,
sugar, gum, extract of liquorice, and water. Each lozenge contains tº
grain (6.4 mgrms.) of extract of opium, or about ºf grain (1.3 mgrm.)
morphine. -
The Ointment of Galls and Opium contains one part of opium in
14-75 parts of the ointment—i.e. opium 67 per cent.
Opium Wine, P. B.-Sherry, opium extract, cinnamon, and cloves.
About 5 parts of opium extract by weight in 100 parts by measure
(22 grains to the ounce). -
Solutions of Morphine, both of the acetate and hydrochlorate, P. B.,
are made with a little free acid, and with rectified spirit. The strength of
each is half a grain in each fluid drachm (10324 grim. in 3-549), or '91
part by weight in 100 parts by measure.
Solution of Bimeconate of Morphine.—One fluid oz. contains 54
grains of bimeconate of morphine. -
Morphia Lozenges are made with the same accessories as opium
* Op. cit.
292 POISONS : THEIR EFFECTS AND DETECTION. [$ 347.
lozenges, substituting morphine for opium ; each lozenge contains ºr
grain of hydrochlorate of morphia (1.8 mgrm.).
Syrup of Poppies.—The ordinary syrup of poppies is sweetened
laudanum. It should, however, be what it is described—viz., a syrup
of poppy-heads. As such, it is said to contain one grain of extract of
opium to the ounce.
(2) PATENT AND OTHER NoN-OFFICINAL PREPARATIONS OF OPIUM.
Godfrey’s Cordial is made on rather a large scale, and is variable in strength and
composition. It usually contains about 1% grains of opium in each fluid ounce,” and,
as other constituents: Sassafras, molasses or treacle, rectified spirit, and various
flavouring ingredients, especially ginger, cloves, and coriander ; aniseed and caraways
may also be detected.
Grinrod's Remedy for Spasms consists of hydrochlorate of morphine, spirit of
sal-volatile, ether, and camphor julep ; strength, 1 grain of the hydrochlorate in
every 6 ounces.
Lemaurier's Odontalgic Essence is acetate of morphine dissolved in cherry-
laurel water ; strength, 1 grain to the ounce.
Nepenthe is a preparation very similar to Liq. Opii sedativ., and is of about the
same strength as laudanum.t
Black Drop (known also by various names, such as Armstrong's Black Drop)
is essentially an acetic acid solution of the constituents of opium. It is usually
considered to be of four times the strength of laudanum. The wholesale receipt
for it is : Laudanum, 1 oz., and distilled vinegar 1 quart, digested for a
fortnight. The original formula proposed by the Quaker doctor of Durham,
Edward Tunstall, is-Opium, sliced, 3 lb. ; good verjuice, f 3 pints; and nutmeg,
1% oz. ; boiled down to a syrup thickness; # lb. of sugar and 2 teaspoonfuls of
yeast are then added. The whole is set in a warm place for six or eight weeks,
after which it is evaporated in the open air until it becomes of the consistence of
a syrup. It is lastly decanted and filtered, a little sugar is added, and the liquid
made up to 2 pints.
“Nurses' Drops” seem to be composed of oil of caraway and laudanum.
Powell’s Balsam of Aniseed, according to evidence in the case of Pharmaceutical
Society v. Armson (Pharm. Jowrm., 1894), contains in every oz. Tº grain of morphine.
Dalby's Carminative—
Carbonate of magnesia, . ſº tº
e 40 grains.
Tincture of castor, and compound tincture of
cardamoms, of each & & te g . 15 drops.
Laudanum, . ſº & ſº * * e 5 ,
Oil of aniseed, g * º * * e . 3 , ,
Oil of nutmeg, ſº g tº g & g . 2 drops.
Oil of peppermint, g e º º º ... 1
3 3
Peppermint water, 2 fl. ounces.
Dose, from a half to one teaspoonful. Another recipe has no laudanum, but instead
syrup of poppies.
* If made according to Dr. Paris’ formula, 1% grains in an ounce.
# It may be regarded as a purified alcoholic solution of meconate of morphia, with
a little excess of acid, and of about the same strength as laudanum.–Taylor.
# Verjuice is the juice of the wild crab.
§ 348.] - OPIUM. 293
Chlorodyne–Brown's Chlorodyne is composed of—
Chloroform, . 6 drachms.
Chloric ether, 1. 5 3
Tincture of capsicum, º # 3 2
Hydrochlorate of morphine, - . 8 grains.
Scheele's prussic acid, º e • e . 12 drops.
Tincture of Indian hemp, 1 drachm.
Treacle, 1 2 3
Atkinson's Infant Preserver—
Carbonate of magnesia, º º g - . 6 drachms.
White sugar, º ſº • {- * º . 2 ounces.
Oil of aniseed, & * - - e - . 20 drops.
Spirit of sal-volatile, . - - - - . 2% drachms.
" Laudanum, * - - º - . 1 2 3
Syrup of saffron, . . º - - 1 ounce.
Caraway water, to make up, e º - . 1 pint.
Boerhaave’s Odontalgic Essence—
Opium, tº e te • e * - . . drachm.
Oil of cloves, e - 2 3 )
Powdered camphor, . b - e - . 5 3 3
Rectified spirit, 1; fl. ounces.
§ 348. Statistics.-During the ten years 1894–1903, 1505 deaths
in England and Wales were attributed to some form or other of opium
or its active constituents; 882 were due to accident or negligence; 621
were suicidal and 2 were homicidal deaths. To these may be added
the deaths of 66 males and 36 females (102 total) from the accidental
taking of chlorodyne, the suicidal deaths of 36 males and 3 females
from the same drug, and 9 children dying from soothing syrup, making
a grand total of 1655 deaths from some form or other of opium or its
active constituents in ten years. The sex distribution of the deaths
ascribed to accident and those ascribed to suicide are detailed in the
following tabular statement:— -
DEATHS IN ENGLAND AND WALES DURING THE TEN YEARS 1894–1903
FROM OPIUM, LAUDANUM, MORPHINE, Etc.
ACCIDENT. SUICIDE.
Males, º s * - . 536 Males, * - - & . 432
Females, , tº e - . 346 Females, . º - e . 189
Total, . 882 Total, . 621
Of European countries, England has the greatest proportional number
of opium poisonings. In France, opium or morphine poisoning accounts
for about 1 per cent. of the whole ; and Denmark, Sweden, Switzerland,
Germany, all give very small proportional numbers; arsenic, phosphorus,
and the acids taking the place of opiates. The more considerable mor-
294 POISONS: THEIR EFFECTS AND DETECTION. [$ 349, 350.
tality arises, in great measure, from the pernicious practice—both of the
hard-working English mother and of the baby-farmer—of giving infants
various forms of opium sold under the name of “soothing syrups,”
“infants' friends,” “infants' preservatives,” “nurses’ drops,” and the like,
to allay restlessness, and to keep them during the greater part of their
existence asleep. Another fertile cause of accidental poisoning is mistakes
in dispensing; but these mistakes seem to happen more frequently on
the Continent than in England. This is in some degree due to the
decimal system, which has its dangers as well as its advantages, e.g.:—A
physician ordered 5 decigrm, of morphine acetate in a mixture for a child,
but omitted the decimal point, and the apothecary, therefore, gave ten
times the dose desired, with fatal effect. Again, morphine hydrochlorate,
acetate, and similar soluble salts are liable to be mistaken for other white
powders, and in this way unfortunate accidents have occurred—accidents
that, with proper dispensing arrangements, should be impossible.
§ 349. Poisoning of Children by Opium.—The drugging of children
by opium—sometimes with a view to destroy life, sometimes merely for
the sake of the continual narcotism of the infant—is especially rife in
India.” A little solid opium is applied to the roof of the mouth, or
smeared on the tongue, and some Indian mothers have been known to
plaster the nipples with opium, so that the child imbibes it with the
milk. Europeans, again and again, have discovered the native nurses
administering opiates to the infants under their care, and it is feared
that in many cases detection is avoided. -
The ignorant use of poppy-tea has frequently caused the death of
young children; thus in 1875 an inquest was held at Chelsea on the
body of a little boy two years and a half old. He had been suffering
from whooping-cough and enlargement of the bowels, and poppy-tea
was by the advice of a neighbour given to him. Two poppy-heads were
used in making a quart of tea, and the boy, after drinking a great
portion of it, fell into a deep sleep, and died with all the symptoms of
narcotic poisoning.
§ 350. Doses of Opium and Morphia.-Opium in the solid state is
prescribed for adults in quantities not exceeding 3 grains, the usual dose
being from 16.2 mgrms. to 64.8 mgrms. (4 to 1 grain). The extract of
opium is given in exactly the same proportions (special circumstances,
such as the habitual use of opium, excepted); the dose of all the com-
pounds of opium is mainly regulated by the proportion of opium contained
in them.
The dose for children (who bear opium ill) is usually very small;
single drops of laudanum are given to infants at the breast, and the dose
cautiously increased according to age. Most practitioners would consider
* See Dr. Chever's Jurisprudence, 3rd ed., 232 et seq.
§ 35 I.] OPIUM. 295
half a grain a very full dose, and, in cases requiring it, would seldom
prescribe at first more than fºr to 4 grain. ar.
The dose of solid opium for a horse is from 177 grms. to 7-08 grims.
(# drachm to 2 drachms); in extreme cases, however, 4 drachms (14:16
grms.) have been given.
The dose for large cattle is from 648 grim. to 3-88 grims. (10 to 60
grains); for calves, 648 grin. (10 grains); for dogs it is greatly regulated
by the size of the animal, 16-2 to 129.6 mgrms. (4 grain to 2 grains).
Fatal Dose.--Cases are recorded of infants dying from extremely
small doses of opium, e.g. 7, 4°3, and 8.1 mgrms. (#3, #, and # of a
grain); but in such instances one cannot help suspecting some mistake.
It may, however, be freely conceded that a very small quantity might
be fatal to infants, and that 3 mgrms. given to a child under 1 year
would probably develop serious symptoms.
The smallest dose of solid opium known to have proved fatal to
adults was equal to 259 mgrms. (4 grains) of crude opium (Taylor),
and the smallest dose of the tincture (laudanum), 7-0 c.c. (2 drachms)
(Taylor); the latter is, however, as already shown, uncertain in its
composition.
A dangerous dose (save under special circumstances) is:—For a
horse, 14:17 grns. (4 drachms); for cattle, 7.04 grms. (2 drachms); for
a dog of the size and strength of a foxhound, 204 mgrms. (3 grains).
Enormous and otherwise fatal doses may be taken under certain con-
ditions by persons who are not opium-eaters. The senior author has
seen 13 cgrms. (2 grains) of morphine acetate injected hypodermically
in a strong man suffering from rabies with but little effect. Tetanus,
strychnine, convulsions, and excessive pain all decrease the sensibility
of the nervous system to opium.
§ 351. General Method for the Detection of Opium.—It is usually
laid down in forensic works that, where poisoning by opium is suspected,
it is sufficient to detect the presence of mecomic acid in order to establish
that of opium. In a case of adult poisoning there is generally substance
enough available to obtain one or more alkaloids, and the presence of
opium may, without a reasonable doubt, be proved, if mecomic acid (as
well as either morphine, marcotine, thebaine, or other opium alkaloid)
has been detected. Pills containing either solid opium or the tincture
usually betray the presence of the drug by the odour, and in such a case
there can be no possible difficulty in isolating morphine and mecomic
acid, with probably one or two other alkaloids. The method of extrac-
tion from organic fluids is the same as before described, but it may, of
course, be modified for any special purpose. If opium, or a preparation
of opium, be submitted to Dragendorff's process (see p. 256), the follow-
ing is a sketch of the chief points to be noticed.
296 POISONS : THEIR EFIFECTS AND DETECTION. [Š 352.
If the solution is acid—
(1) Benzene mainly extracts mecomin, which dissolves in sulphuric
acid very gradually (in twenty-four to forty-eight hours), with a green
colour passing into red. Mecomin has no alkaloidal reaction.
(2) Amyl alcohol dissolves small quantities of mecomic acid, identified
by striking a blood-red colour with ferric chloride.
If now the amyl alcohol is removed with the aid of petroleum ether,
and the fluid made alkaline by ammonia,
(1) Benzene extracts marcotine, codeine, and thebaine. On evapora-
tion of the benzene the alkaloidal residue may be dissolved in water,
acidified with sulphuric acid, and after filtration, on adding ammonia in
eaccess, thebaïne and narcotine are precipitated, codeine remaining in
solution. The dried precipitate, if it contain thebaine, becomes blood-
red when treated with cold concentrated sulphuric acid, while narcotine
is shown by a violet colour developing gradually when the substance
is dissolved in dilute sulphuric acid 1 : 5, and gently warmed. The
codeine in the ammoniacal solution can be recovered by shaking up
with benzene, and recognised by the red colour which the solid substance
gives when treated with a little sugar and sulphuric acid.
(2) Chloroform especially dissolves the narceine, which, on evapora-
tion of the chloroform, may be identified by its general characters, and
by its solution in Fröhde's reagent becoming a beautiful blue colour.
Small quantities of morphine may be extracted with codeine.
(3) Amyl alcohol extracts from the alkaline solution morphine,
identified by its physical characters, by its forming a crystalline precipi-
tate with iodine and hydriodic acid, and the reaction with iodic acid to
be described.
§ 352. Morphine (C, H, NO(OH)2 + H2O).-Morphine occurs in
commerce as a white powder, sp. gr. 1205, usually in the form of more
or less perfect six-sided prisms, but sometimes in that of white silky
needles. When heated in the subliming cell (described at p. 260),
faint nebulae, resolved by high microscopic powers into minute dots,
appear on the upper disc at 150°. As the temperature is raised the
spots become coarser, and at 188” distinct crystals may be obtained, the
best being formed at nearly 200”, at which temperature morphine begins
distinctly to brown, melt, and carbonise. At temperatures below 188”,
instead of minute dots, the sublimate may consist of white circular spots
or foliated patterns. One part of morphine, according to P. Chastaing,
is soluble at a temperature of 3° in 33,333 parts of water; at 22°, in
4545 parts; at 42°, 4280; and at 100”, 4562. It is scarcely soluble in
ether or benzene. Absolute alcohol, according to Pettenkofer, dissolves
in the cold one-fortieth of its weight ; boiling, one-thirtieth. Amyl
alcohol, in the cold, dissolves one-fourth per cent., and still more if the
§ 353.] MORPHINE. - 297
alkaloid be thrown out of an aqueous acid solution by ammonia in the
presence of amyl alcohol; for under such circumstances the morphine
has no time to become crystalline. According to Schlimpert, 1 part
of morphine requires 60 of chloroform for solution; according to
Pettenkofer, 175. 100 parts of tetrachloride of carbon dissolve 032
morphine (J. Schindelmeiser, Chemiker-Zeitung, xxv. 129).
Morphine is easily soluble in dilute acids, as well as in solutions of
the caustic alkalies and alkaline earths; carbonated alkalies and chloride
of ammonium also dissolve small quantities. The acid watery, and the
alcoholic solutions, turn the plane of polarisation to the left; for
sulphuric, nitric, and hydrochloric acids [a]r=89'8"; in alkaline solution
the polarisation is less, [a]r = 45'22". It is alkaline in reaction, neutral-
ising acids fully; and, in fact, a convenient method of titrating morphine
is by the use of a centinormal sulphuric acid—each c.c. equals 2-85
mgrms. of anhydrous morphine.
§ 353. The salts of morphine are for the most part crystalline, and
are all bitter, neutral, and poisonous. They are insoluble in amylic
alcohol, ether, chloroform, benzene, or petroleum ether.
Morphine meconate is one of the most soluble of the morphine
salts; it is freely soluble in water. Of all salts this is most suitable
for subcutaneous injection; it is the form in which the alkaloid exists
in opium.
Morphine hydrochlorate (C7H16NO, HCl) crystallises in silky fibres;
it is readily soluble in alcohol, and is soluble in cold, more freely in
boiling, water. The purest morphine hydrochlorate is colourless, but
that which is most frequently met with in commerce is fawn or buff-
coloured.
Morphine acetate is a crystallisable salt, soluble in water or alcohol;
it is in part decomposed by boiling the aqueous solution, some of the
acetic acid escaping.
Morphine Tartrates.—These are readily soluble salts, and it is im-
portant to note that the morphine might escape detection, if the expert
trusted alone to the usual test of an alkaloidal salt giving a precipitate
when the solution is alkalised by the fixed or volatile alkalies; for the
tartrates of morphine do not give this reaction, nor do they give any
precipitate with calcic chloride. By adding a solution of potassium
acetate in spirit, and also alcohol and a little acetic acid to the com-
centrated solution, the tartrate is decomposed, and acid tartrate of
potassium is precipitated in the insoluble form ; the morphine in
the form of acetate remains in solution, and then gives the usual
reactions.
The solubility of morphine salts in water and alcohol has been in-
vestigated by Mr. J. U. Lloyd. His results are as follows:–
298 POISONS : THEIR EFFECTS AND DETECTION. [$ 354.
Morphine Acetate. -
1170 parts of water by weight at 15:0° dissolve 1 part of morphine
acetate.
61-5 parts of water by weight at 100° dissolve 1 part of morphine
acetate.
68:30 parts of alcohol by weight (820 specific gravity) at 15'0" dissolve
1 part of morphine acetate.
13:30 parts of alcohol by weight (820 specific gravity) at 100 dissolve
1 part of morphine acetate.
Morphine Hydrochlorate.
23:40 parts of water dissolve at 15° 1 morphine hydrochlorate.
‘51 part of water dissolves at 100° 1 morphine hydrochlorate.
62-70 parts of alcohol ('820 specific gravity) dissolve at 15° 1 morphine
hydrochlorate.
30-80 parts of alcohol ('820 specific gravity) dissolve at 100° 1 morphine
hydrochlorate.
Morphine Sulphate.
21:60 parts of water at 15" dissolve 1 morphine sulphate.
‘75 part of water at 100” dissolves 1 morphine sulphate.
701:5 parts of alcohol ('820) at 15° dissolve 1 morphine sulphate.
144:00 parts of alcohol ('820) at 100° dissolve 1 morphine sulphate.
§ 354. Constitution of Morphine and Codeine.—Morphine is a
tertiary base. It forms diacetyl and dibenzoyl derivatives, hence it
contains two hydroxyl derivatives, one a phenol, the other an alcohol.
Morphine when mildly oxidised forms pseudomorphine identical with
natural pseudomorphine.
2C17H16NO3 + O -> (C17HisNO3)2 + H2O
Pseudomorphine.
Sulphuric, hydrochloric, phosphoric and oxalic acids, the alkalies,
and zinc chloride have a twofold action on morphine, giving conden-
sation products and a dehydration product, apomorphine C17H17NO2,
which has a powerful emetic action. Apomorphine is an amorphous base
soluble in alcohol, ether, and chloroform. Codeine is the monomethyl
ester of morphine,
Cº. Hiſ NO(OH)(OH) Cº. Hiſ NO(OH)(OCHA)
Morphine. Codeine.
Codeine by loss of water yields apocodeine CisłłioMO3. By treating
codeine with concentrated hydrochloric acid at 100", chlorcodide,
CisłI2001NO3, is obtained; on heating this with hydrochloric acid at
150°, methyl chloride and apomorphine result. Morphine has been
§ 354.] MORPHINE. 299
converted into codeine by heating with methyl iodide and caustic
potash when the phenol hydroxyl of the morphine is alkylated,
Cly Him NO(OH)2+ CHAI+ KOH → C17H17NO(OH)(OCHA) + KI+ H2O
Morphine. Codeine.
When codeine methyl hydroxide is distilled it yields methyl-
morphimethine (OH)(CH3O)Cl. HigO = N – CH3+H,0; this heated with
HCl gives methyldioxyphenanthrene ºc,B, and dimethyloxethyl-
CH,0
amine OH – C, H, -N(CH3)2. The first of these has been shown to be
the monomethyl ether of dioxyphenanthrene or methyl morphol; the free
base from this is known as morphol, and has been proved to be 3, 4 dioxy-
phenanthrene, and methyl morphol is 3-methoxy-4-oxyphenanthrene,
— *—º OH_OCH3
Cº- > <-TX
Morphol. Methylmorphol.
The nitrogenous base formed on heating methylmorphimethine
CH,OH


with HCl may be represented thus, dimethyl ethyl
CH, N(CH3),
oxethylamine, and from the formation of this compound morphine is
considered to contain an oxazine ring of the form -
O
H2C ſ
CH2
Ho Q/ CH,
* NH
this is called morpholine.
Morphine and codeine thus appear to be ring systems containing the
phenanthrene complex in connection with a morpholine ring, and the
following formula has been proposed for morphine,
CH
Ho-C/N CH
|

CH3 – O
- | ** ºch
| Hº o
Nº ZN/
*s--> n
| HO C H
ch, 20' A Ch.
Sº
Morphine
3OO Poisons: THEIR EFFECTS AND DETECTION. [š 355.
§ 355. Tests for Morphine.—(1) One hundredth of a milligrim. of
pure morphine gives a blue colour to a paste of ammonium molybdate
in sulphuric acid; 20 mgrms. of ammonium molybdate are rubbed with
a glass rod in a porcelain dish, and well mixed with 5 drops of pure
strong sulphuric acid and the morphine in a solid form applied ; titanic
acid and tungstates give similar reactions.
(2) Morphine possesses strong reducing properties; a little solid
morphine dissolved in a solution of ferric chloride gives a Prussian
blue precipitate when ferridcyanide solution is added. A number of
ptomaines and other substances also respond to this test, so that in itself
it is not conclusive.
(3) Kobert's Test.—2–3 drops of formalin are mixed with 3 c.c. of
strong H2SO4; this reagent is mixed in a watch-glass with the dry
substance. Morphine becomes purple-red, then violet, then clear blue.
The solution examined spectroscopically shows a band in the yellow and
Orange ; dionin, codeine, and heroine give similar reactions; methylphen-
morpholin gives an intense red colour.
(4) Iodic Acid Test.—The substance supposed to be morphine is
converted into a soluble salt by adding to acid reaction a few drops of
hydrochloric acid, and then evaporating to dryness. The salt thus
obtained is dissolved in as little water as possible—this, as in toxi-
cological researches only small quantities are recovered, will probably
be but a few drops. A little of the solution is now mixed with a very
small quantity of starch paste, and evaporated to dryness at a gentle
heat in a porcelain dish. After cooling, a drop of a solution of 1 part
of iodic acid in 15 of water is added to the dry residue ; and if even the
goºgo of a grain of morphine be present, a blue colour will be developed.
Another way of working the iodic acid test is to add the iodic acid
solution to the liquid in which morphine is supposed to be dissolved
and then shake the liquid up with a few drops of carbon disulphide. If
morphine be present, the carbon disulphide floats to the top distinctly
coloured pink. Other substances, however, also set free iodine from
iodic acid, and it has, therefore, been proposed to distinguish morphine
from these by the after-addition of ammonia. If ammonia is added to
the solution, which has been shaken up with carbon disulphide, the pink
or red colour of the carbon disulphide is deepened, if morphine was
present ; on the contrary, if morphine was not present, it is either
discharged or much weakened.
(5) Lloyd's Test.—A mixture of hydrastin and morphine mixed
with a few drops of sulphuric acid develops after about five minutes a
blue-violet colour. This reaction has been investigated by J. L. Mayer *
and shown to be almost distinctive.
* Zeit. f. analyt, Chemie, 1902, 576
§ 355.] - MORPHINE. 3OI
(6) Wanadic Acid Test.—Wanadate of ammonia is dissolved in strong
sulphuric acid; the acid must be added until the yellow colour dis-
appears and a colourless solution is obtained; morphine warmed with
a few drops of this solution produces a fine green colour, or, if the
solution is diluted, a bluish-green colour.
(7) Tungstic Acid Test.—A solution of anything like 1 per cent. of
sodium tungstate is inapplicable ; but if a dilute solution of the salt is
taken (say 1 mgrm. per c.c.) and acidified with sulphuric acid, the
solution gives a violet colour with morphine or morphine salts.
(8) Titanic Acid Test.—Titanic acid is dissolved in strong sulphuric
acid by the aid of heat; the solution should be syrupy and clear. A
drop of this solution added to solid morphine strikes immediately a
black colour. * ->
Other Reactions.—There are some very interesting reactions besides
those just mentioned. If a saturated solution of chloride of zinc be
added to a little solid morphine, and heated over the water-bath for
from fifteen minutes to half an hour, the liquid develops a beautiful and
persistent green colour. This would be an excellent test for morphine
were it not for the fact that the colour is produced with only pure
morphine. For example, the reaction is not obtained from morphine
in very well-formed crystals precipitated from ordinary laudanum
by ammonia, the least trace of resinous or colouring matter seriously
interfering. By the action of nitric acid on morphine, the liquid
becomes orange-red, and an acid product of the formula C10HaNO, is
produced, which, when heated in a closed tube with water at 100°,
yields trinitrophenol or picric acid. On adding a drop of sulphuric
acid to solid morphine in the cold, the morphine solution becomes
of a faint pink; on gently warming and continuing the heat until
the acid begins to volatilise, the colour changes through a series
of brownish and indefinite hues up to black. On cooling and
treating the black spot with water, a green solution is obtained,
agreeing in hue with the same green produced by chloride of zinc.
Vidali f has proposed the following test :-Morphine is dissolved in
strong sulphuric acid, and a little arsenate of sodium is added; on
gently warming, a passing blue colour develops; on raising the tempera-
ture higher, the liquid changes into green, then into blue, and finally
again into green. Codeine acts very similarly. C. Reichard (Chem.
Zeit., 1904) uses AsgOs dissolved in strong NaOH solution; to a c.c.
of this is added morphine and then strong H2SO4; an intense and
permanent purple colour develops. The following test originated with
* C. Reichard, Zeit. f. analyt. Chemie, 1903, 95.
t D. Vidali, Bull. Farmaceut., Milano, 1881, p. 197; D. B. Dott, Year Book of
Pharmacy, 1882.
3O2 POISONS : THEIR EFFECTS AND DETECTION, [$ 355.
Siebold (American Journal of Pharmacy, 1873, p. 544):-The supposed
morphine is heated gently with a few drops of concentrated sulphuric
acid and a little pure potassic perchlorate. If morphine be present
the liquid immediately takes a pronounced brown colour—a reaction
said to be peculiar to morphine, and to succeed with fºr of a mgrm. In
order to obtain absolutely pure perchlorate, potassic perchlorate is
heated with hydrochloric acid so long as it disengages chlorine; it is
then washed with distilled water, dried, and preserved for use. There
is also a test known as “Pellagri’s ’’; it depends on the production of
apomorphine. The suspected alkaloid is dissolved in a little strong
hydrochloric acid, and then a drop of concentrated sulphuric acid is
added, and the mixture heated for a little time from 100° to 120°,
until it assumes a purple-black colour. It is now cooled, some hydro
chloric acid again added, and the mixture neutralised with sodic
carbonate. If morphine be present, on the addition of iodine in
hydriodic acid, a cherry-red colour is produced, passing into green.
Morphine and codeine are believed alone to give this reaction.
The acetate of morphine, and morphine itself, when added to ferric
chloride solution, develop a blue colour. When 1 molecule of morphine
is dissolved in alcohol, containing 1 molecule of sodium hydroxide, and
2 vols. of methyl iodide are added, and the mixture gently heated, a
violent reaction sets in and the main product is codeine methiodide
(Cº. His NO,OCH,Meſ). If only half the quantity of methyl iodide is
added, then free codeine is in small quantity produced ; if ethyl iodide be
substituted for methyl, a new base is formed homologous with codeine.
If morphine is heated with iodide of methyl and absolute alcohol in a
closed tube for half an hour at 100°, methyl iodide of morphine is
obtained in colourless, glittering, quadratic crystals, easily soluble in
water (C17H16NO,Meſ + H2O): similarly the ethyl iodide compound can
be produced.
If morphine is heated for from two to three hours in a closed tube
with dilute hydrochloric acid, water is eliminated—
(C17H19NOs = Cl, H17NO2 + H2O),
and the hydrochlorate of apomorphine is produced. This succeeds when
even mgrm. is heated with tº c.c. of strong HCl, and the tests for
apomorphine applied.
If concentrated sulphuric acid be digested on morphine for twelve to
fifteen hours (or heated for half an hour at 100"), on adding to the
cooled violet-coloured solution either a crystal of nitrate of potash or of
chlorate of potash, or a drop of dilute nitric acid, a beautiful violet-blue
colour is produced, which passes gradually into a dārk blood-red.
rig of a mgrm, will respond distinctly to this test. Fröhde's reagent
§ 356.] . MORPHINE. 3O3
strikes with morphine a beautiful violet colour, passing from blue into
dirty green, and finally almost vanishing. ##0 of a mgrm. will respond
to the test, but it is not itself conclusive, since papaverine and certain
glucosides give an identical reaction.
§ 356. Symptoms of Opium and Morphine Poisoning. — The
symptoms of opium and morphine poisoning are so much alike, that -
clinically it is impossible to distinguish them ; therefore they may be
considered together.
Action on Animals—Frogs.-The action of morphine or opium on
frogs is peculiar; the animal at first springs restlessly about, and then
falls into a condition extremely analogous to that seen in Strychnine
poisoning, every motion or external irritation producing a tetanic con-
vulsion. This condition is, however, sometimes not observed. The
tetanic stage is followed by paralysis of reflex movements and cessation
of breathing, the heart continuing to beat.
Dogs.—0-2 to 0.5 grn. of morphine meconate, or acetate, injected
directly into the circulation of a dog, shows its effects almost immediately.
The dog becomes uneasy, and moves its jaws and tongue as if some
peculiar taste were experienced; it may bark or utter a whine, and then
in a minute or two falls into a profound sleep, which is often so deep
that while it lasts—usually several hours—an operation may be per-
formed. In whatever attitude the limbs are placed, they remain. The
respiration is rapid and stertorous, and most reflex actions are extin-
guished. Towards the end of the sleep, any sudden noise may startle
the animal, and when he wakes his faculties are evidently confused.
A partial paralysis of the hind leg has often been noticed, and then the
dog, with his tail and pelvis low, has something the attitude of the
hyena. Hence this condition (first noticed by Bernard) has been
called the “hyenoid" state. If the dose is larger than 2 to 3 grms.
(31 to 46 grains), the symptoms are not dissimilar, save that they
terminate in death, which is generally preceded by convulsions.”
* MM. Grasset and Amblard have studied the action of morphine in causing con-
vulsions in the mammalia. They found that if Small doses of hydrochlorate of
morphine (from 1 to 15 centigrammes) are administered to dogs, the brief sleep
which is produced may be accompanied by partial muscular contractions (in one
paw, for instance), which are renewed at variable intervals. Then occur true con-
vulsive shocks in the whole body or in the hind limbs. After an interval, the
phenomena recur in more intense degree, and are followed by true convulsions.
Regularly, ten or sixteen times a minute, at each inspiration, the hind limbs present
a series of convulsive movements, which may become general. Sometimes they are
excited by external stimulation, but they are usually spontaneous. The sleep may
continue profound during this convulsive period, or it may become distinctly lighter.
These convulsive phenomena may continue, with intervals, for an hour. Differences
are observed with different animals ; but the chief characters of the phenomena are
as described. In certain animals, and with small doses, there may be a brief con-
3O4 POISONS: THEIR EFFECTS AND DETECTION. [$ 357.
Goats.-According to Guinard, goats are proof against the narcotic
influence of morphine. Large doses kill goats, but death is caused by
interference with the respiratory function. A young goat weighing 30
kilos. showed little effect beyond a slightly increased cerebral excitability
after two doses of 8 and 8.5 grns. respectively of morphine hydro-
chlorate had been administered by intravenous injection, the second
being given an hour and a half after the first. To the same animal two
days afterwards 195 grms, were administered in the same way, yet the
goat recovered. The lethal dose for a goat seems to be no less than
1000 times that which will produce narcotism in man, and lies somewhere
between 0.25 to 0:30 per kilo. of the body weight.*
Cats and the Felidae.—According to Guinard, f morphine injected
subcutaneously or intravenously into cats, in doses varying from 0-4
mgrm. to 90 mgrms, per kilo., never produces sleep or narcotic prostra-
tion. On the contrary, it causes a remarkable degree of excitement,
increasing in intensity with the dose given. This excitement is evidently
accompanied by disorder in the functions of the brain, and if the dose is
large convulsions set in, ending in death. According to Milne-Edwards,
the same symptoms are produced in lions and tigers.
Birds, especially pigeons, are able to eat almost incredible quantities
of opium. A pigeon is said to have consumed 801 grains of opium,
mixed with its food, in fourteen days. The explanation of this is that
the poison is not absorbed ; for subcutaneous injections of salts of
morphine act rapidly on all birds hitherto experimented upon.
§ 357. Physiological Action.—From experiments on animals, the
vulsive phase at the commencement of the sleep, but it is much less constant than
the later period of spasm. These convulsions, the authors believe, have not pre-
viously been described, except as a consequence of very large doses, amounting to
grammes. The period of cerebral excitement, described by Claude Bernard as
occurring at the commencement of the sleep from morphine, is a phenomenon of
a different order. The conclusions drawn from the experiments are—(1) That
morphine is not diametrically opposed to thebaine, as is often stated, since it has, to
a certain degree, the convulsive properties of the latter alkaloid. (2) That the
excitomotor action of opium cannot be exclusively attributed to the convulsive alka-
loids, but is, in fact, due to those which are soporific. According to the ordinary
composition of opium, 5 centigrammes of morphine represent about a milligramme
of thebaine. But these experiments show that the quantity of morphine has a much
more powerful convulsive action than a milligramme of thebaine. (3) There is not
the supposed antagonism between the action of morphine on the frog and on the
mammalia. (4) The researches hitherto undertaken on the antagonism between
morphine and other agents need to be repeated, and a separate study made of the
substances which antagonise the convulsive and Soporific action.
* Compt. Rend., t. cxvi. pp. 520–522.
f Compt. Rend., t. Cxi. pp. 981–983. The bovine animals also get excited, and
no marcotic effect is produced by dosing them with morphine. —Compt. Rend. Soc. de
Biologie, t. iv., v.
f Hermann's Lehrbuch der exper. Toaricologie, p. 374.
§ 358.] MORPHINE. 3O5
essential action of morphine on the nervous and arterial systems has in
some measure been examined. There is no very considerable action on
the heart. The beats are first accelerated, then diminished in frequency;
but very large doses introduced directly into the circulation at once
diminish the pulsations, and no acceleration is noticed. The slowing
may go on to heart-paralysis. The slowing is central in its origin, for
on the vagi being cut, morphine always quickens. With regard to the
peripheric ends of the vagi, small doses excite, large paralyse. If all
the nerves going to the heart are divided, there is first a considerable
acceleration, and then a slowing and weakening of the pulsation. The
arterial blood-pressure, at first increased, is afterwards diminished.
This increase of blood-pressure is noticed during the acceleration of the
pulse, and also during some portion of the time during which the pulse
is slowed. Stockman and D. B. Dott,” experimenting on rabbits and
frogs, consider that a medium dose of morphine first of all depresses the
spinal cord and then excites it, for tetanus follows. If morphine is in
sufficient quantity thrown into the circulation, then tetanus at once
occurs. It would thus appear that depression and stimulation is
entirely a matter of dosage. Gescheidlen, in his researches on the frog,
found the motor nerves at first excited, and then depressed. When the
doses were large, there was scarcely any excitement, but the reverse
effect, in the neighbourhood of the place of application. According to
other observers, the function of the motor nerves may be annihilated. †
According to Meihuizen, reflex action, at first much diminished, is later,
after several hours, normal, and later still again increased. The
intestinal movements are transitorily increased. In the dog there has
been noticed a greater flow of saliva than usual, and the flow of bile
from the gall-bladder is diminished. The pupils in animals are mostly
contracted, but, if convulsions occur towards death, they are dilated.
§ 358. Physiological Effect of Morphine Derivatives.—By intro-
ducing methyl, or amyl, or ethyl, into the morphine molecule, the
narcotic action is diminished, while the tetanic effects are increased.
Acetyl, diacetyl, benzoyl, and dibenzoyl morphine, morphine sulphuric
ether, and nitrosomorphine are all weaker narcotics than morphine, but,
on the other hand, they depress the functions of the spinal cord and
bring on, in large doses, tetanus.
The introduction of two methyl groups into morphine, as in metho-
codeine, Cly Hız MeNO(OH) — Me, entirely alters the physiological effect.
This compound has an action on voluntary muscle causing gradual
paralysis.
The chlorine derivatives, trichlormorphine and chlorcodeine, have
the characteristic action of the morphine group on the central nervous
* Brit. Med. Jowrm. (2), 1890, 189–192. f Arch. f. d. Ges. Physiol., vii. p. 201.
2O
306 POISONS : THEIR EFFECTS AND DETECTION, [$ 359.
system and, in addition, act emergetically as muscle poisons, soon
destroying the contractile power of the voluntary muscles with which
they first come into contact at the place of injection, and more gradually
affecting the other muscles of the body.*
§ 359. Action on Man-There are at least three forms of opium
poisoning:—(1) The common form, as seen in about 99 per cent. of
cases; (2) A very Sudden form, in which death takes place with fearful
rapidity (the foudroyante variety of the French); t and (3) a very rare
entirely abnormal form, in which there is no coma, but convulsions.
In the common form there are three stages, viz. –(1) Excitement;
(2) Narcosis; (3) Coma. In from half an hour to an hour ; the first
symptoms commence, the pulse is quickened, the pupils are contracted,
the face flushes, and the hands and feet reddened,—in other words, the
capillary circulation is active. This stage has some analogy to the action
of alcohol; the ideas mostly flow with great rapidity, and instead of a
feeling of sleepiness, the reverse is the case. It, however, insensibly,
and more or less rapidly, passes into the next stage of heaviness and stupor.
There is an irresistible tendency to sleep; the pulse and the respiration
become slower ; the conjunctivae are reddened, the face and head often
flushed. In some cases there is great irritability of the skin, and an
eruption of nettle-rash. If the poison has been taken by the mouth,
vomiting may be present. The bowels are usually—in fact almost invari-
ably—constipated. There is also some loss of power over the bladder.
In the next stage, the marcosis deepens into dangerous coma; the
patient can no longer be roused by noises, shaking, or external stimuli;
the breathing is loud and stertorous; the face often pale; the body
covered with a clammy sweat. The pupils are still contracted, but they
may in the last hours of life dilate; and it is generally agreed that, if a
corpse is found with the pupils dilated, this circumstance, taken in itself,
does not contra-indicate opium or morphine poisoning. Teath occasion-
ally terminates by convulsion. -
The sudden form is that in which the individual sinks into a deep
sleep almost immediately—that is, within five or ten minutes—and dies
in a few hours. In these rapid cases the pupils are said to be constantly
dilated. -
Examples of the convulsive form are to be sought among opium-eaters,
or persons under otherwise abnormal conditions.
A man, 40 years old, who had taken opiates daily since his 22nd
* R. Stockman and Dott, Brit. Med. Journ. (2), 1890, 189–192.
+ Tardieu, Étude Méd. Légale sur l'Empoisonnement.
† In a remarkable case related by Taylor, a lady took a large dose (supposed to be
1% oz.) of laudanum, and there were no symptoms for four and a half hours. She
died in twenty-two hours. - -
§ 359.] MORPHINE. 307
year—his dose being 6 grims. (92.4 grains) of solid opium—when
out hunting, of which sport he was passionately fond, took cold, and,
as a remedy, administered to himself three times his accustomed dose.
Very shortly there was contraction of the left arm, disturbance of vision,
pain in the stomach, faintness, inability to speak, and unconsciousness
which lasted half an hour. Intermittent convulsions now set in, and
pains in the limbs. There was neither somnolence nor delirium, but
great agitation; repeated vomiting and diarrhoea followed. After five
hours these symptoms ceased ; but he was excessively prostrate.* There
was complete recovery.
One may hazard a surmise that, in such a case, tolerance has been
established for morphine, but not for other morphine alkaloids in the
same degree, and that the marked nervous symptoms were in no small
degree the effect of some of the homologous alkaloids, which, in such an
enormous dose, would be taken in sufficient quantity to have a physio-
logical action.
There are several instances of a relapsing or remittent form of
poisoning—a form in which the patient more or less completely recovers
consciousness, and then sinks back into a fatal slumber. One of the
best known is the case of the Hon. Mrs Anson (January 1859), who
swallowed an ounce and a half of laudanum by mistake. After
remaining in a comatose condition for more than nine hours, she
revived. The face became natural, the pulse steady. She was able to
recognise her daughter, and in a thick voice to give an account of the
mistake. But this lasted only ten minutes, when she again became
comatose, and died in fourteen hours. i.
In a Swedish case quoted by Maschka, ; a girl, 9 years old, in
weak health and suffering from slight bronchitis, had been given a non-
officinal acetate of morphia lozenge, which was supposed to contain 5
mgrms. (.075 grain) of morphine acetate. She took the lozenge at
8 in the evening ; soon slept, woke at 10, got out of bed, laughed,
talked, and joked with the nurse, again got into bed, and very quickly
fell asleep. At 4 A.M. the nurse came and found her breathing
with a rattling sound, and the physician, who arrived an hour later,
found the girl in a state of coma, with contracted pupils, breathing
stertorously, and the pulse scarcely to be felt. Despite all attempts
to rouse the patient, she died at 8 in the morning, twelve hours after
taking the lozenge.
* Demontporcellet, De l'Usage Quotidien de l'Opium, Paris, 1874.
t Taylor, op. cit.
# Maschka's Handbuch, Band ii. p. 438 ; also Svenska, Läk-Sällsk. Fürhandl.,
Apr. 1, p. 90 ; Apr. 8, p. 160, 1873. For other cases see Nasmyth, Edin. Med.
Journ., Dec. 1878; Kirby, Dub. Med. Press, Dec. 24, 1845; W. Boyd Muschet,
Med. Times and Gaz., March 20, 1858.
308 . POISONS : THEIR EFFECTS AND DETECTION. [$ 359.
The post-mortem examination showed some hyperaemia of the brain
and serous effusion in the ventricles, and there was also tubercle in the
pleura. Three lozenges similar to the one taken by the patient were
chemically investigated by Hamberg, who found that the amount of
acetate was very small, and that the lozenges, instead of morphine
acetate, might be considered as prepared with almost pure morphine;
the content in the three of morphine being respectively 35, 37, and
42 mgrms. (that is, from half a grain to three-fifths of a grain). There
was a difference of opinion among the experts as to whether in this case
the child died from morphine poisoning or not—a difference solely to
be attributed to the waking up of the child two hours after taking the
poison. Now, considering the great probability that a large dose for
a weakly child of that age had been taken, and that this is not the
only case in which a relapse has occurred, it seems just to infer that it
was really a case of poisoning.
As unusual symptoms (or rather sequelae) may be noted in a few
cases, hemiplegia, which soon passes off; a weakness of the lower
extremities may also be left, and inability to empty the bladder
thoroughly ; but usually on recovery from a large dose of opium, there
is simply heaviness of the head, a dry tongue, constipation, and loss of
appetite. All these symptoms in healthy people vanish in a day or two.
There have also been noticed slight albuminuria, eruptions on the skin,
loss of taste, and numbness of parts of the body. t
Opium, whether taken in substance, or still more by subcutaneous
injection, in some individuals constantly causes faintness.
Some years ago the senior author injected one-sixth of a grain of mor-
phine hydrochlorate subcutaneously into an old gentleman, who was
suffering from acute lumbago, but was otherwise healthy, and had no
heart disease which could be detected ; the malady was instantly relieved,
and he called out, “I am well; it is most extraordinary.” He went out
of the front door, and walked some fifty yards, and then was observed to
reel about like a drunken man. He was supported back and laid in the
horizontal posture; the face was livid, the pulse could scarcely be felt,
and there was complete loss of consciousness. This state lasted about
an hour, and without a doubt the man nearly died. Medical men in
practice, who have been in the habit of using hypodermic injections of
morphine, have had experiences very similar to this and other cases,
and it is evident that morphine, when injected hypodermically even in
a moderate dose, may kill by syncope, and within a few minutes.*
* See a case of morphia poisoning by hypodermic injection, and recovery, by
Philip E. Hill, M.R.C.S., Lancet, Sept. 30, 1882. In this instance a third of a
grain introduced subcutaneously caused most dangerous symptoms in a gardener,
aged 48.
$ 360.] MORPHINE. 3O9
Absorption by hypodermic administration is so rapid that by the time,
or even before the needle of the syringe is withdrawn, a contraction of
the pupil may be observed.
Opium or morphine is poisonous by whatever channel it gains access
to the system; the intestinal mucous membrane absorbs it readily, and
marcotic effects may be produced by external applications, whether a
wound is present or not. A case of absorption of opium by a wound is
related in Chever's Jurisprudence.* A Burmese boy, about 9 or 10 years
of age, was struck on the forehead by a brickbat, causing a gaping
wound about an inch long ; his parents stuffed the wound with opium.
On the third day after the accident, and the opium still remaining in the
wound, he became semi-comatose, and, in short, had all the symptoms
of opium narcosis; with treatment he recovered. The unbroken skin
also readily absorbs the drug. Tardieu states that he had seen 30 grms.
of laudanum, applied on a poultice to the abdomen, produce death.
Christison has also cited a case in which a soldier suffered from erysipelas,
and died in a narcotic state, apparently produced from the too free
application of laudanum to the inflamed part.
To these cases may be added the one cited by Taylor, in which a
druggist applied 30 grains of morphine to the surface of an ulcerated
breast, and the woman died with all the symptoms of narcotic poisoning
ten hours after the application—an event scarcely surprising. It is a
curious question whether sufficient of the poison enters into the secre-
tions—e.g. the milk—to render it poisonous. An inquest was held
in Manchester, Nov. 1875, on the body of a male child 2 days old,
in which it seemed probable that death had occurred through the
mother's milk. She was a confirmed opium-eater, taking a solid ounce
per week.
§ 360. Diagnosis of Opium Poisoning.—The diagnosis is at times
between poisoning by opium or other narcotic substances; at others,
between opium and disease. Insensibility from chloral, from alcohol,
from belladonna or atropine, and from carbon monoxide gas, are all more
or less like opium poisoning. With regard to chloral, it may be that only
chemical analysis and surrounding circumstances can clear up the matter.
In alcohol poisoning, the breath commonly smells very strongly of
alcohol, and there is no difficulty in separating it from the contents of
the stomach, etc., besides which the stomach is usually red and inflamed.
Atropine and belladonna invariably dilate the pupil, and although just
before death opium has the same effect, yet we must hold that mostly
opium contracts, and that a widely-dilated pupil during life would, per se,
lead us to suspect that opium had not been used, although, as before
mentioned, too much stress must not be laid upon the state of the pupils.
* Third ed., p. 228.
3 IO POISONS : THEIR EFFECTS AND DETECTION. [$ 361.
In carbon monoxide, the peculiar rose-red condition of the body affords a
striking contrast to the pallor which, for the most part, accompanies
opium poisoning. In the rare cases in which convulsions are a prominent
symptom, it may be doubtful whether opium or strychnine has been taken;
but the convulsions hitherto noticed in opium poisoning seem to have
been rather of an epileptiform character, and very different from the
effects of strychnine. No rules can be laid down for cases which do not
run a normal course; in medicine such are being constantly met with, and
require all the care and acumen of the trained observer. Cases of disease
render a diagnosis often extremely difficult, and the more so in those in-
stances in which a dose of laudanum or other opiate has been administered.
In a case under the observation of one of us, a woman, suffering from
emphysema and bronchitis, sent to a chemist for a sleeping draught,
which she took directly it arrived. A short time afterwards she fell into
a profound slumber, and died within six hours. The draught had been
contained in an ounce-and-a-half bottle ; the bottle was empty, and the
druggist stated in evidence that it only contained 20 minims of laudanum,
10 grains of potassic bromide, and water. On, however, diluting the
single drop remaining in the bottle, and imitating its colour with several
samples of laudanum diluted in the same way, the conclusion was come to
that the quantity of laudanum which the bottle originally contained was
far in excess of that which had been stated, and that it was over
1 drachm and under 2 drachms. The body was pallid, the pupils
strongly contracted, the vessels of the brain membranes were filled with
fluid blood, and there was about an ounce of serous fluid in each
ventricle. The lungs were excessively emphysematous, and there was
much secretion in the bronchi; the liver was slightly cirrhotic. The
blood, the liver, and the contents of the stomach were exhaustively
analysed with the greatest care, but no trace of morphine, marcotine, or
mecomic acid could be separated, although the woman did not live more
than six hours after taking the draught. It was, in the woman's state,
improper to prescribe a sedative of that kind, and probably death had
been accelerated, if not directly caused, by the opium.
Deaths by apoplexy will only simulate opium-poisoning during life;
a post-mortem examination will at once reveal the true nature of the
malady. In epilepsy, however, it is different, and more than once an
epileptic fit has occurred and been followed by coma—a coma which
certainly cannot be distinguished from that produced by a narcotic
poison. Death in this stage may follow, and on examining the body no
lesion may be found.
§ 361. Opium-eating.—The consumption of opium is a very ancient
practice among Eastern nations, and the picture, drawn by novelist and
traveller, of poor, dried-up, yellow mortals addicted to this vice, with
§ 361.] MORPHINE. 3 II
their faculties torpid, their skin hanging in wrinkles on their wasted
bodies, the conjunctivae tinged with bile, the bowels so inactive that
there is scarcely an excretion in the course of a week, the mental faculties
verging on idiocy and imbecility, is only true of a percentage of those
who are addicted to the habit. In the British Medical Journal for
1894, Jan. 13 and 20, will be found a careful digest of the evidence
collated from 100 Indian medical officers, from which it appears that opium
is taken habitually by a very large number of the population through-
out India, those who are accustomed to the drug taking it in quantities of
from 10 to 20 grains in the twenty-four hours; so long as this amount
is not exceeded they do not appear to suffer ill-health or any injurious
effect. The native wrestlers even use it whilst training. The habitual
consumption of opium by individuals has a direct medico-legal bearing.
Thus in India, among the Rajpoots, from time immemorial, infused
opium has been the drink both of reconciliation and of ordinary greeting,
and it is no evidence of death by poison if even a considerable quantity
of opium be found in the stomach after death, for this circumstance
taken alone would, unless the history of the case was further known, be
considered insufficient proof. So, again, in all climates, and among all
races, it is entirely unknown what quantity of an opiate should be con-
sidered a poisomous dose for an opium-eater. Almost incredible quantities
have, indeed, been consumed by such persons; and the commonly-received
explanation, that the drug, in these cases, passes out unabsorbed,
can scarcely be correct, for Hermann mentions the case of a lady of
Zurich who daily injected subcutaneously 1 to 2 grms. (15–31 grains) of a
morphine salt. In a case of uterine cancer, recorded by Dr. W. C. Cass,”
20 grains of morphine in the twelve hours were frequently used sub-
cutaneously; during thirteen months the hypodermic syringe was used
1350 times, the dose each time being 5 grains. It is not credible that
an alkaloid introduced into the body hypodermically should not be
absorbed.
Opium-smoking is another form in which the drug is used, but it is
an open question as to what poisonous alkaloids are in opium smoke. It
is scarcely probable that morphine should be a constituent, for its sub-
liming point is high, and it will rather be deposited in the cooler portion
of the pipe. Opium, specially prepared for smoking, is called “Chandoo”;
it is dried at a temperature not exceeding 240°. H. Moissan i has
investigated the products of smoking chandoo, but only found a small
quantity of morphine. N. Grehant and E. Martin f have also experi-
mented with opium smoke; they found it to have no appreciable effect
on a dog; one of the writers smoked twenty pipes in succession, contain-
* Lancet, March 25, 1882. See also Dr. Boulton’s case, Lancet, March 18, 1882.
t Compt. Rend., czv. 988–992. f Compt. Rend., CNv. 1012–1014.
3 I2 POISONS: THEIR EFFECTS AND DETECTION. [$ 362, 363.
ing altogether 4 grns, of chandoo. After the fourth pipe there was
some headache, at the tenth pipe and onwards giddiness. Half an hour
after the last pipe the giddiness and headache rapidly went off. In any
case, opium-smoking seems to injure the health of Asiatics but little.
Mr. Vice-Consul King, of Kew-Kiang, in a tour through Upper Yangtse
and Szechuan, was thrown much into the company of junk sailors and
others, “almost every adult of whom smoked more or less.” He says:
—“Their work was of the hardest and rudest, rising at 4 and working
with hardly any intermission till dark, having constantly to strip and
plunge into the stream in all seasons, and this often in the most
dangerous parts. The quantity of food they eat was simply prodigious,
and from this and their work it seems fairly to be inferred that their
constitution was robust. The two most addicted to the habit were the
pilot and the ship's cook. On the incessant watchfulness and steady
nerve of the former the safety of the junk and all on board depended;
while the second worked so hard from 3 A.M. to 10 P.M., and often
longer, and seemed so independent of sleep or rest, that to catch him
seated or idle was sufficient cause for good-humoured banter. This
latter had a conserve of opium and sugar which he chewed during the
day, as he was only able to smoke at might.”
§ 362. Treatment of Opium or Morphine Poisoning.—The first
thing to be done is doubtless to empty the stomach by means of the
flexible stomach-tube; the end of a sufficiently long piece of indiarubber
tubing is passed down into the pharynx and allowed to be carried into
the stomach by means of the natural involuntary movements of the
muscles of the pharynx and gullet; suction is then applied to the free
end and the contents syphoned out ; the stomach is, by means of a
funnel attached to the tube, washed out with warm water, and then
some coffee administered in the same way.
Should morphine have been taken, and permanganate of potash be
at hand, it has been shown that under such circumstances potassic per-
manganate is a perfect antidote, decomposing at once any morphine
remaining in the stomach ; but it, of course, will have no effect upon any
morphine which has already been absorbed. In a case of opium poison-
ing, reported in the Lancet of June 2, 1894, by W. J. C. Merry, M.B.,
inhalations of oxygen, preceded by emptying the stomach and other
means, appeared to save a man, who, three hours before the treatment,
had drunk 2 ozs. of chlorodyne. It is also the received treatment
to ward off the fatal sleep by stimulation ; the patient is walked about,
flicked with a towel, made to smell strong ammonia, and so forth. This
stimulation must, however, be an addition, but must never replace the
measures first detailed.
§ 363. Post-mortem Appearances.—There are no characteristic
§ 364.] MORPHINE. 3I 3
appearances after death save hyperamia of the brain and blood-vessels
of the membranes, with generally serous effusion into the ventricles.
The pupils are sometimes contracted, sometimes dilated, the dilatation
occurring, as before mentioned, in the act of dying. The external
surface of the body is either livid or pale. The lungs are commonly
hyperamic, the bladder full of urine; still, in not a few cases,
there is nothing abnormal, and in no single case could a pathologist,
from the appearance of the organs only, declare the cause of death
with confidence.
§ 364. Separation of Morphine from Animal Tissues and Fluids,-
Formerly a large proportion of the opium and morphine cases submitted
to chemical experts led to no results; but owing to the improved processes
now adopted, failure, though still common, is less frequent. The con-
stituents of opium taken into the blood undergo partial destruction in
the animal body, but a portion may be found in the secretions, more
especially in the urine and faeces. First Bouchardat “ and then Lefort f
ascertained the excretion of morphine by the urine after medicinal
doses; Dragendorff and Kauzmann showed that the appearance of
morphine in the urine was constant, and that it could be easily ascer-
tained and separated from the urine of men and animals; and Levinstein f
has also shown that the elimination from a single dose may extend over
five or six days. The method used by Dragendorff to extract morphine
from either urine or blood is to shake the liquid (acidified with a
mineral acid) several times with amyl alcohol, which, on removal,
separates urea and any bile acids. The liquid thus purified is then
alkalised, and shaken up with amyl alcohol, and this amyl alcohol
should contain any morphine that was present. The alcoholic solution
is treated as detailed on p. 315. Considerable variety of results seems
to be obtained by different experimenters. Landsberg $ injected
hypodermically doses of 2 to 4 grn. of morphine hydrochlorate into
dogs, making four experiments in all, but failed to detect morphine in
the urine. A large dose with 2-4 mgrms. of the salt gave the same
result. On the other hand, 8 grim. of morphine hydrochlorate injected
direct into the jugular vein, was partly excreted by the kidneys, for
90 c.c. of the urine yielded a small quantity of morphine. Voit, again,
examined the urine and faeces of a man who had taken morphine for
years; he could detect none in the urine, but separated morphine from
the faeces.|| Morphine may occasionally be recognised in the blood.
* Bull. Gén. de Thérap., Dec. 1861.
t Journ. de Chim., xi. 93, 1861.
† Berl. klin. Wochenschr., 1876, 27.
§ Pflüger's Archiv., xxiii. 413–433. Chem. Soc. Jowrm., May 1882, 543.
| Arch. Pharm., [3], vii. pp. 23–26.
3I4 POISONS : THEIR EFFECTS AND DETECTION. [$ 365.
Dragendorff” found it in the blood of a cat twenty-five minutes after a
subcutaneous dose, and he also separated it from the blood of a man
who died of morphine poisoning in six hours. Haidlen f recognised
morphine in the blood of a suicide who had taken opium extract.
On the other hand, in a case where a woman died in six hours from
a moderate dose, probably of laudanum, although the quantity of blood
operated upon was over a pound in weight, and every care was taken,
the results were entirely negative. In poisoning by laudanum there
may be some remaining in the stomach, and also if large doses of
morphine have been taken by the mouth ; but when morphine has
been administered hypodermically, and in all cases in which several
hours have elapsed, one may almost say that the organ in which there
is the least probability of finding the poison is the stomach. It may,
in some cases, be necessary to operate on a very large scale;—to
examine the faeces, mince up the whole liver, the kidney, spleen, and
lungs, and treat them with acid alcohol. The urine will also have to be
examined, and as much blood as can be obtained. In cases where all
the evidence points to a minute quantity (under a grain) of morphine,
it is decidedly best to add these various extracts together, to distil off
the alcohol at a very gentle heat, to dry the residue in a vacuum,
to dissolve again in absolute alcohol, filter, evaporate again to dryness,
dissolve in water, and then use the following process:–
§ 365. Extraction of Morphine.—To specially search for morphine in
such a fluid as the urine, it is, according to the authors’ experience, best
to proceed strictly as follows:—The urine is precipitated with acetate of
lead, the powdered lead salt being added to the warm urine contained in
a beaker on the water-bath, until a further addition no longer produces
a precipitate; the urine is then filtered, the lead precipitate washed, and
the excess of lead thrown down by SH2 ; the lead having been filtered
off, and the precipitate washed, the urine is concentrated down to a syrup
in a vacuum. The syrup is now placed in a separating tube (if not acid,
it is acidified with hydrochloric acid), and shaken up successively with
petroleum ether, chloroform, ether, and, lastly, with amylic alcohol (the
latter should be warm); finally, the small amount of amylic alcohol left
dissolved in the liquid is got rid of by shaking it up with petroleum
ether. To get rid of the last traces of petroleum ether, it may be neces-
sary to turn the liquid into an evaporating dish, and gently heat for a
little time over the water-bath. The acid liquid is now again transferred
to the separating tube, and shaken up with ether, after being made
* Kauzmann, Beiträge für den gerichtlich-chemischen Nachweis des Morphia w.
Narcotins, Dissert., Dorpat, 1868. Dragendorff, Pharm. Zeitschr. f. Russland, 1868,
Hft. 4.
+ Wiirtbg. Correspondemzbl., xxxiv. 16, 1896.
§ 366.] NARCOTINE. 3 I 5
alkaline with ammonia; this will remove nearly all alkaloids save mor-
phine,— under the circumstances, a very small quantity of morphine may
indeed be taken up by the ether, but not the main bulk. After separat-
ing the ether, the liquid is again made slightly acid, so as to be able to
precipitate morphine in the presence of the solvent; the tube is warmed
on the water-bath, at least its own bulk of hot amylic alcohol added and
the liquid made alkaline, and the whole well shaken. The amylic
alcohol is removed in the usual way, and shaken with a small quantity
of decinormal sulphuric acid; this washes out the alkaloid from the
amyl alcohol, and the same amyl alcohol can be used again and again.
It is best to extract the liquid for morphine at least thrice, and to
operate with both the solution and the amyl hot. The decinormal acid
liquid is made slightly alkaline with ammonia, and allowed to stand for
at least twelve hours; any precipitate is collected and washed with
ether, and then with water; the alkaline liquid from which the mor-
phine has been separated is concentrated to the bulk of 5 c.c. on the
water-bath, and again allowed to stand for twelve hours; a little more
morphine may often in this way be obtained.
The authors in some test experiments, in which weighed small
quantities of morphine (60–80 mgrms.) were dissolved in a little deci-
normal sulphuric acid, and added to large quantities of urine, found the
process given to yield from 80 to 85 per cent. of the alkaloid added, and
it was always recovered in fine crystals of a slight brown tint, which
responded well to tests.
Various other methods were tried, but the best was the one given ;
the method not only separates the alkaloid with but little loss, but also
in a sufficiently pure state to admit of identification.
From the tissues the alkaloid may be dissolved out by the general
method given at p. 51, and the ultimate aqueous solution, reduced to
a bulk of not more than 25 c.c., treated by the ethereal solvents in the
way just described.
§ 366. Narcotine (Cas Has NO,) crystallises out of alcohol or ether in
colourless, transparent, glittering needles, or groups of needles, belong-
ing to the orthorhombic system. -
It is only slightly soluble in boiling, and almost insoluble in cold
water. One part requires 100 parts of cold, and 20 of boiling 84 per
cent. alcohol; 126 parts of cold, 48 of boiling ether (specific gravity
0-735); 2.69 parts of chloroform ; 400 of olive oil; 60 of acetic ether;
300 of amyl alcohol; and 22 parts of benzene, for solution. The neutral
solution of narcotine turns the plane of polarisation to the left [a]r =
130°6’; the acid solution to the right. Narcotine has no effect on red
litmus-paper.
Narcotine gives no crystalline sublimate; its behaviour in the sublim-
316 POISONS : THEIR EFFECTS AND DETECTION. [$ 366.
ing cell is described at p. 261. Its melting-point, taken in a tube, is
about 176°.
Behaviour of Narcotine with Reagents.—Narcotine, dissolved in
dilute hydrochloric acid, and then treated with a little bromine, gives a
yellow precipitate, which on boiling is dissolved ; by gradually adding
solution of bromine and boiling, a fine rose colour is produced, readily
destroyed by excess of bromine. This is perhaps the best test for the
presence of marcotine. Concentrated sulphuric acid dissolves narcotine;
the solution in the cold is at first colourless, after a few minutes yellow,
and in the course of a day or longer the tints gradually deepen. If the
solution is warmed, it first becomes orange-red, then at the margin
violet-blue; and if heated until hydric sulphate begins to volatilise, the
colour is an intense red-violet. If the heating is not carried so far, but
the solution allowed to cool, a delicate cherry-red hue slowly develops.
If the sulphuric acid solution contains 1: 2000 of the alkaloid, this
test is very evident ; with 1 : 40,000, the colour is only a faint carmine.
—A. Husemann.
A solution of narcotine in pure sulphuric acid, to which a drop of
mitric acid has been added, becomes of a red colour; if the solution is
warmed to 150°, hypochlorite of soda develops a carmine-red; and
chloride of iron, first a violet, then a cherry-red. The precipitants
of narcotine are—phosphomolybdic acid, picric acid, sulphocyanide of
potash, potassio cadmic iodide, mercuric chloride, platinic chloride, auric
chloride, and several other reagents.
Constitution of Narcotine.—Narcotine contains three methoxyl
groups, and also an N-CHA group, for when heated with alkalies
to 220° it yields methylamine, dimethylamine, and trimethylamine.
Heated with water or H2SO, at 140° it yields Clo HoO, opianic acid
and C19H16NOs hydrocotarnine. Hydrocotarmine is the reduction pro-
duct of cotarnine and is a derivative of methyl tetrahydroisoquinoline,
CH,
CH.O. KYS CH,
CH2
Hydrocotarmine,
Opianic acid when oxidised forms hemip'nic acid ; and, when reduced,
mecomine ; and may be represented as
CHO oft
ſ – COOH HC––O
tº e g |
—OCH, or in its tautomeric form as ^ – CO
OCH, – OCHA
Opianic Acid. OCH,
§ 367, 368.] CODEINE. 317
Narcotine is a tertiary base and contains no carboxyl or aldehyde
group, so that its formula is probably
CH,
CH,0, º/N CH,
|
CH-O
|
º
NZ
bon,
Narcotime.
§ 367. Effects.—Narcotime in itself has toxic action only in rather
large doses; from 1 to 2 grms. have been given to man, and slight
hypnotic effects have followed. It is poisonous in very large doses;
an ordinary-sized cat is killed by 3 groms. The symptoms are mainly
convulsions.
§ 368. Codeine (Codomethylene), Cly Hız0CH3(OH)NO + H2O, is the
monomethyl ester of morphine; it is an alkaloid contained in opium
in small quantity only. Mulder, indeed, quotes '66 to 77 per cent, as
present in Smyrna opium, but Merck and Schindler give 25 per cent.
Schindler found in Constantinople, 5 per cent. ; and Merck, in Bengal,
‘5 per cent. also.
Codeine crystallises out of dry ether in small, colourless, anhydrous
crystals; but crystallised slowly from an aqueous solution, the crystals
are either in well-defined octahedra, or in prisms, containing one atom of
water, and melting in boiling water to an oily fluid. The anhydrous
crystals have a melting-point of 155°, and solidify again on cooling. Its
watery solution is alkaline to litmus-paper.
It requires 80 parts of cold, 17 of boiling water, 76 of carbon tetra-
chloride, 10 parts of benzole, and 7 parts of amyl alcohol respectively,
for solution. Alcohol, benzene, ether, carbon disulphide, and chloroform
freely dissolve it, but in petroleum ether it is almost insoluble. Further,
it is also soluble in aqueous ammonia and in dilute acids, but insoluble
in excess of caustic potash or soda, and may thus be thrown out of an
aqueous solution. A solution of codeine turns the plane of polarisation
to the left, [a]r = 118.2°.
Concentrated sulphuric acid dissolves codeine without colour, but after
eight days the solution becomes blue ; this reaction is quicker if the acid
contains a trace of nitric acid. If the sulphuric acid solution be warmed
to 150°, and a drop of nitric acid be added after cooling, a blood-red
colour is produced. Fröhde's reagent produces a dirty green colour,
3.18 POISONS : THEIR EFFECTS AND DETECTION, [$ 369.
soon becoming Prussian blue, and terminating after twenty-four hours
in a pale yellow.
Cyanogen gas, led into an alcoholic solution of codeine, gives first a
yellow and then a brown colour; lastly, a crystalline precipitate falls.
On warming with a little sulphuric acid and ferric chloride, a blue colour
is produced. This blue colour is apparently common to all ethers of the
codeine class.
Of the group reagents, the following precipitate solutions of codeine:
—Mercuric potassium iodide, mercuric chloride, mercuric bromide, picric
acid, and tannin solutions. The following do not precipitate – Mercuric
cyamide and potassium ferrocyanide solutions. Potassium dichromate
gives no immediate precipitate, but crystals form on long standing. It
does not give the reaction with iodic acid like morphine ; it is dis-
tinguished from narceine by dropping a small particle of iodine into the
aqueous solution—the iodine particle does not become surrounded with
fine crystals.
§ 369. Effects.—The physiological action of codeine on animals has
been investigated by Claude Bernard, Magendie, Crum Brown and
Fraser, Falck, and a large number of others.” It has also been ad-
ministered to man, and has taken in some degree the place of morphine.
Claude Bernard showed that, when given to dogs in sufficient quantity
to produce sleep, the sleep was different in some respects to that of
morphine sleep, especially in its after-effects. Thus, in his usual graphic
way, he describes the following experiment:—“Two young dogs, ac-
customed to play together, and both a little beyond the average size,
received in the cellular tissue of the axillae, by the aid of a subcutaneous
syringe, the one 5 centigrammes of morphine hydrochloride, the other
5 centigrammes of codeine hydrochloride. At the end of a quarter of
an hour both dogs showed signs of narcosis. They were placed on their
backs in the experimental trough, and slept tranquilly for three or four
hours. When the animals woke, they represented a striking contrast.
The morphine dog ran with a hyena-like gait (démarche hyénoid), the
eyes wild, recognising no one, not even his codeine comrade, who vainly
bit him playfully, and jumped sportively on his back. It was not until
the next day that the morphine dog regained his spirits and usual
humour. A couple of days after, the two dogs being in good health, I
repeated the same experiment, but in a reverse order—that is to say, I
gave the codeine to that which previously had the morphine, and vice
versa. Both dogs slept about as long as the first time; but on waking
the attitudes were completely reversed, just as the administration of the
two substances had been. The dog which, two days before, after having
* Amn. Chem. Phys. [5], xxvii. pp. 273–288; also, Journ. Chem. Soc., No.
ccxliv., 1883, p. 358. - -
§ 370.] NARCEINE. 319
been codeinised, woke lively and gay, was now bewildered and half
paralysed at the end of his morphine sleep; whilst the other was wide
awake and in the best spirits.”
Subsequent experimenters found what Bernard does not mention—
viz., that codeine produced epileptiform convulsions. Falck made some
very careful experiments on pigeons, frogs, and rabbits. To all these
in high enough doses it was fatal. Falck puts the minimum lethal dose
for a rabbit at 51.2 mgrms. per kilo. Given to man, it produces a sleep
very similar to that described by Claude Bernard—that is, a sleep which
is very natural, and does not leave any after-effect. Therefore it is
declared to be the best alkaloid of a narcotic nature to give when
lengthened slumber is desired, more especially since it does not con-
fine the bowels, nor has it been found to produce any eruption on the
skin. . Before it has a full narcotic effect, vomiting has often been
excited, and in a few cases purging. The maximum dose for an adult
is about 1 grm. (1-5 grain); three times this quantity, 3 grims.
(4.5 grains), would probably produce unpleasant, if not dangerous,
symptoms.”
§ 370. Narceine, C23H31NOs--3H2O. —Two of the three molecules of water are
expelled at 100°; the other molecule requires a higher temperature. Anhydrous
narceine is hygroscopic, and melts in a tube at about 145°; when exposed to air it
unites with one molecule of water, and then melts at about 170°.
The constitution of marceine, according to Freund and Frankforter, f may be
represented thus:—
CH2
|
CO
|
| – COOH
- H
yº
OCH
It therefore contains three methoxyl groups. &
Narceine forms good crystals, the form being that of long, four-sided rhombic
prisms or fine bushy united needles.
Narceine hydrochloride crystallises with 5%H2O and with 3H2O ; the anhydrous
salt melts at 190°–192°. The platinochloride is a definite salt, m.p. 190°–191° ; it
decomposes at 195°-196°. The nitrite forms good crystals, which decompose at 97°.
* For further details as to the action of codeine, the reader is referred to L. O.
Wach's monograph, Das Codein (1868), which contains reference to the earlier
literature. See also Harley, The Old Vegetable Neurotics, London.
+ M. Freund and G. B. Frankforter, Annalem, cclxxvii. pp. 20–58.
32O POISONS: THEIR EFFECTS AND DETECTION. [$ 37 I.
Narceine also forms crystalline salts with potassium and sodium ; these may be
obtained by heating he base at 60°–70° with a 33 per cent. of NaHO or
KHO.
The potassium compound melts at 90°, the sodium at 159°–160°. The alkaloid is
regenerated when the alkali salts are treated with acids or with CO2. Crude narceine
may be purified by means of the sodium salt; the latter is dissolved in alcohol and
precipitated with ether.
It is soluble in alcohol, but almost insoluble in alcohol and ether, or benzene and
ether, as well as in carbon tetrachloride; it is slightly soluble in ether, carbon
disulphide, and chloroform. It has no reaction on moist litmus-paper.
Benzole and petroleum ether extract narceine neither from acid nor alkaline
solutions ; chloroform extracts narceine both from acid and from alkaline solutions,
the latter in small proportion only. Narceine turns the plane of polarisation to the
left, aſ r) = 66.7°. Narceine may be separated from marcotine by the addition of
ammonia to the acid aqueous solution ; narcotine is fully precipitated by ammonia,
but marceine is left in solution.
In the subliming cell it melts at 134°, but gives no crystalline sublimate. The
tube melting-point of the trihydrate is 170°. The melted substance is at first colour-
less; but on raising the temperature, the usual transitions of colour through different
shades of brown to black are observed. If melted, and kept a few degrees above its
melting-point, and then cooled slowly, the residue is straw-coloured, divided into
lobes, most of which contain feathery crystals.
At high temperatures marceine develops a herring-like odour ; the residue
becomes darkish blue with iron chloride. Concentrated nitric acid dissolves it with
a yellow colour; on heating, red vapours are produced ; the fluid contains crystals of
oxalic acid, and develops with potash a volatile base. Concentrated sulphuric acid
colours pure narceine brown ; but if impure, a blood-red or blue colour may be pro-
duced. It does not reduce iron salts.
Fröhde's reagent colours it first brown-green, then red, passing into blue.
Narceine forms precipitates with bichromate of potash, chloride of gold, bichloride of
platinum, and several other reagents. The one formed by the addition of potassio
zinc iodide is in hair-like crystals, which after twenty-four hours become blue.
Weak iodine solution colours narceine crystals a black-blue ; they dissolve in
water at 100° without colour, but on cooling again separate with a violet or blue
colour. If on a saturated solution of marceine a particle of iodine is strewn, fine
needle-like grey crystals form around the iodine. A drop of “Nessler” solution,
added to solid marceine, at once strikes a brown colour ; on diluting the drop with a
little water, beautiful little bundles of crystals appear.—Flückiger.
The following group reagents precipitate marceine :-picric acid, tannin solution,
and potassium dichromate on long standing. The following give no precipitate :-
mercuric cyanide, mercuric potass, iodide, mercuric chloride, mercuric bromide, and
potass, ferrocyanide solutions,
§ 371. Effects. –The physiological action of marceine has been variously inter-
preted by different observers. Claude Bernard” thought it the most somniferous
of the opium alkaloids. He said that “the marceine sleep was characterised
by a profound calm and absence of the excitability of morphine, the animals
narcotised by narceine on awaking returning to their natural state without
enfeeblement of the hind limbs or other sequelae.” It has been amply confirmed
that narceine possesses somniferous properties, but certainly not to the extent that
Bernard’s observations led physiologists to expect. In large doses there is some
irritation of the stomach and intestines, and vomiting occurs, and even diarrhoea;
moderate doses induce constipation. The maximum medicinal dose may be put
* Compt, Remd., lix. p. 406, 1864.
$ 372, 373.] PAPAVERINE. - 32 I
at 14 grm, (or 2.26 grains), and a probably dangerous dose would be three times
that quantity.” -
§ 372. Papaverine (C26H31NO3) crystallises from alcohol in white needles or scales.
It possesses scarcely any alkaline reaction, but its salts have an acid reaction ; it has
but little effect on a ray of polarised light. It is almost insoluble in water; it is
easily soluble in acetone, amyl alcohol, alcohol, and chloroform. One part of the
alkaloid is dissolved in 36-6 of benzene, in 76 parts of amyl alcohol, and in 490 parts
of carbon tetrachloride. Petroleum ether dissolves it by the aid of heat, but the
alkaloid separates in crystals on cooling. Chloroform extracts it from either acid or
alkaline solutions. Papaverine gives no crystalline sublimate. The melting-point
of pure samples in a tube is 147°, with scarcely any colour; it solidifies again to
crystals on cooling; in the subliming cell it melts at 130°, and decomposes about
149° ; the vapours are alkaline; the residue is amorphous, light brown, and is not
characteristic. Concentrated sulphuric acid colours it a deep violet-blue, and
dissolves it to a violet, slowly fading. This solution, by permanganate of potash, is
first green and then grey. Some samples of commercial papaverine consist of
p-papaverine, which dissolves in concentrated H2SO4 to a colourless solution.f Fröhde's
reagent gives a beautiful violet colour, which becomes blue, and vanishes after
twenty-four hours. Diluted solutions of salts of papaverine are not precipitated by
phospho-molybdic acid. It is precipitated by ammonia, by the caustic and carbonated
alkalies, by potassic-cadmic iodide, iodine in hydriodic acid, and by alkaloidal
reagents generally—save by the important exception mentioned above. A solution
in amyl alcohol is also precipitated by bromine; the precipitate is crystalline. An
alcoholic solution of platinic chloride also separates papaverine platin chloride in
crystals. An alcoholic solution of iodine, added to an alcoholic solution of papa-
verine, separates in a little time crystals of the composition C20H21NOAIs. From the
mother-liquor, by concentration, can be obtained needles of another iodine combina-
tion, CooHo, NOAIs; the latter heated above 100° parts with free iodine. These com-
pounds with iodime are decomposed by ammonia and potash, papaverine separating.
The decomposition may be watched under the microscope. Nitric acid precipitates
from a solution of the sulphate a white nitrate soluble in excess; the precipitate does
not appear at once, but forms in the course of an hour ; it is at first amorphous, but
subsequently crystalline; this, with its physical properties, is a great assistance to
identification. Papaverine is a derivative of isoquinoline ; it contains four methoxyl
groups. Goldschmiedt ascribes to it the following formula:—

CHAO ſº
CH,0 Nº. N
NZ
§ 373. Effects.-Claude Bernard ranked papaverine with the convulsants; probably
the papaverine he had was impure. In any case, subsequent observations have shown
* See J. Bouchardat, La Narcéine, These, Paris, 1865; Harley, The Old
Vegetable Newrotics, Lond, ; Ch. Liné, Etudes sur la Narcéine et son Ehmploš
Thérapeutique, Thése, Paris, 1865; also, Husemann’s Pflanzemstoffe, in which these
and other researches are summarised.
+ Oswald Hesse, J. pr. Chem., 1903 (ii.).
322 Poisons: THEIR EFFECTS AND DETECTION. [$ 374, 375.
that it is to be classed rather with the hypnotic principles of opium, Leidesdorf”
administered it to the insane, and noted slowness of the pulse, muscular weakness,
and drowsiness to follow. The doses were given subcutaneously (42 grim, of the
hydrochloride). Baxt,t experimenting with the frog, found that a milligramme
caused deep sleep and slowing of the heart's action. This action on the heart is
witnessed also on the recently-removed frog's heart. Guinea-pigs, and other small
animals poisoned by strychnine or thebaine, and then given papaverine, did not
seem to be so soon affected with tetanus as when no such remedy was administered.
In Bradbury's experiments (Croonian Lectures, Lancet, July 1899) papaverine proved
to be a powerful depressant. In rats 0.3 grim. per kilo, produced muscular weakness,
slowing of the respiration and pulse, distinct narcosis, but no tetanus. 0.2 grm.
per kilo, kills guinea-pigs by paralysis of the respiration in ten minutes. The fatal
dose of papaverine for a man is unknown. The least quantity likely to cause
dangerous symptoms would be 1 grim. (15'4 grains).
§ 374. Thebaine, Clºhit NO(OCH3)2.—Opium seldom contains much more than 1
per cent. of this alkaloid. It usually forms needles or short crystals. It is alkaline,
and by rubbing becomes negatively electric. It is almost insoluble in water, aqueous
ammonia, and solutions of the alkalies. It requires 10 parts of cold alcohol for
solution, and dissolves readily in hot. Ether, hot or cold, is also a good solvent.
100 parts of benzene are required for 5:27 parts of thebaine, and 100 of amyl alcohol
for 1.67 parts. Chloroform dissolves thebaine with difficulty out of both acid and
alkaline solutions; petroleum ether extracts it from neither. Thebaine melts in a
tube at 193°, sublimes at 135°. The sublimate is in minute crystals, similar to
theine; at higher temperatures (160° to 200”) needles, cubes, and prisms are obtained.
The residue is fawn-coloured. Fröhde's reagent (as well as concentrated sulphuric
acid) dissolves it, with the production of a blood-red colour, passing gradually into
yellow. The precipitate with picric acid is yellow and amorphous; with tannic
acid, yellow; with gold chloride, red-yellow ; and with platinic chloride, citron-
yellow, gradually becoming crystalline. A concentrated alcoholic solution of
thebaine, just neutralised with HCl, deposits well-formed rhombic crystals of the
composition ClaRoi NOAHCl 4-H2O. Thebaine is laevorotatory. It is a tertiary base
containing no hydroxyl groups. It contains two methoxyl groups, and is nearly
related to morphine and codeine.
If 200 mgms. of thebaine are heated to boiling with 1.4 c.c. of HCl and 2.8 c.c. of
water, and the solution diluted, after boiling, with 4 c.c. of water, crystals of thebaine
hydrochloride form in the yellow fluid in the course of a few hours.-Flückiger.
§ 375. Effects. –There is no disagreement of opinion as to the action of thebaine.
By the united testimony of all who have experimented with it, the alkaloid belongs
to those poisons which produce tetanus, and the symptoms can scarcely be differ-
entiated from strychnine. In Baxt's experiments on frogs he showed that there was
some considerable difference in details in the general course of the symptoms, accord-
ing to the dose of the poison. A small dose (such, for example, as 75 mgrm.)
injected into a frog subcutaneously produces immediate excitement, the animal
jumping about, and this stage lasting for about a minute; it then becomes quieter,
and has from three to six minutes' sleep; in a little time this comatose state is
followed by reflex tetanic spasms and then spontaneous tetanic spasms. With three
times the dose, the tetanic convulsions commence early, and death takes place in
from two to six hours. Baxt # found 6 to 7 mgrms, kill rabbits with tetanic convul-
* Złschr, d. Wien. Aerzte, pp. 43, 115, 1868.
+ Arch. Amat. Phys., p. 70, 1869.
† Sitzungsber, d. Wien. Akadem., lvi. pp. 2, 89, 1867; Arch. f. Amat, w.
Physiol., Hft. 1, p. 112, 1869.
§ 376–378.] APOMORPHINE. - 323
sions in from fifteen to twenty-five minutes. Crum Brown and Fraser also found
that 12 mgrms, injected into rabbits were fatal; it may then be presumed that the
lethal dose for a rabbit is about 5 mgrms. per kilo. A frog's heart under the action of
thebaine, and removed from the body, beats quicker and ceases earlier than one in
distilled water. Thebaine has been administered to the insane subcutaneously in
doses of from 12 to 40 mgrms., when a rise of temperature and an increase in the
respiratory movements and in the circulation were noticed.”
The fatal dose for a man is not known; 5 grm., or about 8 grains, would prob-
ably be a poisonous quantity.
§ 376. Cryptopine (Cai HºsNOs) was discovered by T. & H. Smith in 1867. It
is contained in very minute traces only in opium—something like '003 per cent. It
is a crystalline substance, the crystals being colourless, six-sided prisms, without
odour, but with a bitter taste, causing an after-sensation like peppermint. The crystals
melt at 213°, and congeal in a crystalline form again at 171°; at high temperatures
they are decomposed with evolution of ammoniacal vapour. Cryptopine is insoluble,
or almost so, in ether, water, and oil of turpentine ; it is soluble in acetone, benzene,
and chloroform ; the latter is the best solvent, or hot alcohol ; it is insoluble in
aqueous ammonia and in solutions of the caustic alkaloids. Cryptopine is strongly
basic, neutralising fully mineral acids. It is optically inactive and contains two
methoxyl groups. Concentrated sulphuric acid colours cryptopine pure blue, the tint
gradually fading from absorption of water from the atmosphere. On a crystal of
potassic nitrate being added, the colour changes into a permanent green. With
ferric chloride cryptopine gives no colour—thus distinguishing it from morphine.
The physiological properties of cryptopine have been investigated by Dr. Harley; †
it has a narcotic action, about double as strong as narceine, and four times weaker
than morphine. Munk and Sippell $ found that it gave rise in animals to paralysis
of the limbs, and occasionally asphyxic convulsions before death.
§ 377. Pseudomorphine (C7H16NO3)2. –Pseudomorphine was discovered by
Pelletier and Thiboumery in 1835. It is non-poisonous, and may be formed by the
condensation of two molecules of morphine and the loss of two atoms of hydrogen.
As precipitated by ammonia out of the hot solution, pseudomorphine falls as a white
crystalline precipitate ; but if the solution is cold, the precipitate is gelatinous. It
possesses no taste, and has no action on vegetable colours. On heating, it decom-
poses and then melts. It dissolves easily in caustic alkalies and in milk of lime, but
is insoluble in all the ordinary alcoholic and ethereal solvents, as well as in diluted
sulphuric acid. The most soluble salt is the hydrochlorate, and that requires 70
parts of water at 20° for solution. Various salts, such as the sulphate, oxalate, etc.,
may be prepared from the hydrochlorate by double decomposition. Concentrated
sulphuric acid dissolves pseudomorphine gradually, with the production of an olive-
green colour.
§ 378. Apomorphine (C17H11NO2).-Apomorphine is a derivative of morphine,
and is readily prepared by Saponifying morphine by heating it with dilute hydro-
chloric acid in sealed tubes. The result is apomorphine hydrochloride, the morphine
losing one molecule of water, according to the equation Cin Hign Os=Cºhn NO3 + H2O.
To extract apomorphine, the bases are precipitated by sodic bicarbonate, and the
precipitate extracted by ether or chloroform, either of which solvents leaves morphine
undissolved. The apomorphine is again converted into hydrochloride, and once
* F. W. Müller, Das Thebaine eine Monographie, Diss., Marburg, 1868.
t Pharm. Journ. Trans. [2], viii. pp. 495 and 716.
# The Old Vegetable Newrotics.
§ Munk, Versuche iber die Wirkung des Cryptopins, Berlin, 1873. Sippell,
Beiträge zwr Kentniss des Cryptopins, Marburg, 1874.
324 Poisons: THEIR EFFECTS AND DETECTION. [$ 379–382.
more precipitated by sodic bicarbonate, and is lastly obtained as a snow-white sub-
stance, rapidly becoming green on exposure to the air. The mass dissolves with a
beautiful green colour in water, and also in alcohol, whilst it colours ether purple-
red, and chloroform violet.
A test for apomorphine is the following:—The chloride is dissolved in a little
acetic acid and shaken with a crystal of potassic iodate (KIO3); this immediately
turns red from liberated iodine on shaking it up with a little chloroform ; on stand-
ing, the chloroform sinks to the bottom, and is coloured by the alkaloid a beautiful
blue colour ; on now carefully pouring a little CS2 on the surface of the liquid at the
point of junction it is coloured amethyst owing to dissolved iodine, and apocodeine
gives a similar reaction.
Apomorphine is the purest and most active emetic known : whether injected
beneath the skin or taken by the mouth, the effect is the same—there is considerable
depression, faintness, and then vomiting. The dose for an adult is about 6 mgrms.
(-092 grain) subcutaneously administered.
§ 379. Laudanine, Cin His N(OH)(OCH3)3, crystallises from alcohol or chloroform
in colourless prisms soluble in benzol, chloroform, and alkalies, not very soluble in
alcohol and ether. Melts at 106°. It is a strong tetanic poison. Laudanidine is
probably the lavo modification of laudanine; it melts at 177°. Laudanosine,
Cº. His N(OCH3), another tetanic poison, has been shown to be dextro-n-methyl-
tetrahydropapaverine ; its inactive form, which may be separated into active lavo-
and dextro-forms, appears to be the monomethyl ester of laudanime. It crystallises in
needles, melting at 89°, and is soluble in alcohol, ether, and chloroform, but not in
water or alkali.
§ 380. Tritopine (C2, H2:NO3)2. —This is a rare alkaloid that hashbeen found in
small quantities in opium. It is crystalline, separating in transparent prisms.
Melting-point 182°. It is soluble in alcohol and chloroform, and slightly soluble in
ether.”
§ 381. Mecomine (Opianyl) (CoH10O3) is in the form of white glittering needles,
which melt at 102°5°. It may be sublimed in beautiful crystals. It is soluble in
22 parts of boiling, and 700 of cold water; dissolves easily in alcohol, ether, acetic
acid, and ethereal oil, and is not precipitated by acetate of lead. It is optically
inactive. Mecomine is the reduction product of opianic acid, and may be formed by
treating narcotine with zinc dust and hydrochloric acid. Its solution in concentrated
sulphuric acid becomes, on warming, purple, and gives, on the addition of water, a
brown precipitate. Meconine, in large doses, is a feeble narcotic ; 125 grim. (20
grains) has been given to man without result.
§ 382. Meconic acid (C, H3O+), or
HC(NCOH
HOOC – J. – COOH
O
crystallises in white shining scales or small rhombic prisms, with three molecules of
water (C.H.O., +3H2O), but at 100° this is lost, and it becomes an opaque white mass.
It reddens litmus, and has a sourish taste. It is soluble in 115 parts of cold, but
dissolves in 4 parts of boiling water ; it dissolves easily in alcohol, less so in ether.
It forms well-marked salts; the barium and calcium salts crystallise with one molecule
of water, the former having the composition BaFI4(C7HOH)2 ; the latter, if ammonium
meconate is precipitated by calcium chloride, CaBA(CºHO), ; but if calcium chloride
is added to the acid itself, the salt has the composition C, H2Ca(); + H2O. If mecomic
* E. Kander, Arch. Pharm., coxxviii., pp. 419–431.
§ 382.] MECONIC ACII). 325
acid is gently heated, it decomposes into carbon dioxide and comenic acid (C6H,05).
If the heat is stronger, pyromeconic acid (C5H4O3–carbon dioxide, water, acetic acid,
and benzole are formed. Pyromecomic acid is readily sublimed in large transparent
tables. Chloride of iron, and soluble iron salts generally, give with meconic acid
(even in great dilution) a lively red colour, which is not altered by heat, nor by the
addition of HCl, nor by that of gold chloride. Sugar of lead and nitrate of silver each
give a white precipitate; and mercurous and mercuric nitrates white and yellow
precipitates. In any case where the analyst has found only meconic acid, the
question may be raised in court as to whether it is a poison or not. The early
experiments of Serturner," Langer, Vogel, Sommering, and Grape f showed that, in
comparatively speaking large doses, it had but little, if any, action on dogs or men.
Albers + has, however, experimented on frogs, and found that in doses of 1 to 2 grm.
there is, first, a narcotic action, and later, convulsions and death. According to
Schroff, Š there is a slight narcotic action on man.
The most generally accepted view at the present time is that the
physiological action of meconic acid is similar to that of lactic acid—
viz., large doses cause some depression and feeble narcosis.
In a special research amongst organic fluids for mecomic acid, the
substances are extracted by alcohol feebly acidulated with nitric acid; on
filtration the alcohol, after the addition of a little water, is distilled off,
and to the remaining fluid a solution of acetate of lead is added, and the
whole filtered. The filtrate will contain any alkaloids, whilst mecomic
acid, if present, is bound up with the lead on the filter. The meconate
of lead may be either washed or digested in strong acetic acid to purify
it, suspended in water, and freed from lead by SH, ; the filtrate from
the lead sulphide may be tested by ferric chloride, or preferably, at once
evaporated to dryness, and weighed. After this operation it is identified.
If the quantity is so small that it cannot be conveniently weighed, it may
be estimated colorimetrically, by having a standard solution of mecomic
acid, containing 1 mgrm. in every c.c. A few drops of neutral ferric
chloride are added in a Nessler cylinder to the liquid under examination;
and the tint thus obtained is imitated in the usual way, in another
cylinder, by means of ferric chloride, the standard solution, and water.
It is also obvious that the weight of the mecomic acid may be increased
by converting it into the barium salt—100 parts of anhydrous baric
meconate, (Ba2C, H20+), being equivalent to 42-3 of mecomic acid
(C.H.O.).
* Amn. Phys., xxv. 56 ; xxvii. 183.
t De opio et de îllis quibus constat partibus, Berol., 1822.
# Arch. Path. Amat., xxvi. 248. § Med. Jahresb., 1869.
326 Poisons: THEIR EFFECTS AND DETECTION. [$ 384, 385.
IV.-The Strychnine or Tetanus-Producing * Group of
Alkaloids.
1. NUX WOMICA GROUP-STRYCHNINE–BRUCINE–IGASURINE.
§ 383. Nux vomica is found in commerce both in the entire state and
as a powder. It is the seed of the Strychnos nua, vomica, or Koochla
tree. The seed is about the size of a shilling, round, flattened, concavo-
convex, of a yellowish-grey or light brown colour, covered with a velvety
down of fine, radiating, silky hairs, which are coloured by a solution of
iodine beautiful gold-yellow ; the texture is tough, leathery, and not
easily pulverised; the taste is intensely bitter. The powder is not
unlike that of liquorice, and, if met with in the pure state, gives a dark
orange-red colour with nitric acid, which is destroyed by chloride of tin;
the aqueous infusion gives a precipitate with tincture of galls, is
reddened by nitric acid, and gives an olive-green tint with persulphate
of iron. The best method, however, of recognising quickly and with
certainty that the substance under examination is nux vomica powder,
is to extract strychnine from it by the following simple process:–The
powder is completely exhausted by boiling alcohol (90 per cent.), the
alcoholic extract evaporated to dryness, and then treated with water ;
the aqueous solution is passed through a wet filter, and concentrated by
evaporation to a small bulk. To this liquid a drop or so of a concen-
trated solution of picric acid is added, and the yellow precipitate
of picrates thus obtained is separated, treated with nitric acid, the
picric acid removed by ether, and the pure alkaloid precipitated by
soda, and shaken out by chloroform.
§ 384. Chemical Composition.—Nux vomica contains two important
alkaloids:—
(1) Strychnine.
(2) Brucine.
§ 385. Strychnine (C, H, N,O3) is contained in the bean of S.
Ignatius, in the bark (false angustura bark) and seeds of the Strychnos
mua, vomica, in the Strychnos colubrina, L., in the Strychnos tiewté, Lesch,
and probably in various other plants of the same genus.
Commercial strychnine is met with either in colourless crystals
or as a white powder, the most usual form being that of the alkaloid
itself; but the nitrate, sulphate, and acetate are also sold to a
small extent.
The microscopical appearance of strychnine, as thrown down by the
solution of vapour of ammonia, may be referred to three leading forms—
* To this group also belong some of the opium alkaloids. See “Thebaine *
“Laudamine,” “Codeine,” “Hydrocotarnine.”
§ 385.] STRYCHNINE. 327
the long rectangular prism, the short hexagonal prism, or the regular
octahedron. If obtained from the slow evaporation of an alcoholic
solution, it is usually in the form of four-sided pyramids or long prisms;
but if obtained by speedy evaporation or rapid cooling, it appears as a
white granular powder. If obtained from a benzene solution, the
deposit is usually crystalline, but without a constant form, though at
times the crystals are extremely distinct, the short six-sided prism
prevailing; but triangular plates, dodecahedral, rhomboidal, and penta-
gonal, may also be met with. An ethereal solution on evaporation
assumes dendritic forms, but may contain octahedra and four-sided
prisms. A chloroform solution deposits rosettes, veined leaves, stellate
dotted needles, circles with broken radii, and branched and reticulated
forms of great delicacy and beauty.—Guy.
Strychnine is very insoluble in water, although readily dissolved by
acidulated water. According to Wormley's repeated experiments, one
part of strychnine dissolves in 8333 parts of cold water; and, according
to Pelletier and Cahours, it dissolves in 6667 parts of cold and 2500
parts of boiling water. It may be convenient, then, to remember that
a gallon of cold water would hardly dissolve more than 10 grains (142
grm. per litre); the same amount, if boiling, about 30 grains (426 grm.
per litre) of strychnine. The solubility of one part of strychnine in
other menstrua is as follows:—Cold alcohol, 0.833 specific gravity, 120,
boiling, 10 parts (Wittstein); cold alcohol, 0.936 specific gravity, 240
parts (Merck); cold alcohol, 0.815 specific gravity, 107 parts (Dragen-
dorff); amyl alcohol, 181 parts; benzene, 164; chloroform, 6-9
(Schlümpert), 5 (Pettenkofer); ether, 1250 parts; carbon disulphide,
485 parts; glycerin, 300 parts. Creosote and essential and fixed oils
also dissolve strychnine.
Of all the above solvents, it is evident that chloroform is the best for
purposes of separation, and next to chloroform, benzene.
If a speck of strychnine be placed in the subliming cell, it will be
found to sublime usually in a crystalline form at 169°. A common
form at this temperature, according to the writers' own observations,
is minute needles, disposed in lines; but, as Dr. Guy has remarked, the
sublimate may consist of drops, of waving patterns, and various other
forms; and, further, while the sublimates of morphia are made up of
curved limes, those of strychnine consist of lines either straight or
slightly curved, with parallel feathery lines at right angles. On
continuing the heat, strychnine melts at about 221°, and the lower disc,
if removed and examined, is found to have a resinous residue ; but it
still continues to yield sublimates until reduced to a spot of carbon.
The melting-point taken in a tube is 268°.
Strychnine is so powerfully bitter, that one part dissolved in 70,000
328 POISONS : THEIR EFFECTS AND DETECTION. [$ 386.
of water is distinctly perceptible; it is a strong base, with a marked
alkaline reaction, neutralising the strongest acids fully, and precipitat-
ing many metallic oxides from their combinations, often with the
formation of double salts. Most of the salts of strychnine are crystal
line, and all extremely bitter. Strychnine, in the presence of oxygen
combines with SH, to form a beautiful crystalline compound:—
2C91 H23N2O3 + 6H, S + Os=2Cs1H23N20,3H5S2 + 3H2O.
On treatment with an acid this compound yields H.S.-Schmidt, Ber
deutsch. chem. Ges., viii. 1267.
In solution in alcohol of density of 0.8543 strychnine polarises light
to the left at 20° [a]b = - 1147° in a concentration of 0.25 per cent. ;
when in a concentration of 0.1 per cent, the specific rotation is – 119.3°
[Tykociner, Rec. Trav. Chim., i. 148]. Oudemans (Liebig's Annalen der
Chemie, clxvi. 76) gives for a solution in alcohol of density 0-865, and a
concentration of 0.91 per cent., a rotation of — 128°. The same author
gives the following:—4 per cent, solution in chloroform, - 130”; 2.25 per
cent, — 137.7°; 1.5 per cent., - 140.7°; and in 0.53 per cent., -235°.
§ 386. Strychnine Salts.--The salts used in medicine are—the
sulphate, officinal only in the French pharmacopoeia; the nitrate, officinal
in the German, Austrian, Swiss, Norse, and Dutch pharmacopoeias; and
the acetate, well known in commerce, but not officinal.
The commercial Sulphate (CºHo, N,0s, H.S.O., + 2 H2O) is an acid salt
crystallising in needles which lose water at 150°, the neutral sulphate
(2C2. Has N.O.,H.S0, 4-7H,0) crystallises in four-sided, orthorhombic
prisms, and is soluble in about 50 parts of cold water.
The Nitrate (CºHo,N,02,HNO3) crystallises on evaporation from a
warm solution of the alkaloid in dilute nitric acid, in silky needles,
mostly collected in groups. The solubility of this salt is considerable,
one part dissolving in 50 of cold, in 2 of boiling water; its solubility in
boiling and cold alcohol is almost the same, taking 60 of the former and
2 of the latter. . -
The Acetate crystallises in tufts of needles; as stated, it is not
officinal in any of the European pharmacopoeias.
The chief precipitates or sparingly soluble crystalline compounds of
strychnine are—
(1) The Chromate of Strychnine (C2H, N,02,OrHO), formed by
adding a neutral solution of chromate of potash to a solution of a strych-
nine salt, crystallises out of hot water in beautiful, very slightly soluble,
orange-yellow needles, mixed with plates of various size and thickness.
The salt is of great practical use to the analyst; for by its aid strychnine
may be separated from a variety of substances, and in part from brucine
—the colour tests being either applied direct to the Strychnine chromate,
§ 387.] STRYCHNINE. 329
or the chromate decomposed by ammonia, and the strychnine recovered
from the alkaline liquid by chloroform.
(2) Sulphocyanide of Strychnine (C, H, N,0,0NHS) is a thick,
white precipitate, produced by the addition of a solution of potassic
sulphocyanide to that of a strychnine salt ; on warming it dissolves, but
on cooling reappears in the form of long silky needles.
(3) Double Salts.—The platinum compound obtained by adding a
solution of platinic chloride to one of strychnine chloride has the com-
position Cai Hog M203, HCIPtCl2, and crystallises out of weak boiling alcohol
(in which it is somewhat soluble) in gold-like scales. The similar
palladium compound (C, H22N402, HClPdCI) is in dark brown needles, and
the gold compound (Cai H23N2O, HCIAuCls) in orange-coloured needles.
(4) Strychnine Trichloride.—The action of chlorine on strychnine—-
by which chlorine is substituted for a portion of the hydrogen—has been
proposed as a test. The alkaloid is dissolved in very dilute HCl, so as
to be only just acid; on now passing through chlorine gas, a white
precipitate is formed, which may be recrystallised from ether; it has
probably the composition C, H10Cls N2O3, and is extremely insoluble in
water.
(5) The Iodide of Strychnine (C, H, N,0, HI.) is obtained by the
action of iodine solution on Strychnine sulphate ; on solution of the
precipitate in alcohol, and evaporation, it forms violet-coloured crystals,
very similar to those of potassic permanganate.
§ 387. Pharmaceutical and other Preparations of Nux Womica and
Strychnine, with Suggestions for their Valuation.
An aqueous extract of nux vomica, officinal in the German phar-
macopoeia, appears to contain principally brucine, with a small percentage
of Strychnine; the proportion of brucine to strychnine being about four-
fifths to one-fifth. Blossfield found in a sample 4:3 per cent. of total
alkaloid, and two samples examined by Grundmann consisted (No. 1) of
Strychnine, 0.6 per cent. ; brucine, 2:58 per cent.—total, 3:18 per cent. ;
(No. 2) Strychnine, 0.68 per cent. ; brucine, 2-62 per cent.—total, 3-3
per cent. A sample examined by Dragendorff yielded—strychnine, 0.8
per cent. ; brucine, 3.2 per cent.—total, 4 per cent. The maximum
medicinal dose is put at 6 grim. (91+ grains).
The spirituous extract of nux vomica, officinal in the British and
all the Continental pharmacopoeias, differs from the aqueous in containing
a much larger proportion of alkaloids, viz., about 15 per cent., and about
half the total quantity being strychnine. The medicinal dose is 21-6–
64'8 mgrms. (3 grain to a grain).
There is also an extract of St. Ignatius bean which is used in the
United States; nearly the whole of its alkaloid may be referred to
strychnine.
33O POISONS : THEIR EFFECTS AND DETECTION. [$387.
The tincture of nux vomica, made according to the British Pharma-
copoeia, contains in 1 fl. Oz. 1 grain of alkaloids, or 0:21 part by weight
in 100 by volume, but the strength of commercial samples often varies.
Lieth found in one sample 0-122 per cent. of strychnine and 0.09 per
cent, brucine; and two samples examined by Wissel consisted respectively
of 0.353 per cent, and 0.346 per cent. of total alkaloids. Dragendorff
found in two samples '2624 per cent. and 244 per cent. of total
alkaloids, about half of which was strychnine. w
Analysis.-Either of the extracts may be treated for a few hours on
the water-bath, with water acidulated by sulphuric acid, filtered, the
residue well washed, the acid liquid shaken up with benzene to separate
impurities, and, on removal of the benzene, alkalised with ammonia,
and shaken up two or three times with chloroform ; the chloroform is
then evaporated in a tared vessel, and the total alkaloids weighed.
The alkaloids can then be either (a) treated with 11 per cent. of nitric
acid on the water-bath until all the brucine is destroyed, and then
(the liquid being neutralised) precipitated by potassic chromate; or (b)
the alkaloids may be converted into picrates. Picrate of strychnine is
very slightly soluble in water, 1 part requiring no less than 10,000 of
water.” The tincture is analysed on precisely similar principles, the
spirit being got rid of by distillation, and the residue treated by acidified
water, etc.
The nux vomica powder itself may be valued as follows:—15 to 20
grims, pulverised as finely as possible, are treated three times with 150
to 300 c.c. of water, acidified with sulphuric acid, well boiled, and, after
each boiling, filtered and thoroughly pressed. The last exhaustion
must be destitute of all bitter taste. The united filtrates are then
evaporated to the consistence of a thick syrup, which is treated with
sufficient burnt magnesia to neutralise the acid. The extract is now
thoroughly exhausted with boiling alcohol of 90 per cent. ; the alcoholic
extract, in its turn, is evaporated nearly to dryness, and treated with
acidulated water; this acid solution is freed from impurities by shaking
up with benzene, and lastly alkalised with ammonia, and the alkaloids
extracted by shaking up with successive portions of chloroform.
The chloroformic extract equals the total alkaloids, which may be
separated in the usual way.
Keller i estimated the alkaloids in nux vomica as follows:—Place
12 grims. of the powder in a flask with 80 grms. of ether and 40 grms, of
chloroform. After half an hour add 10 c.c. of a 10 per cent, solution of
ammonia. Shake at intervals for half an hour, then add 15 to 22 c.c. of
water and again shake. Now pour off 100 c.c. of the ether mixture into
* Dolzler, Arch. Pharm. [3], xxiv. 105–109.
f Chem. Centr., i. 228, 1896.
§ 387.] STRYCHNINE. 33 I
a separating funnel and shake with 50 c.c. of a 0.5 per cent. HCl solu-
tion, draw off the acid, add 20 c.c. more acid, shake, and again draw off.
Add excess of ammonia, and extract the alkaloids with ether and
chloroform; evaporate. The extracted alkaloids represent the quantity
in 10 grnms, of the original powder.
In four samples of nux vomica examined by Dragendorff, the total
alkaloids ranged from 2:33 to 2:42 per cent. Grate found in two
samples 2.88 per cent. and 2.86 per cent. respectively; while Karing
from one sample separated only 165 per cent. The strychnine and
brucine are in about equal proportions, Dragendorff” finding 1.87 per
cent. Strychnine and 1145 per cent. brucine.f
The fact that sodium carbonate precipitates, and sodium bicarbonate
does not precipitate, strychnine, brucine and veratrine may be utilised
as an imperfect group reagent, imperfect because long contact with an
excess of bicarbonate solution precipitates slowly the strychnine alka-
loids; and a few other alkaloids in dilute solution behave somewhat
similarly.
In poisoning by nux vomica there will be the mixed alkaloids to deal
with, and the processes suggested hitherto for their neat quantitative
separation do not lead to very good results. Behrens believes that the
most certain process of recognising strychnine mixed with much brucine
is to precipitate with platinum chloride in presence of free hydrochloric
acid. The brucine and Strychnine precipitates have different forms and
grouping.
The mixed salts may be also turned into the nitrate, potassic nitrate
added, and then the solution almost saturated with common salt; under
these circumstances, tables of brucine nitrate first appear, and later
needles and tufts of strychnine nitrate.
Fractional precipitation with platinum chloride may also be tried in
dilute solutions; with much brucine and very little strychnine the chloro-
platinate of brucine comes down first, and it is only in the last fraction
that strychnine comes down.
To recognise brucine even in traces contaminated with strychnine,
on the other hand, is much easier; the Solution evaporated with nitric
acid shows an orange-red edge.
* Dragendorff, Die chemische Werthbestimmung einiger starkwirkenden Droguen,
St. Petersburg, 1874.
+ These details are very necessary, as bearing on the question of the fatal dose of
nux vomica, which Taylor tells us (Med. Jurisprud., i. 409) was of some importance
in Reg. v. Wren, in which 47 grains were attempted to be given in milk. The
fatal dose of nux vomica must be ruled by its alkaloidal content, which may be so
low as 1 per cent., and as high as nearly 3 per cent. 30 grains have proved fatal
(Taylor); if the powder in this instance was of the ordinary strength, the person
died from less than a grain ('0648 grm.) of the united alkaloids. -
332 POISONS : THEIR EFFECTS AND DETECTION. [$ 388.
A striking and very sensitive test is also the double thiocyanate of
brucine and cobalt.
This is obtained by adding to a solution of the alkaloid a
little cobalt chloride solution, and then an excess of ammonium
sulpho-cyanide; strychnine, veratridine, and the quinine alkaloids give
under these circumstances immediate amorphous blue precipitates,
but brucine crystallises after a minute or two in blue pyramids and
tufts; after a time colourless rods of strychnine thiocyanate make
their appearance.
The vermin-killers in use in this country are those of Miller, Battle
Butler, Clift, Craven, Floyd, Gibson, Hunter, Stenier, and Thurston.
Ten samples from these various makers examined by Mr. Allen (Pharm.
Journal, vol. xii., 1889), gave the following results:—
Strychnine. ;
Name Weight of - - Nature
Ol' Powder Trice. Of Colouring Matter.
Mark. in Grains. Weight in Per- Starch. !
Grains. centage.
--- - --
I 5'6 3d. 0 °61 10 *9 Wheat ! - |
2 11 '8 3d. 0 °80 6-7 Wheat Ultramarine. .
3 13 * 1 3d. 1 12 8-7 | Rice Ultramarine. |
4 11 "G 3d. 1 °28 11 "I Rice Ultramarine.
5 13 "1 3d. 1 '70 13-0 Rice Ultramarine.
6 21 °5 6d. 2°42 11'2 Wheat Prussian blue.
7 49 °2 3d. 2 '85 5 °8 Wheat Soot.
8 30 °5 3d. 3 °45 11 "3 Wheat Prussian blue.
9 16 °6 3d. 3.81 19 "J. Rice Carmine.
I () 10'0 3d. 4:18 41 ‘8 | Rice Ultramarine.
|
§ 388. Statistics.-In England, during the ten years 1884–1903,
strychnine, nux vomica, and vermin-killer account for 308 deaths. Of
these, 64 were ascribed to “vermin-killer.” “Vermin-killer” may be
presumed to include not only strychnine mixtures, but also phosphorus
and arsenic pastes and powders, so that there are no means of ascertain-
ing the number of strychnine cases comprised under this heading.
Taking the deaths actually registered as due to strychnine or nux
vomica, they are about 2.0 per cent, of the deaths from all sorts of
poison. Of these deaths 171 were suicidal, 6 were homicidal, and 67
were accidental. -
Schauenstein has collected from literature 130 cases of poisoning by
Strychnine, and most of these occurred comparatively speaking during
recent years; 62 of the 130, or about one half, were fatal, and 15 were
homicidal. It has been stated that strychnine is so very unsuitable for
the purpose of criminal poisoning as to render it unlikely to be often
used. Facts, however, do not bear out this view ; for, allowing its
§ 388.] STRYCHNINE. 333
intensely bitter taste, yet it must be remembered that bitter liquids,
such as bitter ale, are in daily use, and a person accustomed to drink
any liquid rapidly might readily imbibe sufficient of a toxic liquid to
produce death before he was warned by its bitterness. It is, indeed,
capable of demonstration, that taste is more vivid after a substance
has been taken than just in the act of swallowing, for the function
of taste is not a rapid process, and requires a very appreciable interval
of time.
The series of murders by Thomas Neill, or, more correctly, Thomas
Neill Cream, is an example of the use of strychnine for the purposes
of murder. Thomas Neill Cream was convicted, October 21, 1892,
for the murder of Matilda Clover on October 20, 1891 ; there was
also good evidence that the same criminal had murdered Ellen
Dunworth, October 13, 1891; Alice Marsh, April 12, 1892; Emma
Shrivell, April 12, 1892, and had attempted the life of Louie
Harvey. The agent in all these cases was strychnine. There was
no evidence as to what form of the poison was administered in
the case of Clover, but Ellen Dunworth, who was found dying
in the streets at 7.45 P.M., and died less than two hours after-
wards, stated that a gentleman gave her “two drops” of white stuff
to drink.
In the cases of Marsh and Shrivell, Neill Cream had tea with them
on the night of April 11, and gave them both “three long pills”; half
an hour after Neill Cream left them they were found to be dying, and
died within six hours. From Marsh 7 grains, from Shrivell nearly 2
grains of strychnine were separated; the probability is that each pill
contained at least 3 grains of strychnine. The criminal met Louie
Harvey on the Embankment, and gave her “some pills” to take ; she
pretended to do so, but threw them away. Hence it seems probable that
Neill Cream took advantage of the weakness that a large number of the
population have for taking pills, and mostly poisoned his victims in this
manner. Clover's case was not diagnosed during life, but strychnine was
found six or seven months after burial in the body. It may be men-
tioned incidentally that the accused himself furnished the clue which
led to his arrest, by writing letters charging certain members of the
medical profession with poisoning these poor young prostitutes with
strychnine. -
One of the most famous strychnine poisoning cases was that of
William Palmer. Baron Brampton, in his reminiscences, speaks of this
case as follows:– “William Palmer was a surgeon practising at Rugeley
in Staffordshire. He was a great racing man, and owned one or two
racers. A young gentleman of considerable fortune had taken to the
turf and owned horses. Palmer and he became intimate as companions
334 POISONS : THEIR EFFECTS AND DETECTION, [$ 389.
—in short, they were at Shrewsbury races, where Palmer lost and Cook
won. The latter had considerable sums of money to receive on bets,
and Palmer, desirous of getting hold of it, poisoned the poor man with
Strychnine,” took possession of his betting-book and papers, received all
money due, and then had him hastily buried. Ultimately suspicion fell
on Palmer, he was tried for the murder and hanged. There was little
doubt he had murdered several others for the sake of the money for
which he had insured their lives, notably his wife and mother, whose
name he had forged to several bills. . . . I may also add that at
that time there was no known test for the discovery of strychnine
in the body, and Palmer was convicted entirely upon the symptoms
preceding death, and especially the peculiar arching of the body
after.”
§ 389. Fatal Dose.—In a research, which may, from its painstaking
accuracy, be called classical, F. A. Falck has thrown much light upon
the minimum lethal dose of strychnine for various animals. It would
seem that, in relation to its size, the frog is by no means so sensitive to
strychnine as was believed, and that animals such as cats and rabbits
take a smaller dose in proportion to their body weight. The method
used by Falck was to inject subcutaneously a solution of known strength
of strychnine nitrate, and, beginning at first with a known lethal dose, a
second experiment was then made with a smaller dose, and if that
proved fatal, with a still smaller, and so on, until such a quantity was
arrived at, that the chances as determined by direct observation were
as great of recovery as of death. Operating in this way, and making
no less than 20 experiments on the rabbit, he found that the least fatal
dose for that animal was 6 mgrm. of Strychnine mitrate per kilogramme.
Cats were a little less susceptible, taking 75 mgrm. Operating on
fowls, he found that strychnine taken into the crop in the usual way
was very uncertain; 50 mgrms. per kilo. taken with the food had no
effect, but results always followed if the poison was introduced into
the circulation by the subcutaneous needle—the lethal dose for fowls
being, under those circumstances, 1 to 2 mgrms. per kilo. He made
35 experiments on frogs, and found that to kill a frog by strychnine
nitrate, at least 2 mgrims, per kilo. must be injected. Mice take a
little more, from 2:3 to 2-4 mgrms. per kilo. In two experiments on
the ring adder, in one 62-5 mgrms. per kilo. of strychnine nitrate,
injected subcutaneously, caused death in seven hours; in the second,
23.1 mgrms, per kilo. caused death in five days; hence the last
quantity is probably about the least fatal dose for this particular
snake. -
* Dr. Taylor analysed the stomach and other organs,—he found antimony, but
was not successful in tracing Strychnine.
§ 389.] STRYCHNINE, 335
These observations may be conveniently thrown into the following
table, placing the animals in order according to their relative
sensitiveness.”
TABLE SHOWING THE ACTION OF STRYCHNINE ON ANIMALS.

Reckoned on 1 Kilo. of
Body Weight.
Lowest Highest
Animal. Manner of Application. Experimental | Experimental
- Lethal Dose. Lethal Dose.
Dose of Strychnine Nitrate in
Mgrms.
Rabbit, . -> w º Subcutaneous, 0 °50 0-60
Cat, e - - e 3 2 • - - 0-75
Dog, º º 2 3 - - - 0-75
5 5 Taken by the Stomach, 2-0 3 ‘90
; 5 º . . . e 3 3 Rectum, - - - 2°00
2 3 & - s e 3 7 Bladder, 5-50 - * *
Fox, . - e . . Subcutaneous, t * * * 1:00
Hedgehog, . e e j 3 | 1-00 2:00
Fowl, . . . . y 2 . 2 : 00
Frog, . - e o x 5 ! 2:00 2-10
Mouse, . - g e 2 3 2:36 2 °36
Ring Adder, . * º 3 2 : • - - 23-10
Now, the important question arises as to the place in this series
occupied by man—a question difficult to solve, because so few cases are
recorded in which strychnine has been administered by subcutaneous
injection with fatal result. Eulenberg has observed poisonous
symptoms, but not death, produced by 6 mgrms. (#r grain) and by 10
mgrms. (about , grain). Bois observed poisonous symptoms from the
similar subcutaneous administrations of 8 mgrms. to a child 6 years
old, and 4 mgrms. to another child 4 years old—the latter dose, in a
case recorded by Christison, actually killing a child of 3 years of
age. On the other hand, the smallest lethal dose taken by an adult
was swallowed in solution. Dr. Warner took 32 mgrms. (; grain) of
Strychnine sulphate, mistaking it for morphine sulphate, and died in
twenty minutes. In other cases 48 mgrms. (Fºr grain) have been fatal.
It will be safe to conclude that these doses by the stomach would have
acted still more surely and energetically if injected subcutaneously.
* According to Christison’s researches, 0-2 grm. (about à grain) is fatal to swine ;
‘03 grm. (# grain) to bears, if injected into the pleura. 1 to 3 grains ('0648 to
‘1944 grm.) is given to horses in cases of paralysis, although 3 grains cannot but be
considered a dangerous dose, unless smaller doses have been previously administered
without effect; 10 grains would probably kill a horse, and 15 grains ('972 grim.) have
certainly done so.
336 POISONS : THEIR EFFECTS AND DETECTION. [$ 389.
The case of Warner is exceptional, for he was in weak health; and, if
calculated out according to body weight, presuming that Dr. Warner
weighed 68 kilos., the relative dose as strychnine nitrate would be ‘24
per kilo.—a smaller dose than for any animal hitherto experimented
upon. There is, however, far more reason for believing that the degree
of sensitiveness in man is about the same as that of cats or dogs, and
that the least fatal dose for man is 70 per kilo., the facts on record
fairly bearing out this view. It is, therefore, probable that death would
follow if 48 mgrms. (ſº grain) were injected subcutaneously into a man
of the average weight of 68 kilos. (150 lbs.). Taylor estimates the fatal
dose of strychnine for adults as from 32.4 to 129.6 mgrms. (5 to 2
grains); Guy puts the minimum at 16.2 mgrms. (.25 grain).
Large doses of strychnine may be recovered from if correct medical
treatment is sufficiently prompt. Witness the remarkable instances on
record of duplex poisonings, in which the would-be suicide has unwit-
tingly defeated his object by taking strychnine simultaneously with some
narcotic, such as opium or chloral. In a case related by Schauenstein,”
a suicidal pharmacist took 48 grn. to 6 grim. (7.4 to 9:25 grains) of
strychnine nitrate dissolved in about 30 c.c. of bitter-almond water, and
then, after half an hour, since no symptoms were experienced, 6 grn.
(9:25 grains) of morphine acetate, which he likewise dissolved in bitter-
almond water and swallowed. After about ten minutes, he still could
walk with uncertain steps, and poured some chloroform on the pillow-
case of his bed, and lay on his face in order to breathe it. In a short
time he lost consciousness, but again awoke, and lay in a half-dreamy
state, incapable of motion, until someone entered the room, and hearing
him murmur, came to his bedside. At that moment—two and a quarter
hours after first taking the strychnine—the pharmacist had a fearful
convulsion, the breathing was suspended, and he lost consciousness.
Again coming to himself, he had several convulsions, and a physician
who was summoned found him in general tetanus. There were first
clonic, then tonic convulsions, and finally opisthotonus was fully
developed. The treatment consisted of emetics, and afterwards tannin
and codeine were given separately. The patient slept at short intervals;
in ten hours after the taking of the poison the seizures were fewer in
number and weaker in character, and by the third day recovery was
complete. Dr. Macredy f has also placed on record an interesting case,
in which the symptoms, from a not very large dose of strychnine, were
delayed by laudanum for eight hours. A young woman, 23 years
of age, pregnant, took at 10 A.M. a quantity of strychnine estimated
at 1.5 grain, in the form of Battle's vermin-killer, and immediately after-
* Maschka's Handbuch, from Tschepke, Deutsche Klinik, 1861.
+ Lancet, November 28, 1882.
§ 390.] STRYCHNINE. 337
wards 2 ounces of laudanum. She was seen by Dr. Macredy in four
hours, and was then suffering from pronounced narcotic symptoms. A
sulphate of zinc emetic was administered. In eight hours after taking
the strychnine, there were first observed some clonic convulsive move-
ments of the hands, and, in a less degree, the legs. These convulsions
continued, at times severe, for several hours, and were treated with
chloral. Recovery was speedy and complete.
In a similar case related by Dr. Harrison,” a man, aged 54, took a
packet of Battle's vermin-killer, mixed with about a drachm and a half
of laudanum and some rum. At the time he had eaten no food for
days, and had been drinking freely; yet fifty minutes elapsed before
the usual symptoms set in, and no medical treatment was obtained until
four hours after taking the dose. He was then given chloral and other
remedies, and made a rapid recovery.
§ 390. Action on Animals.-The action of strychnine has been experi-
mentally studied on all classes of animals, from the infusoria upwards.
The effects produced on animal forms which possess a nervous system
are strikingly alike, and even in the cephalapoda, tetanic muscular spasm
may be readily observed. Of all animals the frog shows the action of
Strychnine in its purest form, especially if a dose be given of just suffi-
cient magnitude to produce toxic effects. The frog sits perfectly still
and quiet, unless acted upon by some external stimuli, such as a breath
of air, a loud noise, or the shaking of the vessel which contains it, then
an immediate tetanic convulsion of all the muscles is witnessed, lasting
a few seconds only, when the animal again resumes its former posture.
This heightened state of reflex action has its analogue in hydrophobia as
well as in idiopathic tetanus. If the frog thus poisoned by a weak dose
is put under a glass shade, kept moist, and sheltered from sound or from
other sources of irritation, no convulsions occur, and after some days it is
in its usual health. If, on the other hand, by frequent stimuli, convul-
sions are excited, the animal dies. M. Richet i has contributed a valuable
memoir to the Academy of Sciences on the toxic action of strychnine.
He has confirmed the statement of previous observers that, with artificial
respiration, much larger doses of strychnine may be taken without fatal
result than under normal conditions, and has also recorded some peculiar
phenomena. Operating on dogs and rabbits, after first securing a canula
in the trachea, and then injecting beneath the skin or into the saphena
vein 10 mgrms. of strychnine hydrochlorate, the animal is immediately,
or within a few seconds, seized with tetanic convulsions, and this attack
would be mortal, were it not for artificial respiration. Directly this is
* Lancet, May 13, 1882.
t “De l’Action de la Strychnine à très forte dose sur les Mammiferes,” Comptes
Rend., t. Xci. p. 131.
22
338 POISONS : THEIR EFFECTS AND DETECTION. [š 391.
practised the attack ceases, and the heart, after a period of hurried and
spasmodic beats, takes again its regular rhythm. Stronger and stronger
doses may then be injected without causing death. As the dose is thus
augmented, the symptoms differ. M. Richet distinguishes the following
periods:–(1) A period of tetanus. (2) A period of convulsion, charac-
terised by spasmodic and incessant contraction of all the muscles. (3)
A little later, when the quantity exceeds 10 mgrims, per kilo., a choreic
period, which is characterised by violent rhythmic shocks, very sudden
and short, repeated at intervals of about three to four seconds; during
these intervals there is almost complete relaxation. (4) A period of
relaxation; this period is attained when the dose exceeds 40 mgrms. per
kilo. Reflex action is annihilated, the spontaneous respiratory move-
ments cease, the heart beats tumultuously and regularly in the severe
tetanic convulsions at first, and then contracts with frequency but with
regularity. The pupils, widely dilated at first, become much contracted.
The arterial pressure, enormously raised at the commencement,
diminishes gradually, in one case from 0.34 mm. to 0.05 mm. The
temperature undergoes analogous changes, and during the convulsions
is extraordinarily elevated; it may even attain 41° or 42°, to sink in the
period of relaxation to 36°. Dogs and rabbits which have thus received
enormous quantities of strychnine (e.g. 50 mgrms, per kilo.), may, in this
way, live for several hours, but the slightest interruption to the artificial
respiration, in the relaxed state, is followed by syncope and death.
§ 391. Effects on Man: Symptoms.-The commencement of symp-
toms may be extremely rapid, the rapidity being mainly dependent on the
form of the poison and the manner of application. A soluble salt of strych-
mine injected subcutaneously will act within a few seconds; * in a case of
amaurosis, related by Schuler,t 5:4 mgrms, of a soluble strychnine salt were
introduced into the punctum lachrymale ; in less than four minutes there
were violent tetanic convulsions. In a case related by Barker, the symp-
toms commenced in three minutes from a dose of 37 grm. (5:71 grains).
* In one of M. Richet's experiments, a soluble strychnine salt injected into a dog
subcutaneously acted in fourteen seconds.
+ Quoted by Taylor from Med. Times and Gazette, July 1861.
# A non-fatal dose may show its effects rapidly, e.g. there is a curious case of symp-
toms of poisoning caused by the last dose of a mixture which is recorded in Pharm.
Journ., 1893, 799. A medical practitioner prescriled the following mixture:—
B. Tr. strophanthi, º e e e e º e e 3i.
Liq, strychni hydrochlorici, º © * * e e 3iiss.
Sol. bismuthi et pepsin. (Richardson's), g e º 3iss.
Sp. ammon. aromat., e e - º e - e.
Sp. chloroformi, . e e o - e - & aa. 3iss.
Aquam ad, . g º e º o e - º º 3vi.
- ft. mist.
Shake the bottle.
$ 391.] STRYCHNINE. 339
Here the poison was not administered subcutaneously. Such short
periods, to a witness whose mind was occupied during the time, might
seem immediate. On the other hand, when nux vomica powder has been
taken, and when strychnine has been given in the form of pill, no such
rapid course has been observed, or is likely to occur, the usual course
being for the symptoms to commence within half an hour. It is, how-
ever, also possible for them to be delayed from one to two hours, and
, under certain circumstances (as in the case related by Macredy) for
eight hours. In a few cases, there is first a feeling of uneasiness and
heightened sensibility to external stimuli, a strange feeling in the
muscles of the jaw, and a catching of the respiration ; but generally
the onset of the symptoms is as sudden as epilepsy, and previous to
their appearance the person may be pursuing his ordinary vocation,
when, without preliminary warning, there is a shuddering of the whole
frame, and a convulsive seizure. The convulsions take the form of
violent general tetanus; the limbs are stretched out involuntarily, the
hands are clenched, the soles of the feet incurved, and, in the height
of the paroxysm, the back may be arched and rigid as a board, the
sufferer resting on head and heels, and the abdomen tense. In the
grasp of the thoracic muscles the walls of the chest are set immovable,
and from the impending suffocation the face becomes congested, the
eyes prominent and staring. The muscles of the lower jaw—in “disease
tetanus” the first to be affected—are in “strychnos tetanus,” as a rule,
the last ; a distinction, if it were more constant, of great clinical value.
The convulsions and remissions recur until death or recovery, and, as a
rule, within two hours from the commencement of the symptoms the
case in some way or other terminates. The number of the tetanic
seizures moted has varied—in a few cases the third spasm has passed
into death, in others there have been a great number. The duration of
the spasm is also very different, and varies from thirty seconds to five or
Two teaspoonfuls when the attack threatens, and repeat in an hour if necessary.
Richardson's liquor bismuth contains sº grain of strychnine in each drachm.
The mixture was alkaline; it contained 17 grain of strychnine and 38.25 minims of
chloroform. , *
The patient, a woman, 54 years of age, had taken the previous doses with con-
siderable relief; but ten minutes after the last dose, which she described as far more
bitter than those she had taken previously, she was seized with the usual symptoms
of strychnine poisoning, but recovered after five hours.
The explanation is pretty obvious ; the mixture was alkaline, so that the strych-
nine was not in the form of a salt, but in the free state, and was therefore dissolved
by the chloroform ; the amount of strychnine taken in each dose wholly depended
on whether or not the mixture was shaken violently and poured out into the tea-
spoon immediately after shaking; if allowed to repose, the globules of chloroform
Saturated with strychnine would settle at the bottom, and there form a stratum rich
in Strychnine; so that the last dose would certainly contain an excess.
34O POISONs: THEIR EFFECTS AND DETECTION. [$ 392, 393.
even eight minutes, the interval between lasting from forty-five seconds*
to one or even one and a half hours, f
$392. Diagnosis of Strychnine Poisoning.—However striking and
well defined the picture of strychnine tetanus may be, mistakes in
diagnosis are rather frequent, especially when a medical man is hastily
summoned, has never seen a case of similar poisoning, and has no
suspicion of the possible nature of the seizure. If a young woman, for
instance, is the subject, he may put it down to hysteria, and certainly
hysteria not unfrequently affects somewhat similar convulsions. In a
painful case in which the senior author was engaged, a young woman
either took or was given (for the mystery was never cleared up fully) a
fatal dose of strychnine, and though the symptoms were well marked, the
medical attendant was so possessed with the view that the case was due
to hysteria, that, even after making the post-mortem examination, and
finding no adequate lesion, he theorised as to the possibility of some
fatal hysteric spasm of the glottis, while there was ample chemical
evidence of strychnine, and a weighable quantity of the alkaloid was
actually separated from the contents of the stomach. The medical
attendant of Matilda Clover, one of Neill's victims, certified that the
girl died from delirium tremens and syncope, although the symptoms
were typically those produced by strychnine. Such cases are par-
ticularly sad, for we now know that, with judicious treatment, a rather
large dose may be recovered from.
If the case be a male, a confusion with epilepsy is possible, though
hardly to be explained or excused ; while in both sexes idiopathic
tetanus is so extremely similar as to give rise to the idea that all cases
of idiopathic tetanus are produced by poison, perhaps secreted by the
body itself. As for the distinction between idiopathic and strychnine
tetanus, it is usually laid down (1) that the intervals in the former are
characterised by no relaxation of the muscles, but that they continue
contracted and hard ; and (2) that there is a notable rise of temperature
in disease tetanus proper, but not in strychnine tetanus. Both state-
ments are misleading, and the latter is not true, for in strychnic poison-
ing the relaxation is not constant, and very high temperatures in
animals have been observed. -
§ 393. Physiological Action.—The tetanic convulsions are essentially
reflex, and to be ascribed to a central origin; the normal reflex
sensibility is exaggerated and unnaturally extended. If the ischiatic
plexus supplying the one leg of an animal is cut through, that leg takes
no part in the general convulsions, but if the artery of the leg alone is
tied, then the leg suffers from the muscular spasm, as well as the limbs
in which the circulation is unrestrained. In an experiment by Sir
* White, Brit. Med. Jowrm., 1867. f Folkes, Med. Times, 1869.
$ 394.] STRYCHNINE. 34. I
B. W. Richardson, a healthy dog was killed, and, as soon as practicable,
a solution of strychnine was injected through the systemic vessels by
the aorta—the whole body became at once stiff and rigid as a board.
These facts point unmistakably to the spinal marrow as the seat of the
toxic influence. Strychnine is, par eacellence, a spinal poison. On
physiological grounds the grey substance of the cord is considered to
have an inhibitory action upon reflex sensibility, and this inhibitory
power is paralysed by strychnine. The spinal cord, it would appear,
has the power of collecting strychnine from the circulation and storing
it up in its structure.”
Much light has been thrown upon the cause of death by Richet's
experiments.f. It would seem that, in some cases, death takes place by
a suffocation as complete as in drowning, the chest and diaphragm being
immovable, and the nervous respiratory centres exhausted. In such a
case, immediate death would be averted by a tracheal tube, by the aid
of which artificial respiration might be carried on ; but there is another
asphyxia due to the enormous interstitial combustion carried on by
muscles violently tetanised. “If,” says Richet, “after having injected
into a dog a mortal dose of strychnine, and employed artificial respira-
tion according to the classic method twenty or thirty times a minute,
the animal dies (sometimes at the end of ten minutes, and in every case
at the end of an hour or two), and during life the arterial blood is
examined, it will be ascertained that it is black, absolutely like venous
blood.”
This view is also supported by the considerable rise of temperature
noticed: the blood is excessively poor in oxygen, and loaded with carbon
dioxide. That this state of the blood is produced by tetanus, is proved
by the fact that an animal poisoned by strychnine, and then injected
subcutaneously with curare in quantity just sufficient to paralyse the
muscular system, does not exhibit these phenomena. By the aid of
artificial respiration, together with the administration of Curare, an
animal may live after a prodigious dose of strychnine.
Meyer i has investigated carefully the action of strychnine on the
blood-pressure—through a strong excitement of the vaso-motor centre,
the arteries are narrowed in calibre, and the blood-pressure much in-
creased; the action of the heart in frogs is slowed, but in the warm-
blooded animals quickened. -
§ 394. Post-mortem. Appearances.—There is but little characteristic
in the post-mortem appearances from strychnine poisoning. The body
becomes very stiff a short time after death, and this rigidity remains
generally a long time. In the motorious Palmer case, the body was rigid
* R. W. Lovett, Jowrm. Physiol, ix. 99–111. t Op. cit,
f Wiemer Akad. Sitzwmgsber., 1871.
342 POISONS: THEIR EFFECTS AND DETECTION. [$ 395, 396.
two months after death, but, on the other hand, the rigor mortis has
been known to disappear within twenty-four hours. If the convulsions
have been violent, there may be minute haemorrhages in the brain and
other parts. The senior author has seen considerable haemorrhage in
the trachea from this cause. When death occurs from asphyxia, the
ordinary signs of asphyxia will be found in the lungs, etc. The heart
mostly has its right side gorged with blood, but in a few cases it is
empty and contracted. -
In a case which Schauenstein has recorded * he found strychnine still
undissolved, coating the stomach as a white powder; but this is very
unusual, and probably unique. The bladder often contains urine,
which, it need scarcely be said, should be preserved for chemical
investigation. -
§ 395. Treatment.—From the cases detailed, and from the experi-
ments on animals, the direction which treatment should take is very
clear. As a matter of course, if there is the slightest probability of any
strychnine remaining in the stomach, the poison should be removed. It is
doubtful whether the stomach-pump can be ever applied with benefit in
strychnine poisoning, the introduction of the tube is likely to aggravate
the tetanus, but apomorphine can be injected subcutaneously. Large
and frequent doses of chloral should be administered in order to lessen
the frequency of convulsions, or prevent their occurrence, and it may be
necessary in a few cases, where death threatens by suffocation, to per-
form tracheotomy, and to use artificial respiration. Where chloral or
chloroform is not at hand, and in cases of emergency, where this may
easily happen, the medical man must administer in full doses the nearest
marcotic at hand.t
§ 396. Separation of Strychnine from Organic Matters.-The
separation of strychnine from organic matters, etc., is undertaken strictly
on the general principles already detailed. It may happen, however,
that in cases of poisoning there is the strongest evidence from symptoms
in the person or animal that Strychnine alone is to be sought for. In an
instance of the kind, if a complex organic liquid (such as the contents of
the stomach) is under examination, it is best to remove the solid sub-
stances by filtration through glass, wool, or linen, and evaporate nearly
to dryness over the water-bath, acidifying with acetic acid, and then
exhausting the residue repeatedly with boiling alcohol of 80 per cent.
* Op. cit.
# It is certain that lutidine would be a valuable antidote for strychnine, C. G.
Williams found that lutidine injected into frogs already under the influence of
strychnine, arrested the convulsions, or if given first, and then followed by a fatal
dose of strychnine, it prevented the appearance of the tetanus. (See ante, p. 280,
footnote.) i.
§ 396.] STRYCHNINE. 343
The alcoholic extract is in its turn evaporated to dryness, and taken up
with water; the aqueous solution is passed through a wet filter, and
then shaken up with the usual succession of fluids, viz., petroleum ether,
benzene, chloroform, and amyl alcohol, which will remove a great
number of impurities, but will not dissolve the strychnine from the acid
solution. The amyl alcohol may lastly be removed by petroleum ether;
and on removal of the final extractive (which should be done as
thoroughly as possible) chloroform is added, and the fluid is alkalised
by ammonia, which precipitates the alkaloid in the presence of the
solvent. Should the reverse process be employed—that is, ammonia
added first, and then chloroform—the strychnine is not so perfectly
dissolved, since it has time to assume a crystalline condition. On
separation and evaporation of the chloroform, the residue (if much dis-
coloured, or evidently impure) may be dissolved in alcohol or benzene,
and recrystallised several times. Cushman has published an improved
method of separating strychnine, which, according to test experiments,
appears to give good results. He describes the method as follows:*—
“The stomach contents or viscera properly comminuted are weighed, and an
aliquot part taken for analysis. The mass is digested in a beaker over-night, at a
warm temperature, with water acidulated with acetic acid. The contents of the
beaker are filtered by pressing through muslin, and then passing through paper.
The clear filtrate is evaporated on the water-bath to soft dryness, an excess of
ordinary 80 per cent. alcohol added, and boiled ten minutes with stirring, and
allowed to stand one half-hour at a warm temperature. This extraction is repeated,
the alcohol extracts united, filtered, evaporated to soft dryness, and the residue
taken up with a little water acidulated with acetic acid, and shaken out with pure
acetic ether in a separating funnel. Successive fresh portions of acetic ether are
used until the solvent shows by its colour, and by the evaporation of a few drops,
that it does not contain extractive matter. As many as twelve extractions are some-
times necessary to accomplish this. Care should be taken in each case to allow time
for as complete separation as possible between the two layers. The purified acid
aqueous liquid, which need not exceed in bulk 50 c.c., is now returned to the
separator, an equal quantity of fresh acetic ether added, and enough sodic carbonate
in solution to render the mixture slightly alkaline, and the separator is then
thoroughly shaken for several minutes. All the alkaloid should now be in solution
in the acetic ether, but a second shaking of the alkaline liquid, with acetic ether, is
always made, the two extracts united, and evaporated in a glass dish over hot water
to dryness. It will now be found that the residue shows the alkaloid fairly pure,
but not pure enough for quantitative results. The residue is dissolved in a few drops
of dilute acetic acid, warmed to complete solution, filtered if necessary, diluted to
about 30 c.c., and the solution transferred to a small separating funnel; 30 c.c. of
ether-chloroform (1–1) are now added, and the separator shaken. After separation
the heavier ether-chloroform is allowed to run off, another lot of 30 c.c. of ether-
chloroform is added, the separator shaken, and immediately enough ammonia-water
added to render the mixture alkaline, and the whole vigorously agitated for several
* “The Post-mortem Detection and Estimation of Strychnine,” by Allerton S.
Cushman, Chem. News, vol. lxx. 28.
344 POISONS : THEIR EFFECTS AND DETECTION. [$ 396.
minutes. After separation is complete, the ether-chloroform layer is run out into a
clean 50 c.c. glass-stoppered burette. The alkaline water solution is agitated with
20 c.c. more of the ether-chloroform, separated, and this extract added to that in
the burette. The burette is now supported over a small weighed glass dish, which
is kept warm on a water-bath, and the liquid allowed to evaporate gently, drop by
drop, until a sufficient quantity of the pure alkaloid has collected in the centre of
the dish to render an accurate weighing possible, or else all of the alkaloid may be
collected and weighed at once. After all possible tests have been made upon the
weighed alkaloid, the remainder is re-dissolved in a drop or two of acetic acid, a little
water added, and the dish exposed under a bell-glass to the fumes of ammonia. After
standing some time all the strychnine is found crystallised out in the beautiful charac-
teristic needle-formed crystals. The mother-liquor is drawn off with a small fine-
pointed tube and rubber bulb, the crystals carefully washed with a little water and
dried over sulphuric acid. The glass dish containing these crystals is kept as the
final exhibit, and is shown in evidence. Another convenient exhibit may be pre-
pared by moistening a small filter-paper with a solution of the alkaloid in dilute
acetic acid, then moistening with a solution of potassium dichromate ; this paper,
on being dried, may be kept indefinitely. On moistening it, and touching it at any
time with a drop of strong sulphuric acid, a violet film, changing to cherry-red, is
formed at the place of contact.”
Should search be made for minute portions of strychnine in the
tissues, considering the small amount of the poison which may produce
death, it is absolutely necessary to operate on a very large quantity of
material. It would be advisable to take the whole of the liver, the
brain, spinal cord, spleen, duodenum, kidneys, all the blood that can
be obtained, and a considerable quantity of muscular tissue, so as to
make in all about one-eighth to one-tenth of the whole body; this may
be cut up into small pieces, and boiled in capacious flasks with alcohol
acidified with acetic acid. Evaporation must be controlled by adapting
to the cork an upright condenser.
Should the analyst not have apparatus of a size to undertake this at
one operation, it may be done in separate portions—the filtrate from
any single operation being collected in a flask, and the spirit distilled
off in order to be used for the next. In this way, a large quantity of
the organs and tissues can be exhausted by half a gallon of alcohol.
Finally, most of the alcohol is distilled off, and the remainder evaporated
at a gentle heat in a capacious dish, the final extract being treated,
evaporating to a syrup, and using Cushman's process (ante, p. 343) as
just described. It is only by working on this large scale that there is
any probability of detecting absorbed strychnine in those cases where
only one or two grains have destroyed life, and even then it is possible
to miss the poison. -
Strychnine is separated by the kidneys rapidly. In a suicidal case
recorded by Schauenstein,” death took place in an hour and a half after
taking strychnine, yet from 200 c.c. of the urine, Schauenstein was able
** * Maschka's Handbuch, Band 2, p. 620.
§ 397.] STRYCHNINE. 345
to separate nitrate of strychnine in well-formed crystals. Dr. Kratter *
has made some special researches on the times within which strychnine
is excreted by the kidneys. In two patients, who were being treated by
subcutaneous injection, half an hour after the injection of 7.5 mgrms. of
strychnine nitrate the alkaloid was recognised in the urine. The strych-
nine treatment was continued for eight to ten days, and then stopped ;
two days after the cessation, strychnine was found in the urine, but none
on the third day, and the inference drawn is that the elimination was
complete within forty-eight hours. -
Strychnine has been detected in the blood of dogs and cats in re-
searches specially undertaken for that purpose, but sometimes a negative
result has been obtained without apparent cause. Dragendorfff gave
dogs the largest possible dose of strychnine daily. On the first few days
no strychnine was found in the urine, but later it was detected, especially
if food was withheld. M*Adam was the first who detected the absorbed
poison, recognising it in the muscles and urine of a poisoned horse, and
also in the urine of a hound. Dragendorff has found it in traces in the
kidneys, spleen, and pancreas; Gay, in different parts of the central
nervous system, and in the saliva. So far as the evidence goes, the liver
is the best organ to examine for strychnine; but all parts supplied with
blood, and most secretions, may contain small quantities of the alkaloid.
At one time it was believed that strychnine might be destroyed by
putrefaction, but the question of the decomposition of the poison in
putrid bodies may be said to be settled. So far as all evidence goes,
strychnine is an extremely stable substance, and no amount of putrescence
will destroy it. M*Adam found it in a horse a month after death, and
in a duck eight weeks after; Nunneley in fifteen animals forty-three
days after death, when the bodies were much decomposed; Roger in a
body after five weeks' interment; Richter in putrid tissues exposed for
eleven years to decomposition in open vessels; and, lastly, W. A. Noyes }
in an exhumed body after it had been buried 308 days.
It would appear from Ibsen's S experiments that strychnine gets
dissolved in the fluids of the dead body—so that whether strychnine
remains or not, greatly depends as to whether the fluids are retained
or are allowed to soak away ; it is, therefore, most important in exhuma-
tions to save as much of the fluid as possible. -
§ 397. Identification of the Alkaloid.—A residue containing strych-
nine, or strychnine mixed with brucine, is identified—
* Ibid.
f In an animal rapidly killed by a subcutaneous injection of acetate of strych-
nine, no strychnine was detected either in the blood or liver.—Dragendorff.
: Journ. Americ. Chem. Soc., xvi. 2.
§ Viertel. f. gericht. Med., Bd. viii.
346 POISONS : THEIR EFFECTS AND DETECTION. [$ 397.
(1) By its alkaline reaction and its bitter taste. No substance can
possibly be strychnine unless it tastes remarkably bitter.
(2) By the extremely insoluble chromate of strychnine, already
described.* A fluid containing 1 : 1000 of strychnine gives with
chromate of potash (if allowed to stand over-night) a marked precipi-
tate, dissimilar to all others, except those of lead and baryta chromates,
neither of which can possibly occur if any of the processes described are
followed,
(3) If the chromate just described is treated on a porcelain plate
with a drop of pure strong sulphuric acid, a deep rich blue colour,
passing through purple into red, rapidly makes its appearance. This
colour possesses an absorption spectrum (figured at p. 58). Dr. Guy,
neglecting intermediate colours, aptly compares the succession—(1) to
the rich blue of the Orleans plum ; (2) to the darker purple of the
mulberry; and (3) to the bright clear red of the sweet orange. These
characters—viz., alkalinity, bitterness, and the property of precipitation
by potassic chromate in a definite crystalline form, the crystals giving
the colours detailed—belong to no other substance known save strych-
nine, and for all purposes sufficiently identify the alkaloid. The same
colour is obtained by mixing a drop of sulphuric acid with strychnine
and a crystal, or speck, of any one of the following substances:—Ferrid-
cyanide of potash, permanganate of potash, peroxide of lead, peroxide of
manganese, and cerous hydroxide.
Potassic permanganate and sulphuric acid is the most delicate,
and will detect 0-001 mgrm, of strychnine ; cerous hydroxide is, on
the other hand, most convenient, for cerous hydroxide is white; all
the others have colours of their own. Cerous hydroxide is prepared
by dissolving cerium oxalate in dilute sulphuric acid and precipitating
with ammonia, filtering and well washing the precipitate; and the
atter may be used while moist, and responds well to rāg mgrm. of
Strychnine.
The influence of mixtures on the colour reactions of strychnine have
been studied by Flückiger, who states:—
“No strychnine reaction appears with sulphuric acid containing
chromic acid (made by dissolving 0.02 grim. of pot. bichromate in 10 c.c.
of water, and then adding 30 grms, strong sulphuric acid) when brucine
and strychnine mixed in equal parts are submitted to the test ; it
succeeds, however, in this proportion with sulphuric acid containing
potassium permanganate ('02 grm. pot. permanganate in 10 c.c. of
water, and 30 grms, of strong sulphuric acid).
“If the brucine is only one-tenth of the mixture, the blue-violet
* 1 grm. of strychnine gave 1280 grns. of the chromate, -78°1 per cent. of
strychnine ; 3 gave 3-811 of the chromate, = 78°77 per cent. of strychnine. —Mohr.
$ 398.] STRYCHNINE. 347
colour is obtained. A large excess of atropine does not prevent or
obscure the strychnine reaction. A solution of 1 milligrom. atropine
sulphate evaporated to dryness, together with 5 c.c. of a solution of
strychnine (1:100,000), has no influence on the reaction, neither in the
proportion of 1 mgrm. to 1 c.c. of the same solution; neither has
cinchonine nor quinine any effect.
“Morphine obscures the reaction in the following proportions:—
“A solution of 0.01 mgrm. Strychnine evaporated with a solution of
1 mgrum. of morphine sulphate on a water-bath, yields a blurred strych-
nine reaction when the residue is dissolved in sulphuric acid, and a
crystal of potassic permanganate added. But still there is evidence
whereby to suspect the presence of strychnine.
“A solution of 2 mgrms. of morphine sulphate treated in like manner
with 0:01 mgrm. of strychnine yields like results.
“A solution of 3 mgrms. of morphine sulphate evaporated to
dryness, with a solution of 0.01 mgrim. Strychnine yielded results
with the potassic permanganate test the same as if no strychnine
was present.
“A solution of 1 mgrm. of morphine sulphate, treated as above, with
a solution of 0-1 mgrm. Strychnine, offered positive proof of the presence
of the latter.”” -
Dragendorff was able to render evident 025 mgrm, mixed with
twenty times its weight of quin. Sulphate ; the same observer likewise
recognised '04 mgrm. of Strychnine in thirty-three times its weight of
caffeine. Veratrine is likewise not injurious.
$ 398. The physiological test consists in administering the substance
to some small animal (preferably to a frog), and inducing the ordinary
tetanic symptoms. It may be at once observed that if definite chemical
evidence of strychnine has been obtained, the physiological test is quite
unnecessary; and, on the other hand, should the application of a liquid
or substance to a frog induce tetanus, while chemical evidence of the
presence of strychnine was wanting, it would be hazardous to assert that
strychnine was present, seeing that caffeine, carbolic acid, picrotoxin,
certain of the opium alkaloids, hypaphorine, some of the ptomaines, and
many other substances induce similar symptoms. The best method (if
the test is used at all) is to take two frogs,f and insert under the skin of
the one the needle of a subcutaneous syringe, previously charged with a
solution of the substance, injecting a moderate quantity. The other frog
is treated similarly with a very dilute solution of strychnine ; the
two are then placed under small glass shades, and the Symptoms
* Flückiger's Reactions, translated by Nagelvoort, Detroit, 1893.
+ A very practical disadvantage of the physiological test is the great difficulty of
obtaining frogs exactly when wanted.
348 POISONS: THEIR EFFECTS AND DETECTION, [$ 399, 40O.
observed and compared. It is not absolutely necessary to inject the
solution under the skin, for if applied to the surface the same effects
are produced; but, if accustomed to manipulation, the operator will find
the subcutaneous application more certain, especially in dealing with
minute quantities of the alkaloid.*
§ 399. Hypaphorine.--One substance is known which neither physiological test
nor the colour reactions suffice to distinguish from strychnine, viz., hypaphorine,t
the active matter of a papilionaceous tree growing in Java–the Hypaphorus
subwmbrams; a small quantity of the alkaloid is in the bark, a larger quantity is in
the seed.
Hypaphorine forms colourless crystals which brown, without melting, above 220°,
and exhale a vapour smelling like naphthylamine. The free alkaloid is soluble in
water, but has no action on litmus. The salts are less soluble than the free alkaloid,
so that acids, such as nitric or hydrochloric, produce in a short time precipitates on
standing. Solutions of the salts are not precipitated by alkalies; chloroform, ether,
benzene, all fail to extract it from either alkaline or acid solutions. It gives no
precipitate with potassic chromate, but most general alkaloidal reagents precipitate.
It gives a precipitate with iodine trichloride, and has therefore probably a
pyridine nucleus, it may be an acid anilide.f. It gives the same colours as strychnine
with sulphuric acid and potassic permanganate or potassic chromate; it causes in frogs
tetanus, but the dose has to be much larger than that of strychnine. The duration
of life in doses of 15 mgrms, may extend to five days, and frogs may even recover
after 50 mgrims.
The distinction between strychnine and hypaphorine is therefore easy ; besides it
will not occur in a chloroform extract, and it will not give a precipitate with potassic
chromate.
§ 400. Quantitative Estimation of Strychnine.—The best process of estimating
the proportion of each alkaloid in a mixture of strychnine and brucine, is Keller's
method. They may also be precipitated as picrates, and the brucine picrate destroyed
by nitric acid after obtaining the combined weight of the mixed picrates; then
weighing the undestroyed strychnine picrate. -
To carry out the latter process, the solution of the mixed alkaloids must be as
neutral as possible. A saturated solution of picric acid is added drop by drop to com-
plete precipitation. A filter-paper is dried and weighed, and the precipitate collected
on to this filter-paper; the precipitate is washed with cold water, dried at 105°, and
weighed. This weight gives the combined weight of both strychnine and brucine
picrates.
The precipitate is now detached from the filter, washed into a small flask, and
heated on the water-bath for some time with nitric acid diluted to 1:056 gravity
(about 11 per cent. HNO3). This process destroys the brucine picrate, but leaves
the strychnine picrate untouched. The acid liquid is now neutralised with ammonia
or soda, and a trace of acetic acid added ; the precipitate of Strychnine picrate is now
* Methyl strychnine, as well as methyl brucine, has been shown by Brown and
Fraser to have an effect exactly the opposite to that of Strychnine, paralysing the
muscles like curare. In the case, therefore, of the methyl compounds, a physiological
test would be very valuable, since these compounds do not respond to the ordinary
tests.
+ Dr. C. Plugge, Arch, f, ea.p. Path, w, Ph., Bd. xxxii. 313.
† Julius Tafel (Ber., 1890, 412) has shown that the colour reaction with H2SO,
and oxidising agents are the characteristic tests of an acid anilide.
$ 40I.] BRUCINE. 349
collected and weighed. The weight of this subtracted from the first weight, of course,
gives that of the brucine picrate.
One part of strychnine picrate is equal to 0'5932 strychnine ; and one part of
brucine picrate is equal to 0-6324 brucine.
From the strychnine picrate the picric acid may be recovered and weighed by
dissolving the picrate in a mineral acid and shaking out with ether; from the acid
liquid thus deprived of picric acid the alkaloid may be separated by alkalising with
almmonia and shaking out with chloroform. -
Keller's method is based on the conversion of the brucine into dinitro-brucine,
which is insoluble in chloroform. From 0-2 to 0-3 grm. of the crude alkaloids is
dissolved in 10 c.c. of 10 per cent. H.SO4; when cold, 1.5 c.c. of 50 per cent. nitric
acid (sp. gr. 1'42) is added. After one and a half hours pour into a separating funnel,
make alkaline with ammonia, and shake out with chloroform. The chloroform takes
up dinitro-strychnine but not dinitro-brucine.
$ 401. Brucine (C, H, N,0, +4H,0) occurs associated with strych-
nine in the plants already mentioned; its best source is the so-called
false angustura bark, which contains but little strychnine. Its action is
similar to that of strychnine. If crystallised out of dilute alcohol it con-
tains 4 molecules of water, easily expelled either in a vacuum over sul-
phuric acid or by heat. Crystallised thus, it forms transparent four-sided
prisms, or arborescent forms, like boric acid, `If thrown down by
ammonia from a solution of the acetate, it presents itself in needles or
in tufts.
Brucine and strychnine contain the same group C15H17N,03, but
brucine contains two methoxyl groups thus:—
C15H17N2O2 - CoPIs C15H17N2O2 amº CaFIg(OCH3)2
Strychnine. Brucine.
The recently-crystallised alkaloid has a solubility different from that
which has effloresced, the former dissolving in 320 parts of cold, and
150 parts of boiling water; whilst the latter (according to Pelletier and
Caventou) requires 500 of boiling, and 850 parts of cold water for
solution. Brucine is easily soluble in absolute, as well as in ordinary
alcohol; 1 part dissolves in 17 of chloroform, in 60.2 of benzene. Petro-
leum ether, the volatile and fatty oils and glycerine, dissolve the alkaloid
slightly, amyl alcohol freely; it is insoluble in anhydrous ether. The
behaviour of brucine in the subliming cell is described at p. 261. Anhy-
drous brucine melts in a tube at 178°. A solution of anhydrous brucine
in absolute alcohol dissolved in the proportion of 2:129 grnms, in 100 c.c.
of alcohol has a specific rotation [an] at 20° = – 80.1 (Tykociner). The
taste is bitter and acrid. Soubeiran maintains that it can be recognised if
1 part is dissolved in 500,000 parts of water. If nitric trioxide be passed
into an alcoholic solution of brucine, first brucine nitrate is formed ; but
this passes again into solution, from which, after a time, a heavy,
granular, blood-red precipitate separates: it consists of dinitro-brucine
350 POISONS : THEIR EFFECTS AND DETECTION, [$ 4O2.
(Cºsho;(NO)N30). Brucine fully neutralises acids, and forms salts,
which are for the most part crystalline. The neutral sulphate
(C28H2;N30;SH2O, +3%H,0) is in long needles, easily soluble in water.
The acetate is not crystalline, that of strychnine is so (p. 328).
Brucine is precipitated by ammonia, by the caustic and carbonated
alkalies, and by most of the group reagents. Ammonia does not preci-
pitate brucine, if in excess; on the other hand, strychnine comes down if
excess of ammonia is added immediately. This has been proposed as a
method of separation; if the two alkaloids are present in acid solution,
ammonia in excess is added, and the solution is immediately filtered ;
the quantitative results are, however, not good, the strychnine precipitate
being invariably contaminated by brucine.
Chromate and dichromate of potassium give no precipitate with neutral
salts of brucine; on the other hand, strychnine chromate is at once
formed if present. It might, therefore, be used to separate strychnine
from brucine. The authors and others have attempted this method, but
the results were not satisfactory.
§ 402, Physiological Action.—The difference between the action of
strychnine and that of brucine on man or animals is not great. Mays
states that strychnine affects more the anterior, brucine the posterior
extremities. In strychnine poisoning, convulsions occur early, and
invariably take place before death; but death may occur from brucime
without any convulsions, and in any case they develop late. Brucine
diminishes local sensibility when applied to the skin; strychnine does
not.” In a physiological sense, brucine may be considered a diluted
strychnine. The lethality of brucine, especially as compared with
strychnine, has been investigated by F. A. Falck.f. He experimented on
11 rabbits, injecting subcutaneously brucine nitrate in doses of varying
magnitude, from 100 mgrms, down to 20 mgrms, per kilogram of body
weight. He found that brucine presented three stages of symptoms.
In the first, the respiration is quickened; in 3 of the 11 cases a strange
injection of the ear was noticed; during this period the pupils may be
dilated. In the second stage, there are tetanic convulsions, trismus,
opisthotomus, oppressed respiration, and dilated pupils. In the third
stage the animal is moribund. Falck puts the minimum lethal dose for
rabbits at 23 mgrms. per kilo. Strychnine kills 3-06 times more quickly
than brucine, the intensity of the action of strychnine relative to that of
brucine being as 1 : 117:4. Falck has also compared the minimum lethal
dose of strychnine and brucine with the tetanising opium alkaloids, as
shown in the following table:–
* Journ. Physioſ., viii. 391–403.
t Brucin w. Strychnim, ; eine toacikologische Parallele, von Dr. F. A. Falck.
Vierteljahrsschr. f. gerichtl, Med., Band xxiii. p. 78.
$ 403.] BRUCINE. 35 I
TABLE SHOWING THE LETHAL DOSES OF WARIOUS
TETANISING POISONS.
Minimum Lethal
Dose for every Proportional
Kilogram Weight Strength.
of Rabbit.
Mgr.ms.
Strychnine nitrate, . * * º e 0-6 e tº º
Thebaine nitrate, . nº * - g 14 °4 24 °0
Brucine nitrate, ſº & g º g 23:0 38°33
Laudanine nitrate, . & ſº * g 29'6 49 °33
Codeine nitrate, * tº s * 51-2 85 °33
Hydrocotarnine nitrate, . g º g 203'8 339°66
If these views are correct, it follows that the least fatal dose for an
adult man would be 1:64 grm. (about 24-6 grains) of brucine nitrate.
$ 403. Tests.—If to a solution of brucine in strong alcohol a little
methyl iodide is added, at the end of a few minutes circular rosettes of
crystal groups appear (see fig., p. 352): they are composed of methyl
brucine iodide (Cash;(CH3)N30, HI). Crystals identical in shape are also
obtained if an alcoholic solution of iodine, or hydriodic acid with iodine,
is added to an alcoholic solution of brucine. A solution of Strychnine
gives with methyl iodide no similar reaction. Strychnine in alcoholic
solution, mixed with brucine, in no way interferes with the test. The
methyl iodide test may be confirmed by the action of nitric acid. With
that reagent it produces a scarlet colour, passing into blood-red, into
yellow-red, and finally ending in yellow. This can be made something
more than a mere colour test, for it is possible to obtain a crystalline
body from the action of mitric acid on brucine. If a little of the latter
be put in a test tube and treated with nitric acid of 1:4 specific gravity
(immersing the test tube in cold water to moderate the action), the red
colour is produced. On spectroscopic examination of the blood-red
liquid a broad, well-marked absorption band is seen, the centre of which
(see page 58) is between E. and F. [W. L. about 500]. There is also a
development of nitric oxide and carbon dioxide, and the formation of
methyl nitrite, oxalic acid and kakotelin (Cash, N20, 4-5NHOs–-
CºoHo, N.O., + N(CH3)O3 + C3H2O, +2NO + 2H2O). On diluting abun-
dantly with water, the kakotelin separates in yellow flocks, and may be
crystallised out of dilute hydrochloric or dilute nitric acid in the form of
yellow or orange-red crystals, very insoluble in water, but dissolving
readily in dilute acid. On removal by dilution of the product just
named, neutralisation with ammonia, and addition of a solution of
chloride of calcium, the oxalate of lime is thrown down. The nitric acid
test is, therefore, a combined test, consisting of-the production by the
352 POISONS : THEIR EFFECTS AND DETECTION. [š 403.
action of nitric acid (1) of a red colour; (2) of yellow scales or crystals
insoluble in water; (3) of oxalic acid. No alkaloid save brucine is
known to give this reaction. -
There are other methods of producing the colour test. If a few
drops of nitric acid are mixed with the substance in a test tube, and
then sulphuric acid cautiously added, so as to form a layer at the bottom,
at the junction of the liquids a red zone, passing into yellow, is seen.
A solution of brucine is also coloured red by chlorine gas, ammonia
changing the colour into yellow.
Flückiger * has proposed as a test mercurous nitrate, in aqueous
solution with a little free nitric acid. On adding this reagent to
Crystals of Methyl-brucine Iodide. (From a photograph.)
a solution of brucine salt, and gently warming, a fine carmine colour
is developed.
In regard to the separation of brucine from organic fluids or tissues,
the process already detailed for strychnine suffices. It is of very great
importance to ascertain whether both strychnine and brucine are present
or not—the presence of both pointing to nux vomica or one of its pre-
parations. The presence of brucine may, of course, be owing to impure
strychnine; but if found in the tissues, that solution of the question is
improbable, the commercial strychnine of the present day being usually
pure, or at the most containing so small a quantity of brucine as would
hardly be separated from the tissues.
* Archiv f. Pharm. (3), vi. 404.

$404–408.] GELSEM.INE. 353
2. THE QUEBRACHO GROUP OF ALKALOIDS.
§ 404. The bark of the Quebracho Blanco” (Aspidosperma quebracho) contains,
according to Hesse's researches, no fewer than six alkaloids—Quebrachine, Aspido-
spermine, Aspidospermatine, Aspidosamine, and Hypoquebrachine. The more
important of these are Aspidospermine and Quebrachine.
§ 405. Aspidospermine (C23Had N2O2) forms colourless needles which melt at
206°. They dissolve in about 6000 parts of water at 14°–48 parts of 90 per cent.
alcohol, and 106 parts of pure ether. The alkaloid gives a fine magenta colour with
perchloric acid.
§ 406. Quebrachine (Cai HosN2O3) crystallises in colourless needles, melting-
point (with partial decomposition) 215°. The crystals are soluble in chloroform,
with difficulty soluble in cold alcohol, but easily in hot. The alkaloid, treated with
sulphuric acid and peroxide of lead, strikes a beautiful blue colour. It also gives
with sulphuric acid and potassic chromate the strychnine colours. Quebrachine,
dissolved in sulphuric acid containing iron, becomes violet-blue, passing into brown.
The alkaloid, treated with strong sulphuric acid, becomes brown; on adding a
crystal of potassic nitrate, a blue colour is developed ; on now neutralising with
caustic soda no red coloration is perceived. Dragendorff has studied the best method
of extracting these alkaloids for toxicological purposes. He recommends extraction
of the substances with sulphuric acid holding water, and shaking up with solvents.
Aspidospermine is not extracted by petroleum ether or benzene from an acid watery
extract, but readily by chloroform or by amyl alcohol. It is also separated from the
same solution, alkalised by ammonia, by ether, amyl alcohol or chloroform ; with
difficulty by petroleum cther ; some is dissolved by benzene. Quebrachine may be
extracted from an acid solution by chloroform, but not by petroleum ether. Alka-
lised by ammonia, it dissolves freely in chloroform and in amyl alcohol. Traces are
taken up by petroleum, somewhat more by benzene. Aspidospermine is gradually
decomposed in the body, but Quebrachine is more resistant, and has been found in
the stomach, intestines, blood, and urine. The toxicological action of the bark
ranks it with the tetanic class of poisons. In this country it does not seem likely
to attain any importance as a poison. .
3. PEREIRINE.
§ 407. Pereirine (C15H23N2O)—an amorphous alkaloid from pereira bark—gives
a play of colours with sulphuric acid and potassic bichromate similar to but not
identical with that of strychnine. Fröhde's reagent strikes with it a blue colour.
On dissolving pereirine in dilute sulphuric acid, and precipitating by gold chloride,
the precipitate is a beautiful red, which, on standing and warming, is deepened.
Pereirine may be extracted from an acid solution, after alkalising with ammonia, by
ether or benzene.
4. GELSEM.INE.
§ 408. Gelsemine (C23H2s N2O4) and gelseminine (C22H23N2O3) are two alkaloids
which have been separated from Gelsemium sempervirens, the Carolina jessamine, a
plant having affinities with several natural orders, and placed by De Candolle among
the Loganiaceae, by Chapman among the Rubiaceae, and by Decaisne among the
Apocynaceae. It grows wild in Virginia and Florida. i Gelsemine is a strong base ;
* See Liebig’s Annal., ccxi. 249–282; Ber. der deutsch. chem. Gesellsch., xi.
2189 ; xii., 1560.
+ The following are its botanical characters:—Calyx five-parted, corolla funnel-
shaped, five-lobed, somewhat oblique, the lobes almost equal, the posterior being
innermost in bud; stamens five ; anthers oblong Sagittate, style long and slender ;
23
354 POISONS: THEIR EFFECTS AND DETECTION. [$ 409, 410.
it is yellowish when impure, but a white amorphous powder when pure. It fuses
below 100° into a transparent vitreous mass, at higher temperatures it condenses on
glass in minute drops ; its taste is extremely bitter; it is soluble in 25 parts of ether,
in chloroform, bisulphide of carbon, benzene, and in turpentine ; it is not very
soluble in alcohol, and still less soluble in water, but it freely dissolves in acidulated
water. The caustic alkalies precipitate it, the precipitate being insoluble in excess;
it is first white, but afterwards brick-red. Tannin, picric acid, iodised potassic
iodide, platinic chloride, potassio-mercuric iodide, and mercuric chloride all give
precipitates. Fröhde's reagent gives with gelsemine a brown changing to green.
Sulphuric acid dissolves gelsemine with a reddish or brownish colour; after a
time it assumes a pinkish hue, and if warmed on the water-bath, a more or less
purple colour; if a small crystal of potassic bichromate be slowly stirred in the
sulphuric acid solution, reddish purple streaks are produced along the path of the
crystal ; ceric oxide exhibits this better and more promptly, so small a quantity as
‘001 grain showing the reaction. This reaction is something like that of strychnine,
but nitric acid causes gelsemine to assume a brownish-green, quickly changing to a
deep green—a reaction which readily distinguishes gelsemine from strychnine and
other alkaloids.
$ 409. Fatal Dose.-10 mgrms, killed a frog within four hours, and 8 mgrms, a
cat within fifteen minutes. A healthy woman took an amount of concentrated
tincture, which was equivalent to 11 mgrms. (# grain), and died in seven and a half
hours.
§ 410. Effects on Animals—Physiological Action.—Gelsemine acts powerfully
on the respiration ; for example, Drs. Sydney Ringer and Murrell” found, on operating
on the frog, that in two minutes the breathing had become distinctly slower; in
three and a half minutes, it had been reduced by one-third; and in six minutes, by
one-half; at the expiration of a quarter of an hour, it was only one-third of its
original frequency ; and in twenty minutes, it was so shallow and irregular that it
could no longer be counted with accuracy. In all their experiments they found
that the respiratory function was abolished before reflex and voluntary motion had
become extinct. In several instances the animals could withdraw their legs when
their toes were pinched, days after the most careful observations had failed to detect
the existence of any respiratory movement. The heart was seen beating through
the chest wall long after the complete abolition of respiration.
In their experiments on warm-blooded animals (cats), they noticed that in a few
minutes the respirations were slowed down to 12 and even to 8, and there was
loss of power of the posterior extremities, while at short intervals the upper half of
the body was convulsed. In about half an hour paralysis of the hind limbs was
almost complete, and the respiratory movements so shallow that they could not be
counted. In the case of a dog, after all respiration had ceased tracheotomy was
performed, and air pumped in : the animal recovered.
Ringer and Murrell consider that gelsemine produces no primary quickening of
the respiration, that it has no direct action on either the diaphragm or intercostal
muscles, that it paralyses neither the phrenic nor the intercostal nerves, and that it
diminishes the rate of respiration after both vagi have been divided. They do not
stigmas two, each two-parted, the divisions being linear ; fruit elliptical, flattened
contrary to the narrow partition, two-celled, septicidally two-valved, the valves
keeled ; seeds five to six in each cell, large, flat, and winged ; embryo straight in
fleshy albumen; the ovate flat, cotyledons much shorter than the slender radicle ;
stem smooth, twining and shrubby ; leaves opposite, entire, ovate, or lanceolate,
shining on short petioles, nearly persistent; flowers large, showy, very fragrant,
yellow, one to five in the axil of the leaves.
* Lancet, 1876, vol. i. p. 415.
§ 4II, 412.] •. GELSEMINE. 355
consider that gelsemine acts on the cord through Setschenow's inhibitory centre, but
that it destroys reflex power by its direct action on the cord, and that probably it
has no influence on the motor nerves. Dr. Burdon Sanderson has also investigated
the action of gelsemine on the respiration, more especially in relation to the move-
ments of the diaphragm. He operated upon rabbits; the animal being narcotised
by chloral, a small spatula, shaped like a teaspoon, was introduced into the peri-
toneal cavity through an opening in the linea alba, and passed upwards in front of
the liver until its convex surface rested against the under side of the centrum ten-
dineum. The stem of the spatula was brought into connection with a lever, by
means of which its to-and-fro movements (and consequently that of the diaphragm)
were inscribed. The first effect is to augment the depth but not the frequency of the
respiratory movements; the next is to diminish the action of the diaphragm both in
extent and frequency. This happens in accordance with the general principle
applicable to most cases of toxic action—viz., that paresis of a central organ is
preceded by over-action. The diminution of movement upon the whole is pro-
gressive, but this progression is interrupted, because the blood is becoming more and
more venous, and, therefore, the phenomena of asphyxia are mixed up with the
toxical effects. Dr. Sanderson concludes that the drug acts by paralysing the
automatic respiratory centre ; the process of extinction, which might be otherwise
expected to be gradual and progressive, is prevented from being so by the inter-
vention of disturbances of which the explanation is to be found in the imperfect
arterialisation of the circulating blood. Ringer and Murrell have also experimented
upon the action of gelsemine on the frog's heart. In all cases it decreased the
number of beats; a small fatal dose produced a white contracted heart, a large
fatal dose, a dark dilated heart; in either case arrest of the circulation of course
followed.
§ 411. Effects on Man.—The preparations used in medicine are the fluid extract
and the tincture of gelsemine ; the latter appears to contain the resin of the root as
well as the active principle. There are several cases on record of gelsemine, or the
plant itself, having been taken with fatal effect.* Besides a marked effect on the
respiration, there is an effect upon the eye, better seen in man than in the lower
animals; the motor nerves of the eye are attacked first, objects cannot be fixed,
apparently dodging their position, the eyelids become paralysed, droop, and cannot
be raised by an effort of the will ; the pupils are largely dilated, and at the same
time a feeling of lightness has been complained of in the tongue; it ascends gradually
to the roof of the mouth, and the pronunciation is slurred. There is some paresis of
the extremities, and they refuse to support the body; the respiration becomes
laboured, and the pulse rises in frequency to 120 or 130 beats per minute, but the
mind remains clear. The symptoms occur in about an hour and a half after taking
an overdose of the drug, and, if not excessive, soon disappear, leaving no unpleasant-
ness behind. If, on the other hand, the case proceeds to a fatal end, the respiratory
trouble increases, and there may be convulsions, and a course very similar to that
seen in experimenting on animals. Large doses are especially likely to produce
tetanus, which presents some clinical differences distinguishing it from strychnine
tetanus. Gelsemine tetanus is always preceded by a loss of voluntary reflex power,
respiration ceases before the onset of convulsions, the posterior extremities are most
affected, and irritation fails to excite another paroxysm till the lapse of some seconds,
as if the exhausted cord required time to renew its energy; finally, the convulsions
only last a short time. 4.
§ 412. Extraction from Organic Matters, or the Tissues of the Body.—Dragen-
dorff states that, from as little as half a grain of the root, both gelsemine and gelsemic
* See Lancet, 1873, vol. ii. p. 475; Brit. Med, and Surg. Journ., April 1869;
Phil. Med, and Surg. Reporter, 1861.
356 POISONS : THEIR EFFECTS AND DETECTION. [$ 413.
acid may be extracted with acid water, and identified. On extracting with water
acidified with sulphuric acid, and shaking up the acid liquid with chloroform, the
gelsemic acid (aesculin ) is dissolved, and the gelsemine left in the liquid. The
chloroform on evaporation leaves gelsemic acid in little micro-crystals; it may be
identified by (1) its crystallising in little tufts of crystals; (2) its strong fluorescent
properties, 1 part dissolved in 15,000,000 parts of water showing a marked fluores-
cence, which is increased by the addition of an alkali; and (3) by splitting up into
sugar and another body on boiling with a mineral acid. After separation of gelsemic
acid, the gelsemine is obtained by alkalising the liquid, and shaking up with fresh
chloroform ; on separation of the chloroform, gelsenline may be identified by means
of the reaction with nitric acid, and also the reaction with potassic bichromate and
sulphuric acid.
5. COCA ALKALOIDS—COCAINE.
$ 413. The leaves of Erythroacylon coca contain a number of alkaloids, of which
the following have been investigated :—
Cocaine, C17H31NO4.
Cinnamyl cocaine, Cho H23NO4.
a-Truxilline (C19H23NO3)2.
B-Truxilline (C19H23NO3)2.
Benzoyl ecgonine, Clghia NO4.
Tropa-cocaine, Cashion O2.
Hygrine, CsPHis NO.
Cuscohygrine, C15H23NO2.
All these alkaloids are esters of ecſſonine, and on saponification they yield ecgonine,
methyl alcohol, and an aromatic acid. -
Cocaine, Cºhol NO4, is the only coca alkaloid of any great present importance, and
the other alkaloids are commercially converted into cocaine by first obtaining ecgonine
from them, treating this with benzoic anhydride which converts it into benzoyl ecgo-
nine, benzoyl ecgonine being converted into cocaine by treating its methyl alcohol
solution with HCl. Thus—
Cin H2NO3 + 2.H2O -> º + Cº. HaO2+ CH3OH
Cocaine. cgomine. Benzoic Methyl
acid. alcohol.
2C9His NO34-(C6H,CO),0->2C9H11NO3(COCSH)4-H,O
Ecgonine. Benzoic Benzoyl ecgonine.
anhydride.
CigFilon Oa + CH3OH -> Cin HeinO, + H2O
Benzoyl Methyl Cocaine.
ecgonine. alcohol.
Cocaine crystallises from alcohol in prisms melting at 98°. Not very soluble in
water, Soluble in ether, alcohol, benzene, chloroform, and CS2. Natural cocaine is
bitter, alkaline to methylorange, and laºvorotatory; the specific rotatory power of its
hydrochloride in water = -7195°, and it yields l-cegonine. From d-ecgonine may
be prepared d-cocaine which melts at 46–47°C., and from inactive ecgonine may be
prepared inactive cocaine, melting at 80°C. ; this variety is soluble in alcohol and
ether, and is probably a racemic variety of natural cocaine. Also from a-ecgonine
may be obtained a-cocaine, melting at 305°C., insoluble in ether, not very soluble in
alcohol, and a little more soluble in water. Eucaine, which is n-methyl benzoyl
triacetone alcamine carboatylic acid methyl ester, is used as an artificial substitute for
cocaine ; it crystallises in prisms melting at 104° C., and has similar properties to
natural cocaine, as also have d-cocaine and i-cocaine. On the other hand, a-cocaine
has no anaesthetic properties. If in the reaction forming cocaine from ecgonine
$ 414–416.] COCAINE. 357
higher alcohols be substituted for methyl alcohol, higher homologues of cocaine are
formed, having much the same physiological properties as cocaine.
The constitution of ecgonine and a-ecgonine may be represented as follows:—
CH2—CH-CH-COOH CH2—CH —CH2
/ - / COOH
Š-cºchon 8-ch) có
N COOH
CH2—CH-CH2 CH2 CH CH2 -
Ecgonine. a-Ecgonine.
§ 414. Cocaine Hydrochlorate (C17H31NO, HCl).--Crystallised from
alcohol, cocaine hydrochlorate appears in prismatic crystals; these
crystals, according to Hesse,” when perfectly pure, should melt at
186", although the melting-point is generally given as 200° or even
202°. Cocaine hydrochlorate is soluble in half its weight of water,
insoluble in dry ether, but readily soluble in alcohol, amyl alcohol,
or chloroform. -
$ 415. Pharmaceutical Preparations.—Cocaine hydrochlorate is
officinal. Gelatine discs, weighing 131 mgrms. (#y grain), and each
containing 0-33 mgrrm. (gåg grain) of the salt are officinal, and
used by ophthalmic surgeons. A solution of the hydrochlorate, con-
taining 10 per cent. of cocaine hydrochlorate and (for the purposes
of preserving the solution) 0.15 per cent. of salicylic acid is also
officinal. Stronger solutions may also be met with ; for instance, a
20 per cent. Solution in oil of cloves for external application in cases
of neuralgia.
§ 416. Separation of Cocaine and Tests.-Cocaine may be shaken
out of solutions made slightly alkaline by ammonia by treatment with
benzene; it also passes into petroleum ether under the same circum-
stances. The best method is to extract a solution, made feebly alkaline,
thoroughly by ether, and then shake it out by benzene and evaporate
the separated benzene at the ordinary air temperature. The property
of the alkaloid to melt at or below the temperature of boiling water, and
the ready decomposition into benzoic acid and other products, render
cocaine easy of identification. If, for instance, a small particle of cocaine
is put in a tube, a drop of strong sulphuric acid added and warmed by
the water-bath, colourless crystals of benzoic acid sublime along the tube,
and an aromatic odour is produced. -
Flückiger has recommended the production of benzoate of iron as a
useful test both for cocaine and for cocaine hydrochlorate.
One drop of a dilute solution of ferric chloride added to a solution of
20 mgrms. of cocaine hydrochlorate in 2 c.c. of water, gives a yellow
fluid, which becomes red on boiling from the production of iron benzoate.
This reaction is of little use unless a solution of the same strength of
* O. Hesse, Annalem, cclxxvi. 342–344.
358 POISONS : THEIR EFFECTS AND DETECTION. [$ 417.
ferric chloride, but to which the substance to be tested has not been
added, is boiled at the same time for comparison, because all solutions of
ferric chloride deepen in colour on heating.
A solution of the alkaloid evaporated to dryness on the water-
bath, after being acidulated with nitric acid, and then a few drops
of alcoholic solution of potash or soda added, develops an odour of
benzoic ethyl ester. Cocaine hydrochlorate, when triturated with
calomel, blackens by the slightest humidity or by moistening it with
alcohol. Cocaine in solution is precipitated by most of the group
reagents, but is not affected by mercuric chloride, picric acid, nor
potassic bichromate.
Added to the tests above mentioned, there is the physiological
action; cocaine dilates the pupil, tastes bitter, and, for the time,
arrests sensation; hence the after-effect on the tongue is a sensation
of numbness.
Cocaine may be estimated in fairly strong pure solutions (1 per cent.)
by adding a N/10 iodine until the iodine is in excess; the hydriodide
periodide is filtered off and the excess of iodine in the filtrate determined
by N/10 sodium thiosulphate. The iodine compound formed is
Cº. H.O.NHII.”
$417. Symptoms.-A large number of accidents occur each year
from the external application of cocaine; few, however, end fatally.
Cocaine has thus produced poisonous symptoms when applied to the eye,
to the rectum, to the gums, to the urethra, and to various other parts.
There have been a few fatal cases, both from its external and internal
administration; Mannheim, for example, has collected eleven of such
instances.
The action of cocaine is twofold; there is an action on the central
and the peripheral nervous system. In small doses cocaine excites the
spinal cord and the brain; in large it may produce convulsions and then
paralysis. The peripheral action is seen in the numbing of sensation.
There is always interference with the accommodation of vision, and
dilatation of the pupil. The eyelids are wider apart than normal, and
there may be some protrusion of the eyeball.
The usual course of an acute case of poisoning is a feeling of dryness
in the nose and throat, difficulty of swallowing, faintness, and there is
often vomiting; the pulse is quickened; there is first cerebral excitement,
followed usually by great mental depression. Occasionally there is an
eruption on the skin. Hyperaesthesia of the skin is followed by great
diminution of sensation, the pupils, as before stated, are dilated, the eyes
protruding, the eyelids wide open, the face is pale, and the perspiration
profuse. Convulsions and paralysis may terminate the scene. Death
* W. Garsed and J. N. Collie, Jowr. Chem. Soc., lxxix., 1901.
$ 418–42O.] CORYDALINE. - 359
takes place from paralysis of the breathing centre; therefore the heart
beats after the cessation of respiration. As an antidote, nitrite of amyl
has apparently been used with success.
There is a form of chronic poisoning produced from the taking of
small doses of cocaine daily. The symptoms are very various, and are
referable to disturbance of the digestive organs, and to the effect on the
nervous system. The patients become extremely emaciated, and it seems
to produce a special form of mania.
§ 418. Post-mortem Appearances.—The appearances found in acute
cases of poisoning have been hyperamia of the liver, spleen, and kidneys,
as well as of the brain and spinal cord.
In the experimental poisoning of mice with cocaine Ehrlich * found
a considerable enlargement of the liver.
§ 419. Fatal Dose.—The fatal dose, according to Mannheim, f must
be considered as about 1 grn. (15:4 grains); the smallest dose known to
have been fatal is 0.08 grim. (1-2 grain) for an adult, and 0.05 grim. (0-7
grain) for a child.
6. CORYDALINE.
§ 420. From the root of Corydalis cava, eight alkaloids have been isolated, viz.,
Corydaline, C22H22NOI, Corybulbine, Cai H2:NOA, Isocorybulbine Cel H2:NO3, Bulbo-
capnine, C19H29NO4, Corytuberine, C19H23NO4, Corycavine, C23H23NO3, Corycavamine,
Col.BaNOR, and Corydine, C2i}{2|NO4.
These alkaloids are not of any great toxicological importance, but corydaline in
large doses causes epileptiform convulsions. Death takes place from respiratory
paralysis.
Corydaline crystallised in the cold and away from light, out of a mixture of
absolute alcohol and ether, forms colourless, flat, prismatic crystals, which quickly
turn yellow on exposure to light or heat. It is bitter to the taste and its solutions
are dextro-rotatory. Pure corydaline changes colour at about 125°, softens at about
133°, and melts finally at 134° to 135°. It dissolves in ether, chloroform, carbon
disulphide, and benzene, but not so readily in alcohol. It is almost insoluble in cold
water, and but slightly soluble in boiling water. Water precipitates it from a
solution in alcohol. It is also soluble in dilute hydrochloric and sulphuric acids.
It gives a precipitate with potassium iodide if a solution of the hydrochloride be used.
The precipitate crystallises out of hot water in clusters of short lemon-yellow pris-
matic crystals, and has the formula of CºRº;NOAHI. Corydaline platinochloride has
the composition of (C23H2:NOA), HaPtCls, containing Pt. 16'94 per cent., and 2:44 per
cent. of N.
An alcoholic solution of iodine oxidises corydaline to dehydrocorydaline
hydriodide, C2H3NO.H.I. Dehydrocorydaline is very like berberine. The relation
of corydaline to berberine is further shown by the formation of corydaldine when
corydaline is oxidised, *
CHAO CO – NH
XC.H.3
CHAO CO – NEI
Corydaldine.
* Deutsche med. Wochens., 1890, No. 32.
f Deutsch. Arch. f. klin. Med., Bd. viii., 1891, 380.
36O POISONS: THEIR EFFECTS AND DETECTION. [Š 421, 422.
Dobbie and Lauder, as the result of a number of researches, have provisionally
adopted the following formula for corydaline,”
CH
HC ſ| C—OCH,

C 2's C–O CH
H3C ſ N/6 3
on Hg
CHCH.
CH,0–c ºn 3
0's. A "*
CH (CH,
CH,0–
W.—The Aconite Group of Alkaloids.
§ 421. The officinal aconite is the Aconitum napellus—monkshood or
Wolfsbane—a very common garden plant in this country, and one
cultivated for medicinal purposes. The root of A. napellus is from 2 to
4 inches long, conical in shape, brown externally, and white internally.
The leaves are completely divided at the base into five wedge-shaped
lobes, each of the five lobes being again divided into three linear
segments. The numerous seeds are three-sided, irregularly twisted,
wrinkled, of a dark-brown colour, in length one-sixth of an inch, and
weighing 25 to the grain (Guy). The whole plant is one of great beauty,
from 2 to 6 feet high, and having a terminal spike of conspicuous
blue flowers. The root has been fatally mistaken for horseradish, an
error not easily accounted for, since no similarity exists between them.
§ 422. Pharmaceutical Preparations of Aconite.-The preparations
of aconite used in medicine are—
Aconitine, officinal in all the pharmacopoeias. -
Aconite liniment (linimentum aconiti), made from the root with
spirit, and flavoured with camphor; officinal in the British Pharma-
copoeia. It may contain about 2.0 per cent. of aconitine.
Aconite tincture, officinal in all the pharmacopoeias.
Aconite ointment, 8 grains of aconitine to the oz. (i.e., l'66 per
cent.); officinal in the British Pharmacopoeia.
Aconite extract, the juice of the leaves evaporated; officinal in
most of the pharmacopoeias. The strength in alkaloid of the extract
varies; in six samples examined by F. Casson, the least quantity was
0-16 per cent., the maximum 0.28 per cent.f
* Journ. Chem. Soc. T., 1892, 244; 1895, 67 ; 1897, 71 ; 1901, 79; 1902, 145.
t Pharm. Journ., 1894, 901.
§ 423.] ACONITE GROUP OF ALKALOIDS. 361
Fleming's tincture of aconite is not officinal, but is sold largely in
commerce. It is from three to four times stronger than the B.P.
tincture.
§ 423. The species of aconite are numerous; the few that have been
investigated clearly indicate that the genus is rich in poisonous alkaloids
and that there are several aconitines.
Professor Dunstan,” who has been for many years investigating this
subject, summarises the results obtained up to the present somewhat as
follows:—
The alkaloids of aconite plants may be divided into two groups; the
first, a toxic group, of which the type is ordinary aconitine, contains
alkaloids which are diacyl esters of a series of poly-hydric bases con-
taining four methoxyl groups, the aconines.
The members of this group are—
Aconitine from Aconitum napellus.
Japaconitine from Aconitum deinorrhysum.
Bikhaconitine from Aconitum spicatus.
Indaconitine from Aconitum chasmanthum.
All these are highly poisonous and exert a very similar physiological
action. When the acetyl group is removed by hydrolysis the resulting
benzoyl or veratroyl base is but feebly poisonous; still hydrolysing
leads to the splitting off of the aconines, bases not only destitute of
toxic power, but in some respects acting in an antagonistic way to the
aconitine parent.
The second group is the atisine group, which contains atisine from
Aconitum heterophyllum and palmatine from Aconitum palmatum ; these
two alkaloids are not poisonous and therefore will not be described.
The aconitine group of alkaloids is divided into (1) Aconitines, (2)
Pseudaconitines, and these may provisionally be represented by the
following formulae:— -
1. ACONITINEs.
Aconitine (acetyl-benzoyl-aconine),
OCO-CH,
Csabia,011N = Cs1H2O3 Né-(OCH3),
OCO-Cahs
Japaconitine (acetyl-benzoyl-japaconine),
- OCO-CH,
Cºah,00un = Calhº,0sNé-(OCH3),
OCO'Csh;
Indaconitine (acetyl-benzoyl-pseudaconine),
OCO-CH,
CsáHanoion == C21BI2;O2N *-º (OCH3)4
OCO-CeBIs
* W. R. Dunstan, F.R.S., and T. Anderson Henry, Journ. Chem. Soc. Trans.,
1905, 1650.
362 POISONS : THEIR EFFECTS AND DETECTION. [$ 423.
2. PSEUDACONITINES.
Pseudaconitine (acetyl-veratroyl-pseudaconine),
º
Cºg H51Ois N = Calho,02N4-(OCH3)
36 1 \'l 211–127V2 o66&H,(0:CH.),
Bikhaconitine (acetyl-veratroyl-bikhaconine),
CCO-CH,
C36H51On N = cahºosé;
OCO-Cºha(0°CH3)2
Each of the aconitines contains four methoxyl groups, and on
hydrolysis furnish one molecular proportion of acetic and one of benzoic
acid; thus aconitine should yield 18.9 benzoic, 9.3 per cent. acetic acids,
and 79.8 per cent. aconine; similarly japaconitine breaks up into acetic,
benzoic acids and japaconine (C28H18O16M). Indaconitine into acetic
and benzoic acids and pseudaconine, C25H410s N. The pseudaconitines
yield on hydrolysis acetic and veratric acids and a base ; pseudaconitine
giving the base pseudaconine (C25H410s N), and bikhaconitine breaking
up into the organic acids already mentioned and the base bikhaconine
thus;–
Bikhaconine. Acetic Weratric
Acid. Acid.
Cash;1011N = C25H110/N + C3H4O2 + CoH16O4.
The saponification of the various aconite alkaloids is apparently best
effected by dissolving in alcohol, making the solution alkaline with soda
and digesting at ordinary temperatures for twenty-four hours, at the
end of which time the solution is neutralised by sulphuric acid, and the
alcohol got rid of by evaporation in a vacuum at a very gentle heat.
The aqueous solution can now be acidified again by sulphuric acid, and
the benzoic or veratric acid, as the case may be, shaken out with benzene.
The base is now liberated by alkalising with NaOH and shaking out
with ether, while the acetic acid can be distilled off, first acidifying with
sulphuric acid. -
The ethereal solution of the base Dunstan appears to usually treat
with fused calcic chloride for some time in order to have a dry ether
solution.
The aconitines and pseudaconitines rotate a ray of polarised light to
the right; on the other hand the salts, such as the hydrochloride and
the hydrobromide, are lavo-rotatory. -
The melting-points and specific rotations of the alkaloids are as
follows:–
Melting-point. Specific Rotation.
Aconitine . ſº {º º 196°–197° 12°32 in alcoholic solution
Japaconitine * © * 204 °2° 23 °36 2 3
Indaconitine te tº & 202°–203° 1817 5 y
Pseudaconitine . e ſº 211°–212° 18 °6
2 3
Bikhaconitine . ge & 113°–116° 12'21
2 3
$424, 425.] ACONITINE. 363
The following are the melting-points of the gold salts:—
Melting-point of Gold Salts.
- (a) 135.5°
Aconitine aurichloride | (b) 152°
(c) 176°
tº 3 º' (a) 153°
Japaconitine , , (b) 231°
Indaconitine ,, • o - º g º º 147°–152°
Pseudaconitine, © - º sº tº * ſº 235°–236°
Bikhaconitine ,, te - - º º e e 232°–233°
§ 424. Aconitine.—Aconitine from the English A. napellus is repre-
sented as Cash,501,N, has a melting-point of 188:5°, and specific rotation
of [a]p + 10:47° – 11.1° in alcoholic solution, and the hydrobromide melts
at 163°. English aconitine is scarcely in commerce now, having been
supplanted by the German aconitine, which has the melting-point and
other characters given in the preceding tables.
The behaviour of a sample of Merck's aconitine in the subliming
cell, which has a melting-point of 184”, was as described at page 260.
Aconitine dissolves in water at 22° in the proportion of 1 in 4431
(Dunstan); it is soluble in 37 of absolute alcohol, 64 of anhydrous ether,
5-5 parts of chloroform and benzene (A. Jurgens); it has basic pro-
perties, and a cold watery solution has an alkaline reaction to cochineal,
but not to litmus nor to phenol-phthalein. Aconitine is not precipitated
by mercuric potassium iodide, but gives a voluminous precipitate with
an aqueous solution of iodine in potassium iodide and a crystalline
compound with gold chloride. -
Aconitine is best extracted from the plant, or from organic matters
generally, by a 1 per cent. Sulphuric acid; this strength is stated not to
hydrolyse aconitine if acting in the cold; after purifying the acid liquid
by shaking it with amyl alcohol, and then with chloroform, always
operating in the cold, the liquid is precipitated by ammonia in very
slight excess, and the liquid shaken with ether; the ether is removed,
dehydrated by standing over calcium chloride, and then evaporated
spontaneously; should the aconitine be mixed with the other alkaloids,
advantage can be taken of the method of separating aconitine by con-
verting it into hydrobromide, as described under “Benzoyl-aconine.”
§ 425. Tests for Aconitine.—The most satisfactory and the most
delicate is the physiological test; the minutest trace of an aconite-holding
liquid, applied to the tongue or lips, causes a peculiar numbing tingling
sensation which, once felt, can readily be remembered. * -
An alkaloidal substance which, heated in a tube, melts approximately
near the melting-point of aconitine, and gives off an acid vapour, would
render one suspicious of aconitine, for most alkaloids give off alkaline
vapours. Aconitine also may, by heating with dilute acids, be made to
364 POISONS : THEIR EFFECTS AND DETECTION. [Š 426.
readily yield benzoic acid, an acid easy of identification. Aconitine dis-
solved in nitric acid, evaporated to dryness, and then treated with
alcoholic potash, gives off an unmistakable odour of benzoic ester.
Should there be sufficient aconitine recovered to convert it into the
gold salt, the properties of the gold salt (that is, its melting-point, and
the percentage of gold left after burning) assist materially in the
identification.
A minute quantity of aconitine dissolved in water, acidified with acetic
acid, and a particle of KI added and the solution allowed to evaporate,
gives crystals of aconitine hydriodide, from which water will dissolve
out the KI. Iodine water gives a precipitate of a reddish-brown colour
in a solution of 1:2000.*
The chemical tests are supplementary to the physiological ; if the
alkaloidal extract does not give the tingling, numbing sensation, aconitine
cannot be present.
§ 426. Benzoyl-aconine (“isaconitine”), Cash is NOu, is obtained
from aconitine by heating an aqueous solution of the sulphate or hydro-
chloride in a closed tube at 120°-130° for two or three hours, a molecule
of acetic acid (9.3 per cent.) being split off, and benzoyl-aconine left.
It may be separated from the mixed alkaloids of the Aconitum
napellus by dissolving in a 5 per cent solution of hydrobromic acid
(excess of acid being avoided), precipitating with a slight excess of
ammonia, and shaking out with ether. The residue left after the ether
is evaporated chiefly consists of aconitine; it is dissolved in just suffi-
cient hydrobromic acid and the exactly neutral hydrobromate solution
allowed to evaporate spontaneously in a desiccator; crystals of aconitine
hydrobromide separate out, the mother-liquor containing some benzoyl-
aconine and “homonapelline.” The aqueous solution which has been
exhausted with ether is now shaken out with chloroform. This chloro-
form solution contains most of the benzoyl-aconine, and on separation
the residue is dissolved in just sufficient hydrochloric acid to form a
neutral solution ; this solution is concentrated on the water-bath with
constant stirring, crystals of the hydrochloride form, and are filtered off
from time to time and washed with a little cold water, the washings
being added to the original liquid ; the different fractions are mixed
together, and the process repeated until they have a melting-point of
268". Benzoyl-aconine is obtained from the hydrochloride by precipi-
tating the aqueous solution by the addition of dilute ammonia, and
extracting the solution with ether; the solution in ether is washed with
water, dried by means of calcium chloride, and then distilled off.
Benzoyl-aconine is left as a transparent colourless non-crystalline varnish
of a melting-point near 125°.
* A. Jurgens, Arch. Pharm. (3), xxiv. 127, 128.
§ 427.] ACONITINE. 365
The solution in water is alkaline to litmus. The base is readily
soluble in alcohol, in chloroform, and in ether. The alcoholic solution
is dextrorotatory. The solutions are bitter, but do not give the tingling
sensation characteristic of aconitine. The hydrochloride, the hydro-
bromide, the hydriodide, and the nitrate have been obtained in a
crystalline state. The most characteristic salt is, however, the aurochlor
derivative. When aqueous solutions of benzoyl-aconine chloride and
auric chloride are mixed, a yellow precipitate is thrown down, which
(dissolved in alcohol, after being dried over calcium chloride, and slowly
evaporated in a desiccator) deposits colourless crystals entirely different
from the yellow crystals of aconitine gold chloride. These crystals have
the composition Cagha,(AuCl2)NO11, and therefore, by theory, should
yield 22.2 per cent. of gold, and 8 per cent. of chlorine. Professor
Dunstan * found, as a means of two determinations, 21.6 per cent. of
gold, and 7.8 per cent. of chlorine.
By hydrolysis benzoyl-aconine yields benzoic acid, which can be
shaken out of an acid solution by ether and identified; one molecule of
benzoic acid is formed from one molecule of benzoyl-aconine. 19.7 per
cent. of benzoic acid should, according to the formula, be obtained ;
Professor Dunstan found 18.85 per cent.
Benzoic acid in the subliming cell begins to give a cloud at about
77°–80°, and at or near 100° sublimes most rapidly.
Benzoic acid, recovered from an acid solution by shaking out with
ether, may be recognised as follows:—To the film left on evaporating
off the ether add a drop of H.SO4, and a few crystals of sodic nitrate,
and heat gently for a short time; pour the clear liquid into ammonia
water, and add a drop of ammonium sulphide. A red-brown colour
indicates benzoic acid. The rationale of the test is as follows:—Dinitro-
benzoic acid is first formed, and next, by the action of ammonium
sulphide, this is converted into the red-brown ammonium diamidoben-
zoate.—E. Mohler, Bull. Soc. Chem. (3), iii. 414–416.
§ 427. The Lethal Dose of Aconitines.—Commercial aconitine has
in the past varied in appearance from that of a gummy amorphous
mass up to a purer kind in white crystals.
Professor Dunstan f examined in 1893 fourteen samples, some of
them of considerable age, and only found two samples (one of English,
another of German make) which approached in melting-point and
crystalline appearance pure aconitine; the one, the English, melted at
186°-187°, and contained about 3 per cent. of benzoyl-aconine; the
other, a German specimen, was almost pure ; the melting-point was
187°5°. At the present time, however, fairly pure crystalline aconitine
* Journ. Chem. Soc. (Trans.), 1893.
+ Op. cit., 491.
366 , POISONS : THEIR EFFECTS AND DETECTION. [$ 428.
may be obtained and assayed accurately by determining the proportion
of acetic and benzoic acids. The physiological action of commercial
aconitine is, however, in all cases the same, the difference being in
quantitative, not qualitative action; in the small doses usually adminis-
tered, the physiological action depends wholly upon the toxic bases
present.
Cash and Dunstan give the lethal doses for cats per kilo. of body
weight as follows:—
Aconitine, . & - & § * * . 0-134 mgrm.
Diacetylaconitine, e ſº & e t . 4-5 2 3
Benz-aconine, . e t- e • e , 24' 5 2 3
Aconine, . g º sº g º . 160–400 , ,
It is difficult to say what would be the minimum fatal dose of pure
aconitine for a man; the more so, since there is reason for believing that
human beings are more sensitive to aconitine than dogs or cats; prob-
ably it would be about tº mgrm. per kilo. of body weight; and taking
the average weight of an adult at 70 kilos, this would mean 7 mgrims.
or about fºr of a grain ; but such calculations can only be applied to
the pure crystalline substance, the lethality of commercial tinctures
and pharmaceutical preparations generally is best settled by recorded
CàSéS.
In 1863 a woman took 70 minims of Fleming's tincture, and a
grain of acetate of morphine, and died in about four hours; but as this
was a complex case of poisoning, it is not of much value. Fifteen
minims of the tincture caused very serious symptoms in the case of a
woman under the care of Dr. Topham,” the effects lasting many hours.
Probably the smallest quantity of the tincture recorded as having
destroyed life is in the case of Dr. Male, of Birmingham.f. He died
from the effects of 80 drops taken in ten doses, extending over a period
of four days—the largest dose at any one time being 10 drops, the
total quantity would perhaps equal '08 grain of aconitine. -
With regard to the root itself, 38 grms. (60 grains) have been known
to produce death.
§ 428. Effects of Aconitine on Animal Life. i-There are few sub-
* Lancet, July 19, 1851, p. 56.
+ Med. Gaz., vol. xxxvi. p. 861, quoted by Taylor, Prin. of Med. Juris., vol. i.
. 426.
p † GIULINI, P,-Eagerimentelle Unterswchwrigen weber die Wºrkung des Acomitins
auf das Nervensystem, das Herz, w, die Athmung, 8vo, Erlangen, 1876.
HARLEY, Dr. JoHN.—“On the Action and Uses of Aconitia,” St. Thos. Hosp.
Reports, 1874.
W. ScHROFF, C. Jr.—Beitrag zur Kenntniss des Acomit., 8vo, Wien, 1876.
PLUGGE, P. C.—“Untersuchungen ueber die physiologische Wirkung verschie-
dener Handelssorten von Aconitin, u. Pseudoaconitin auf Muskeln u. Nerven,” Virch.
Archiv, Bd. lxxxvii., 1882, S. 410.
§ 428.] - ACONITINE. 367
stances which have been experimented upon in such a variety of ways
and upon so many classes of animals as aconitine in different forms ;
but there does not seem to be any essential difference in the symptoms
produced in different animals save that which is explained by the
organisation of the life-form under experiment.
Insects.—The senior author has made experiments with the active
principles of aconite upon blow-flies. An extract was made by allowing
the ordinary tincture to evaporate spontaneously at the temperature of
the atmosphere. If a minute dot of this is placed upon the head of a
blow-fly, absorption of the active principle takes place in from fifteen to
thirty minutes, and marked symptoms result. The symptoms consist
essentially of muscular weakness, inability to fly, and to walk up per-
pendicular surfaces; there is also, in all cases, a curious entanglement
of the legs, and very often extrusion of the proboscis; trembling of the
legs and muscular twitchings are frequent. A progressive paralysis
terminates in from four to five hours in death ; the death is generally
so gradual that it is difficult to know when the event occurs, but
in one case there were violent movements of the body, and sudden
death.
Fish.-The action on fish has been studied by Schulz and Praag.
There is rapid loss of power and diminished breathing; the respiration
seems difficult, and the fish rapidly die.
Reptiles—Frogs.-Plugge, in experiments on frogs, found no
qualitative difference in the action of any of the commercial samples of
aconitine. This fact gives the necessary value to all the old experiments,
for we now know that, although they were performed with impure or
weak preparations, yet there is no reason to believe that the symptoms
described were due to any other but the alkaloid aconitine in varying
degrees of purity or dilution. Frogs show very quickly signs of weak-
ness in the muscular power; the respiration invariably becomes laboured,
and ceases after a few minutes; the heart's action becomes slowed,
irregular, and then stops in diastole. The poisoned heart, while still
pulsating, cannot be arrested either by electrical stimulation of the
vagus or by irritation of the sinus, nor when once arrested can any
further contraction be excited in it. Opening of the mouth and
apparent efforts to vomit, Plugge observed both with Rana esculenta
and Rana temporaria. He considers them almost invariable signs of
aconitine poisoning. A separation of mucus from the surface of the
body of the frog is also very constantly observed. Dilatation of the
pupils is frequent, but not constant ; there may be convulsions, both of
a clonic and tonic character, before death, but fibrillar twitchings are
seldom.
368 POISONS : THEIR EFFECTS AND DETECTION. [$ 428.
Action of Aconitine on the Heart.
Bohm * has made researches on the action of aconitine on the frog's
heart. After a subcutaneous injection of 5 mgrims, the heart beats
quicker owing to stimulation of the motor ganglion ; then, as the motor
ganglion begins to be paralysed and simultaneously the brake-apparatus
(Hemmungs-worrichtungen) stimulated, the beats are slowed and
become irregular as in the action of the digitalis group. There is finally
arrest in diastole; at first removed by atropine, but in the next stage
atropine has no effect, for there is complete paralysis of the brake
nervous centre as well as the vaso-motor centre; if, however, the vagus
is stimulated the beats may recommence, to be followed by final com-
plete arrest.
This sequence is not always easy to follow because the least overdose
obscures the successive stages by almost at once paralysing the nervous
centres. Durdufi t has shown that, contrary to the poisons of the
digitalis group, the extensibility of the heart is diminished, that is to
say, its volume is lessened. .
The mammalian heart is similarly affected to that of the frog.
With small doses of aconitine, the relation of pulse frequency and
blood-pressure varies somewhat according to the particular aconitine, as
it affects the central origin of the nerves of the vessels and the vagus.
Thus sometimes the pulse slows without sinking of the blood-pressure,
and sometimes there is increase of pulse and rise of blood-pressure.
Matthews has registered by means of a myocardiagraph the movements
of the exposed heart of a dog after aconitine had been introduced into
the circulation, and seen arhythmic beats and fibrillar contractions of
the ventricle, results of exalted sensibility and excitability of the heart
muscle. All researches show that aconitine is extremely poisonous to
the mammalian heart; so minute a quantity as 1 part of aconitine to 5
million of the blood notably quickens the pulse even up to 109–131,
the pulse at once sinking to normal if unpoisoned blood is allowed to
replace the blood containing aconitine. Doses of 1 of aconitine to 1%
million of blood are fatal within 7 minutes by arrest of the heart beat.
In fatal cases the enormous rise of frequency of heart beat is followed by
sudden arrest of the left ventricle, whilst the right auricle and wentricle
may continue to beat for a quarter to half an hour. In this condition
the beat of the left ventricle cannot be restored by normal blood or by
any stimulating means whatever.
The effects of indaconitine f are strikingly similar to those of aconi-
* Studiem, iiber Herzgifte. i Archiv f. Eacper. Path., Bd. xxv.
† The “Pharmacology of Indaconitine,” by J. Theod. Cash, M.D., and
Wyndham R. Dunstan, M.D., Proc. Roy. Soc., vol. lxxvi.
§ 428.] ACONITINE, 369
tine; the phases of slowing of the pulse and marked quickening and
subsequent arhythmia due to inco-ordinate action of auricles and ven-
tricles are all present. 06 mgrm. administered to etherised cats subcu-
taneously every forty-five minutes was fatal seventy minutes after the
third dose.
1st injection. Temporary acceleration, then slowing of the pulse
and respiration, moderate fall of arterial pressure.
2nd injection. Similar effects, but no acceleration of pulse or re-
spiration.
3rd injection. Great acceleration of heart beats. Immediately
before death, when blood-pressure = 28 mm., the rhythm became regular.
In the earlier part of this period vagus stimulation co-ordinated the
action of the auricles and ventricles, temporarily raising the blood-
pressure, but this effect was lost later. Splanchnic reaction was never
entirely abolished.
Artificial respiration prolonged life for over twenty minutes; 0.01
mgrm. per kilo. of atropine sulphate fully antagonised 0.09 mgrm. per
kilo. of indaconitine.
Bikhaconitine acts quite similarly, save that its action on the respira-
tion is stronger than that of aconitine.
Birds.-There is a discrepancy in the descriptions of the action of
aconitine on birds. L. v. Praag thought the respiration and circulation
but little affected at first ; while Achscharumow witnessed in pigeons
dyspnoea, dilatation of the pupils, vomiting, shivering, and paresis. It
may be taken that the usual symptoms observed are some difficulty in
breathing, a diminution of temperature, a loss of muscular power
generally (but not constantly), dilatation of the pupils, and convulsions
before death.
Mammals.-The effects vary somewhat, according to the dose. Very
large doses kill rabbits rapidly. They fall on their sides, are violently
convulsed, and die in an asphyxiated condition ; but with smaller doses
the phenomena first observed are generally to be referred to the respira-
tion. Thus, in an experiment on the horse, Dr. Harley found that the
subcutaneous administration of 6 mgrm. (.01 grain) caused in a weakly
colt some acceleration of the pulse and a partial paralysis of the dilator
narium. Double the quantity given to the same animal some time
after caused, in six hours and a half, some muscular weakness, and an
evident respiratory trouble. The horse recovered in eighteen hours.
27 mgrims. (ºr grain) given in the same way, after a long interval of
time, caused, at the end of an hour, more pronounced symptoms; the
pulse, at the commencement 50, rose in an hour and a half to 68, then
the respiration became audible and difficult. In an hour and three-
quarters there were great restlessness and diminution of muscular power.
24
37O POISONS: THEIR EFFECTS AND DETECTION. [$ 429–431.
Two hours after the injection the muscular weakness increased so much
that the horse fell down ; he was also convulsed. After eight hours he
began to improve. In another experiment, 32°4 mgrms. (; grain) killed
a sturdy entire horse in two hours and twenty minutes, the symptoms
commencing within the hour, and consisting of difficulty of breathing,
irregularity of the heart's action, and convulsions.
The general picture of the effects of fatal, but not excessive, doses
given to dogs, cats, rabbits, etc., resembles closely that already described.
The heart's action is at first slowed, then becomes quick and irregular;
there is dyspnoea, progressive paralysis of the muscular power, convul-
sions, and death in asphyxia. Vomiting is frequently observed, some-
times salivation, and very often dilatation of the pupil. Sometimes
the latter is abnormally active, dilating and contracting alternately.
Diarrhoea also occurs in a few cases. Vomiting is more frequent
when the poison is taken by the mouth than when administered
subcutaneously.
§ 429. Statistics.-During the ten years ending 1903 there were
recorded in England and Wales 25 accidental deaths from the various
forms of aconite (22 males, 3 females); and 23 suicidal deaths (16 males,
7 females) from the same cause, which makes a total of 48.
$430. Effects on Man.-Eighty-seven cases of poisoning by aconite
in some form or other, collected from European medical literature, com-
prise only 2 cases of murder, 7 of suicide, and 77 which were more or
less accidental. Six of the cases were from the use of the alkaloid
itself; 10 were from the root ; in 2 cases children eat the flowers; in
1, the leaves of the plant were cooked and eaten by mistake ; in 7, the
tincture was mistaken for brandy, sherry, or liqueur; the remainder
were caused by the tincture, the liniment, or the extract.
§ 431. Poisoning by the Root.—A case of murder which occurred
Some years ago in America, and also the Irish case which took place in
1841 (Reg. v. M'Conkey), were, until the trial of Lamson, the only
instances among English-speaking people of the use of aconite for
criminal purposes; but if we turn to the Indian records, we find that it
has been largely used from the earliest times as a destroyer of human
life. In 1842 a tank of water destined for the use of the British army
in pursuit of the retreating Burmese, was poisoned by intentional con-
tamination with the bruised root of Aconitum ferox, ; it was fortunately
discovered before any harm resulted. A preparation of the root is used
in all the hill districts of India to poison arrows for the destruction of
wild beasts. A Lepcha described the root to a British officer as being
“useful to sportsmen for destroying elephants and tigers, useful to the
rich for putting troublesome relations out of the way, and useful to
jealous husbands for the purpose of destroying faithless wives.” From
§ 431.] ACONITINE. 37 I
the recorded cases, the powdered root, mixed with food, or the same
substance steeped in spirituous liquor, is usually the part chosen for
administration. In M'Conkey's case, the man's wife purchased powdered
aconite root, mixed it with pepper, and strewed it over some greens,
which she cooked and gave to him. The man complained of the sharp
taste of the greens, and soon after the meal vomited, and suffered from
purging, became delirious with lockjaw, and clenching of the hands;
he died in about three hours. The chief noticeable post-mortem
appearance was a bright red colour of the mucous membrane of
the stomach.
The symptoms in this case were, in some respects, different from those
met with in other cases of poisoning by the root. A typical case is given
by Dr. Chevers (op. cit.), in which a man had taken by mistake a small
portion of aconite root. Immediately after chewing it he felt a sweetish
taste, followed immediately by tingling of the lips and tongue, numbness
of the face, and severe vomiting. On admission to hospital he was
extremely restless, tossing his limbs about in all directions and constantly
changing his position. He complained of a burning sensation in the
stomach, and a tingling and numbness in every part of the body,
excepting his legs. The tingling was specially marked in the face and
tongue—so much so that he was constantly moving the latter to and fro
in order to scratch it against the teeth. Retching and vomiting occurred
almost incessantly, and he constantly placed his hand over the cardiac
region. His face was anxious, the eyes suffused, the lips pale and
exsanguine, the eyelids swollen, moderately dilated, and insensible to
the stimulus of light; the respiration was laboured, 64 in a minute; the
pulse 66, small and feeble. There was inability to walk from loss of
muscular power, but the man was perfectly conscious. The stomach-
pump was used, and albumen and milk administered. Three and three-
quarter hours after taking the root the symptoms were increased in
severity. The tongue was red and swollen, the pulse intermittent, feeble,
and slower. The tingling and numbness had extended to the legs. On
examining the condition of the external sensibility with a pair of scissors,
it was found that, on fully separating the blades and bringing the points
in contact with the skin over the arms and forearms, he felt them as
one, although they were 4 inches apart. But the sensibility of the
thighs and legs was less obtuse, for he could feel the two points distinctly
when they were 4 inches apart, and continued to do so until the distance
between the points fell short of 2% inches. He began to improve about
the ninth hour, and gradually recovered, although he suffered for one
or two days from a slight diarrhoea. As in the case detailed (p. 373),
no water was passed for a long time, as if the bladder early lost
its power.
372 POISONS : THEIR EFFECTS AND DETECTION. [$ 432.
§ 432. Poisoning by the Alkaloid Aconitine.—Probably the earliest
instance on record is the case related by Dr. Golding Bird in 1848.*
What kind of aconitine was then in commerce is not known, and since
apparently a person of considerable social rank was the subject of the
poisoning, the case has been imperfectly reported. It seems, however,
that, whether for purposes of suicide, or experiment, or as a medicine,
two grains and a half of aconitine were swallowed. The symptoms were
very violent, consisting of vomiting, collapse, and attacks of muscular
spasm; the narrator describes the vomiting as peculiar. “It, perhaps,
hardly deserved that title; the patient was seized with a kind of general
spasm, during which he convulsively turned upon his abdomen, and with
an intense contraction of the abdominal muscles, he jerked out, as it
were, with a loud shout the contents of his stomach, dependent appar-
ently on the sudden contraction of the diaphragm.” On attempting to
make him swallow any fluid, a fearful spasm of the throat was produced ;
it reminded his medical attendants of hydrophobia. The patient recovered
completely within twenty-four hours. - .
One of three cases reported by Dr. Albert Busscher, f of poisoning
by aconitine nitrate, possesses all the exact details of an intentional
experiment, and is of permanent value to toxicological literature.
A labourer of Beerta, 61 years of age, thin, and of somewhat
weak constitution, suffered from neuralgia and a slight intermittent
fever; Dr. Carl Meyer prescribed for his ailment:—
- B. Aconiti Nitrici, 2 grn.
& Tr. Chenopodii Ambrosioid., 100 grms. M.D.S.
Twenty drops to be taken four times daily. The patient was instructed
verbally by Dr. Meyer to increase the dose until he attained a maximum
of sixty drops per day. -
The doses which the man actually took, and the time of taking them,
are conveniently thrown into a tabular form as follows:—
No. 1. March 14, 7 P.M., 5 drops equal to aconitine nitrate, 4 mgrm.
, , 2, , , 9 P.M., 20 , , 5 y 3 3 1-6 , ,
,, 3. March 15, 8 A.M., 20 , , 2 3 5 5 1-6 , ,
! } 4. 3 y 11 A. M., 20 3 } } $ 2 1 *6 5 3
, , 6. , 4 P.M., 20 , , y 5 9 3 1“6 , ,
5, 6, , , 9 P.M., 20 , , 9 3 3 5 1 ‘6 , ,
, , 7. March 16, 10 P.M., 10 , , 5 5 * 3 ‘8 , ,
In the whole seven doses, which were distributed over forty-eight hours,
he took 9.2 mgrms. (14 grain) of aconitine nitrate.
On taking dose No. 1, he experienced a feeling of constriction
* Lancet, vol. i. p. 14.
# Intoxicationsfille durch Aconilin Nitricum Gallicum, nebst Sections Bericht,
von Dr. Albert Busscher; Berl. klinische Wochenschrift, 1880, No. 24, pp. 338, 356
§ 432.] - ACONITINE. 373
(Zusammenziehung), and burning spreading from the mouth to the
stomach, but this after a little while subsided. Two hours afterwards
he took No. 2, four times the quantity of No. 1. This produced the
same immediate symptoms, but soon he became cold, and felt very ill.
He had an anxious oppressive feeling about the chest, with a burning
feeling about the throat; the whole body was covered with a cold
sweat, his sight failed, he became giddy, there was excessive muscular
weakness, he felt as if he had lost power over his limbs, he had great
difficulty in breathing. During the night he passed no water, nor
felt a desire to do so. About half an hour after he had taken the
medicine, he began to vomit violently, which relieved him much ; he
then fell asleep. - .
Dose No. 3, equal as before to 1-6 mgrm., he took in the morning.
He experienced almost exactly the same symptoms as before, but con-
vulsions were added, especially of the face; the eyes were also prominent;
twenty minutes after he had taken the dose vomiting came on, after
which he again felt better.
He took dose No. 4, and had the same repetition of symptoms, but
in the interval between the doses he felt weaker and weaker; he had no
energy, and felt as if paralysed. No. 5 was taken, and produced, like
the others, vomiting, after which he felt relieved. Neither he nor his
wife seemed all this time to have had any suspicion that the medicine
was really doing harm, but thought that the effects were due to its
constant rejection by vomiting, so, in order to prevent vomiting with
No. 6, he drank much cold water. After thus taking the medicine,
the patient seemed to fall into a kind of slumber, with great restlessness;
about an hour and a half afterwards he cried, “I am chilled ; my heart,
my heart is terribly cold. I am dying; I am poisoned.” His whole
body was covered with perspiration ; he was now convulsed, and lost
sight and hearing; his eyes were shut, his lips cracked and dry, he
could scarcely open his mouth, and he was extremely cold, and thought
he was dying. The breathing was difficult and rattling : from time to
time the muscular spasms came on. His wife now made a large quantity
of hot strong black tea, which she got him to drink with great difficulty;
although it was hot, he did not know whether it was hot or cold. About
five minutes afterwards he vomited, and did so several times; this
apparently relieved him, and he sank into a quiet sleep; during the
night he did not urinate. In the morning the wife went to Dr. Carl
Meyer, described the symptoms, and accused the medicine. So convinced
was Dr. Meyer that the medicine did not cause the symptoms, that he
poured out a quantity of the same, equal to 4 mgrms, of aconitine
nitrate, and took it himself in some wine, to show that it was harmless,
and ordered them to go on with it. The unhappy physician died of
374 POISONS : THEIR EFFECTS AND DETECTION, [$ 433.
aconitine poisoning five hours after taking the medicine.” In the
meantime, the woman went home, and her husband actually took a
Seventh, but smaller dose, which produced similar symptoms to the
former, but of little severity; no more was taken.
The absence of diarrhoea, and of the pricking sensations so often
described, is in this case noteworthy. Both diarrhoea and formication were
also absent in a third case reported by Dr. Busscher in the same paper.
§ 433. The most important criminal case is undoubtedly that of
Lamson:—At the Central Criminal Court, in March 1882, George
Henry Lamson, surgeon, was convicted of the murder of his brother-
in-law, Percy Malcolm John. The victim was a weakly youth of 18
years of age, paralysed in his lower limbs from old standing spinal
disease. The motive for perpetrating the crime was that Lamson,
through his wife (Malcolm John's sister), would receive, on the death of
his brother-in-law, a sum of £1500, and, according to the evidence, it is
probable that there had been one or more previous attempts by Lamson
on the life of the youth with aconitine given in pills and in powders.
However this may be, on November 24, 1880, Lamson purchased 2
grains of aconitine, came down on December 3 to the school where the
lad was placed, had an interview with his brother-in-law, and, in the
presence of the headmaster, gave Malcolm John a capsule, which he
filled then and there with some white powder, presumed at the time to
be sugar. Lamson only stayed altogether twenty minutes in the house,
and directly after he saw his brother-in-law swallow the capsule, he left.
Within fifteen minutes Malcolm John became unwell, saying that he
felt as if he had an attack of heartburn, and then that he felt the same
as when his brother-in-law had on a former occasion given him a quinine
pill. Violent vomiting soon set in, and he complained of pains in his
stomach, a sense of constriction in his throat, and of being unable
to swallow. He was very restless—so much so that he had to be
restrained by force from injuring himself. There was delirium a few
minutes before death, which took place about three hours and three-
quarters after swallowing the fatal dose. The post-mortem appearances
essentially consisted of redness of the greater curvature of the stomach,
and the posterior portion of the same organ. In one part there was a
little pit, as if a blister had broken ; the rest of the viscera were
congested, and the brain also slightly congested.i.
* The symptoms suffered by Dr. Meyer are to be found in Neder. Tijdschrift van
Geneeskwnde, 1880, No. 16.
t To these cases of poisoning by the alkaloid aconitine may be added one recorded
in Bouchardat’s Annuaire de Thérapeutie, 1881, p. 276. The case in itself is of but
little importance, save to illustrate the great danger in permitting the dispensing of
such active remedies of varying strength. A gentleman suffering from “angina
pectoris” was prescribed “Hottot's aconitine” in granules, and directed carefully to
§ 434–436.] ACONITINE. 375
§ 434. The symptoms of poisoning by the tincture, extract, or other
preparation, do not differ from those detailed. As unusual effects,
occasionally seen, may be noted profound unconsciousness lasting for two
hours (Topham's case), violent twitching of the muscles of the face,
opisthotonos, and violent convulsions. It is important to distinguish
the symptoms which are not constant from those which are constant, or
nearly so. The tingling and creeping sensations about the tongue,
throat, lips, etc., are not constant : they certainly were not present in the
remarkable German case cited at p. 373. Speaking generally, they seem
more likely to occur after taking the root or the ordinary medicinal pre-
parations. A dilated state of the pupil is by no means constant, and
not to be relied upon. Diarrhoea is seen after taking the root or tincture
by the stomach, but is often absent. In short, the only constant symp-
toms are difficulty of breathing, progressive muscular weakness, generally
vomiting, and a weak intermittent pulse.
$435. Physiological Action.—Aconitine, according to Dr. S. Ringer,
is a protoplasmic poison, destroying the functions of all nitrogenous
tissue—first of the central nervous system, next of the nerves, and last
of the muscles. Aconitine without doubt acts powerfully on the heart,
ultimately paralysing it ; there is first a slowing of the pulse, ascribed to
a central excitation of the vagus; then a quickening, due to paralysis of
the peripheral termination of the vagus in the heart ; lastly, the heart's
action becomes slow, irregular, and weak, and the blood-pressure sinks.
The dyspnoea and convulsions are the usual result, seen among all warm-
blooded animals, of the heart affection. Plugge found that the motor
nerves, and more especially their intra-muscular terminations, were
always paralysed ; but if the dose was small the paralysis might be
incomplete. Boehm and Wartmann, on the other hand, considered that
the motor paralysis had a central origin, a view not supported by recent
research. The action of aconitine in this way resembles curare. The
muscles themselves preserve their irritability, even after doses of aconi-
tine which are five to ten times larger than those by which the nerve
terminations are paralysed. -
$436. Post-mortem Appearances.—Among animals (mammals) the
appearances most constantly observed have been hyperaemia of the
increase the dose up to four granules, according to the effect produced. The pre-
scription was taken to a pharmacist, who, instead of supplying Hottot's aconitine,
supplied some other of unknown origin. The medicine was taken daily, and the
dose raised to four granules, which were taken with benefit until the whole was
exhausted. He then went to Hottot's establishment, and had a fresh supply, pre-
sumably of the same substance, but a very little time after he had taken his usual
dose of four granules, he suffered from symptoms of aconitine poisoning, headache,
vertigo, feebleness of the voice, and muscular weakness, and was alarmingly ill. He
recovered after some hours of medical treatment.
376 POISONS : THEIR EFFECTS AND DETECTION. [$ 437.
cerebral membranes and brain, a fulness of the large veins, the blood
generally fluid—sometimes hyperaemia of the liver, sometimes not.
When acomitime has been administered subcutaneously, there have
been no inflammatory appearances in the stomach and bowels.
In the case of Dr. Carl Meyer, who died in five hours from swallow-
ing 4 mgrms, of acomitine nitrate, the corpse was of a marble paleness,
the pupils moderately dilated. The colour of the large intestine was
pale ; the duodenum was much congested, the congestion being most
intense the nearer to the stomach; the mucous membrane of the stomach
itself was strongly hyperaemic, being of an intense red colour; the spleen
was enlarged, filled with much dark blood. The liver and kidneys were
deeply congested, the lungs also congested; the right ventricle of the
heart was distended with blood; in the pericardium there was a quantity
of bloody serum. The brain was generally blood-red; in the cerebral
hemispheres there were several large circumscribed subarachnoid extra-
vasations. The substance of the brain on section showed many red
bloody points.
In a case recorded by Taylor, in which a man died in three hours
from eating a small quantity of aconite root, the only morbid
appearance found was a slight reddish-brown patch on the cardiac end
of the stomach, of the size of half a crown ; all the other organs being
healthy.
§ 437. Separation of Aconitine from the Contents of the Stomach
or the Organs.—It would appear certain that in all operations for the
separation of aconite alkaloids (whether from the organic matters which
make up the plant, or from those constituting animal tissues), mineral
acids and a high heat should be avoided. A 1 per cent. Sulphuric acid
does not, however, hydrolyse, if acting in the cold, so that the process
already given, p. 363, may be followed.
The chemical examination in the Lamson case was entrusted to Dr.
Stevenson, assisted by Dr. Dupré, and was conducted on the principles
detailed. The contents of the stomach were treated with alcohol, and
digested at the ordinary temperature of the atmosphere; the contents
were already acid, so no acid in this first operation was added. The mix-
ture stood for two days and was then filtered. The insoluble portion
was now exhausted by alcohol, faintly acidulated by tartaric acid, and
warmed to 60° ; cooled and filtered, the insoluble part being washed again
with alcohol. The two portions—that is, the spirituous extract acid
from acids pre-existing in the contents of the stomach, and the alcohol
acidified by tartaric acid—were evaporated down separately, exhausted
by absolute alcohol, the solutions filtered, evaporated, and the residue dis-
solved in water. The two aqueous solutions were now mixed, and shaken
up with ether, which, as the solution was acid, would not remove any
§ 438.] ATROPINE. - 377
alkaloid, but might remove various impurities; the residue, after being
thus partially purified by ether, was alkalised by sodic carbonate, and the
alkaloid extracted by a mixture of chloroform and ether. On evapora-
tion of the chloroform and ether, the resulting extract was tested
physiologically by tasting, and also by injections into mice. By means
analogous to those detailed, the experts isolated aconitine from the vomit,
the stomach, liver, spleen, and urine, and also a minute quantity of mor-
phine, which had been administered to the patient to subdue the pain
during his fatal attack. When tasted, the peculiar numbing, tingling
sensation lasted many hours. These extracts were relied upon as evidence,
for their physiological effect was identical with that produced by aconi-
time. For example, the extract obtained from the urine caused symp-
toms to commence in a mouse in two minutes, and death in thirty
minutes, and the symptoms observed by injecting a mouse with known
aconitine coincided in every particular with the symptoms produced by
the extraction from the urine.
With regard to the manner of using “life tests,” since in most cases
extremely small quantities of the active principle will have to be identi-
fied, the choice is limited to small animals, and it is better to use mice or
birds, rather than reptiles. In the Lamson case, subcutaneous injections
were employed, but it is a question whether there is not less error in
administering it by the mouth. If two healthy mice are taken, and the
one fed with a little meal, to which a weighed quantity of the extract
under experiment has been added, while to the other some meal mixed
with a supposed equal dose of aconitine is given, then the symptoms
may be compared; and several objections to any operative proceeding
on such small animals are obviated. It is certain that any extract which
causes distinct numbness of the lips will contain enough of the poison to
kill a small bird or a mouse, if administered in the ordinary way.*
WI.-The Mydriatic Group of Alkaloids—Atropine—
Hyoscyamine—Solanine—Cytisine.
§ 438. The family of the Solanaceae contains several plants which
yield certain alkaloids having very similar properties, the chief amongst
which are the following:—
Atropine, Hyoscyamine, Pseudohyoscyamine, Hyoscine, all having
* Dr. A. Langaard has described a species of aconite root, named by the Japanese
Riisa-úsū. From his experiments on frogs and rabbits, its physiological action
seems not to differ from that of aconitine generally.—Ueber eine Art Japanische
Akonit-knollen, Kitsa-úsū, gemannt, w. iiber das in denselben workommende Akomitin.
Virchow's Archiv, B. lxxix. p. 229, 1880.
378 POISONS : THEIR EFFECTS AND DETECTION. [$ 439.
the formula C17H3s NO, ; Atropamine, C17H31NO2; Belladonnine,
Cly H21NO2; and Scopolamine, C17H31NO.
$ 439. Atropine (Daturine), Cº. His NO3−This important alkaloid
has been found in all parts of the Atropa belladonna, or deadly night-
shade, and in all the species of Datura.
The Atropa belladonna is indigenous, and may be found in some parts
of England, although it cannot be said to be very common. It belongs
to the Solanacea', and is a herbaceous plant with broadly ovate entire
leaves, and lurid purple axillary flowers on short stalks; the berries are
violet-black, and the whole of the plant is highly poisonous. The juice
of the leaves stains paper a purple colour. The seeds are very small,
kidney-shaped, weighing about 90 to the grain; they are covered closely
with small round projections, and are easily identified by an expert, who
may be supposed to have at hand (as is most essential) samples of different
poisonous seeds for comparison. The mightshade owes its poisonous
properties to atropine.
The yield of the different parts of belladonna, according to
Gunther,” is as follows:— -
TABLE SHOWING THE ALKALOIDAL CONTENT OF WARIOUS PARTS
OF THE BELLADONNA PLANT.
Quantity of Alkaloids in the Quantity of Alkaloids in the
Fresh Substance, per cent. Dry Substance, per cent.
(a) By (b) By (a) By (b) By
Weighing. Titration. Weighing. Titration.
Leaves, 0 °2022 0 20072 0 '838 0 °828
Stalk, 0 °0422 º a º 0 °] 46 & B tº
Ripe fruit, 0 2128 0 °20258 0 '821 0°805
Seed, e o o e 0.26676 * * * 0 °407 * * *
Unripe fruit, . s e 0°1870 0 °1930 0 °955 0 °955
Root, * e © sº 0.0792 - - - 0 °210 e tº wº
Atropine appears to exist in the plant in combination with malic
acid. According to a research by Ladenburg, hyoscyamine is associated
with atropine, both in the Belladonna and Datura plants.f
From a research by W. Schütte,f it appears that the younger roots
of wild belladonna contain hyoscyamine only, whilst the older roots
contain atropine as well as hyoscyamine, but only in small proportion;
the same was observed to be the case in the older cultivated roots.
* Pharm. Zeitschr, f. Russl., Feb. 1869 ; Dragendorff, Die chemische Werth,
bestimmung einiger starkwirkenden Droguén, St. Petersburg, 1874,
† Ber. der deutsch. chem. Ges., Bd. xiii.
# Arch. Pharm., ccxxix. 492-531 ; Journ. Chem. Soc. (abstract), February
1892, 231. -
§ 440.] DATURA STRAMONIUM.
379
The ripe berries of Atropa belladonna nigra and alba contain
chiefly atropine, hyoscyamine and a little scopolamine; seeds of Datura
stramonium also contain atropine, hyoscyamine, and a little Scopolamine.
§ 440. The Datura Stramonium or Thorn-apple is also indigenous
in the British Islands, but, like belladonna, it cannot be considered a
common plant. Datura belongs to the Solanaceae; it grows from 1 to
2 feet in height, and is found in waste places. The leaves are smooth,
the flowers white; the fruit is densely spinous (hence the name thorn-
apple), and is divided into four dissepiments below, two at the top, and
containing many seeds.
The Datura, or the Dhatura-plants, of India have in that country a
great toxicological significance, the white-flowered datura, or Datura
alba, growing plentifully in waste places, especially about Madras.
The purple-coloured variety, or Datura fastuosa, is also common in
certain parts.
the coast of Malabar.
most marked differences:—
SEEDS OF THE COMMON OR
WHITE DATURA.
(1) Outline angular.
(2) Attached to the placenta by
a large, white, fleshy mass separat-
ing easily, leaving a deep furrow
along half the length of the seed's
concave border.
(3) Surface scabrous, almost
reticulate, except on the two com-
pressed sides, where it has become
almost glaucous from pressure of
the neighbouring seeds.
(4) Convex border thick and
bulged with a longitudinal depres-
sion between the bulgings, caused
by the compression of the two sides.
(5) A suitable section shows the
embryo curved and twisted in the
fleshy albumen.
(6) The taste of the datura seeds
is very feebly bitter. The watery
decoction causes dilatation of the
pupil.
There is a third variety, the Datura atroac, found about
The seeds of the white datura have been mis-
taken in India for those of capsicum.
The following are some of the
SEEDS OF CAPSICUM.
Outline rounded.
Attached to the placenta by a
cord from a prominence on the
concave border of the seed.
Uniformly scabrous, the sides
being equally rough with the
borders.
Convex border thickened, but
uniformly rounded.
The embryo, exposed by a suit-
able section, is seen to resemble in
outline very closely the figure 6.
Thetasteofcapsicum is pungent;
a decoction irritates the eye much,
but does not cause dilatation of the
pupil.
38O POISONs: THEIR EFFECTS AND DETECTION. [$ 441, 442.
The identity of the active principle in both the datura and bella-
donna tribes is now completely established.* .
§ 441. Pharmaceutical Preparations.—(a) Of the leaves. ...Extract
of Belladonna.-This contains, according to Squire, f from 0.73 to 1-7
per cent. of total alkaloids. Belladonna Juice (succus belladonna),—
Strength in alkaloid about 0.05 per cent. Tincture of Belladonna. –
Half the strength of the juice, and therefore yielding about 0.025 per
cent. of alkaloid. -
(b) Belladonna Root.—Belladonna plaster contains 20 per cent. of
alcoholic extract of belladonna. Alcoholic Extract of Belladonna.-This
extract, according to Squire,” contains from 1:6 to 4'45 per cent. of
alkaloid. Belladonna limiment is an alcoholic extract with the addition
of camphor; its strength is about equal to 0.2 per cent of alkaloid.
Belladonna ointment contains about 10 per cent. of the alcoholic extract.
(c) The Alkaloid.—Atropine Discs (lamellae atropinae).-These are
discs of gelatine, each weighing about ºf grain, and containing for
ophthalmic use goºd grain of atropine sulphate. Similar discs are
made for hypodermic use, but stronger; each containing Hºp grain.
Solution of Atropine Sulphate.—Strength about 1 per cent. Atropine
Ointment.—Strength about 1 in 60, or 1.66 per cent. of atropine.
(d) Stramonium.—An extract of the seeds is officinal in Britain ;
the alkaloidal content is from 1:6 to 1.8 per cent. There is also a
tincture which contains about 0.06 per cent. of alkaloid.
§ 442. Properties of Atropine, Clºh as NOs–Atropine, hyoscyamine,
and hyoscine have all the same formula, but differ in their molecular
constitution. Atropine on hydrolysis, either by heating it with hydro-
chloric acid or baryta water, is decomposed into tropine and inactive
tropic acid :—
Cly H23NO3 + H2O = CsPilºn O + Co.H16O.
Atropine. Tropine. º
On the other hand, by heating tropic acid and tropine together,
atropine is regenerated. - - s
Tropic acid crystallises in prisms which melt at 117°-118°.
Dehydrating agents convert it into atropic acid (a-phenyl-acrylic
acid),
CH,OH CH -
C6H5– CHK * → C.H. -Cô " +Ho
COOH
Tropic acid. Atropic acid.
* See a research by Ernst Schmidt, “Ueber die Alkaloide der Belladonna-Wurzel
u. des Stechapfel-Samens,” Lieb. Anni., Bd., ceviii. 1881. - -
+ Companion to the British Pharmacopoeia, 1894.
§ 443.] ATROPINE. 381
: Atropic acid is an isomer of cinnamic acid; it crystallises in tablets
which melt at 106.5°.
, Tropine is a white crystalline strongly alkaline substance, melting
at 63°, and boiling at 233”. It has no action on polarised light. It
is soluble in water, alcohol, and ether, and gives precipitates with tannic
acid, iodised hydriodic acid, Mayer's reagent, gold chloride, and
mercuric chloride. - -
As a result of the researches of Ladenburg, Merling, and Willstätter,
tropine has been found to contain the piperidine, pyrrolidine, and hepta-
methylene nuclei united thus:–
H H
H2C–C––C

/ N
N-OH, XchoH
H2C C –C
H H2
Tropine.
Thus the constitutional formulae of atropine (as well as hyoscyamine)
may be represented as follows:—
H. H.
H3C C—C
/ / \ - CH2OH
N–C , º f mºs- sº- º f l （; ~ *
N Ha º O—CO º
H2C C—C C6H5
PH H2

Atropine.
Atropine forms colourless crystals (mostly in groups or tufts of
needles and prisms), which are heavier than water, and possess no
smell, but an unpleasant, long-enduring, bitter taste. The experiments
of E. Schmidt place the melting-point between 115° and 115'5". It is
said to sublime scantily in a crystalline form, but we have been unable
to obtain any crystals by sublimation ; faint mists collect on the upper
disc, at about 123", but they are perfectly amorphous.
Its reaction is alkaline; one part requires, of cold water, 300; of
boiling, 58; of ether, 30; of benzene, 40; and of chloroform, 3 parts
for solution. In alcohol and amyl alcohol it dissolves in almost every
proportion. x
§ 443. Tests.-Atropine mixed with nitric acid exhibits no change
of colour. The same is the case with concentrated sulphuric acid in
the cold; but on heating, there ensues the common browning, with
development of a peculiar odour, likened by Gulielmo to orange flowers,
by Dragendorff to the flowers of the Prunus padus, and by Otto to the
Spiraea ulmaria—a sufficient evidence of the untrustworthiness of this
382 POISONS : THEIR EFFECTS AND DETECTION, [$ 443.
as a distinctive test. The odour, indeed, with small quantities, is
certainly not powerful, nor is it strongly suggestive of any of the
plants mentioned. A far more intense odour is given off if a speck of
atropine is evaporated to dryness with a few drops of strong solution of
baryta, and heated strongly; the scent is decidedly analogous to that
of hawthorn-blossom, and unmistakably agreeable.
By heating a small quantity of atropine, say 1 mgrm, with 2
mgrms, of calomel and a very little water, the calomel blackens, and
crystals may be obtained of a double salt; this reaction is, however,
given also by hyoscyamine and homatropine. Mercuric potassium
iodide solution, and mercuric bromide solution give amorphous pre-
cipitates, which, after a time, become crystalline, and have character-
istic forms.
A solution of iodine in potassium iodide gives a precipitate with
acidulated solutions of atropine in even a dilution of 1 : 10,000.
Tannin precipitates, and the precipitate is soluble in excess of the
reagent. If atropine be dissolved in dilute hydrochloric acid, and a 5
per cent. of gold chloride solution be added, a precipitate of a gold
compound (C17Has NO, HCl AuCl2) separates. The precipitate is in the
form of rosettes or needles; melting-point 137°. On boiling it with
water, however, it melts into oily drops, and this peculiar behaviour
distinguishes it from the analogous salt of hyoscyamine, which does
not melt in boiling water. The percentage of gold left on a combustion
of atropine gold chloride is 31:35 per cent. 100 parts of the gold salt
are equal to 46.2 of atropine. A platinum salt may also be obtained,
(C17H3s NOAHCl), PtCl, containing 29.5 per cent. of platinum.
Vitali’s test is important; it consists in the production of a violet
colour with alcoholic potash after oxidation.
The test may be applied as follows:–Equal parts, say 1 mgrm., of
nitrate of sodium and of the substance to be tested, are rubbed together
with a glass rod on a porcelain slab, and to this mixture 1 drop of
sulphuric acid is added; the mixture is spread out in a thin film ;
upon this is strewn a little powdered potassium hydrate, and finally
1 drop of alcohol added; a violet colour is produced which passes into
a fine red; according to the author of the test, 0.001 mgrm. of atropine
sulphate can by this test be detected. Strychnine obscures this
reaction.
Atropine, homatropine, and hyoscyamine show an alkaline reaction
with phenolphthalein: atropine and homatropine give a precipitate
with HgCl, Hyoscyamine, not cocaine, precipitates HgCl2, and is
alkaline to litmus, but not to phenolphthalein. Atropine behaves as
follows:—(1) Sodium nitrate, sulphuric acid, and afterwards sodium
hydroxide, gives a violet colour; (2) the test as before, but with nitrite
§ 443.] ATROPINE. - 383
instead of nitrate, gives an orange colour, which, on dilution with sodium
hydroxide solution, changes to red, violet, or lilac ; (3) when heated
with glacial acetic acid and sulphuric acid for a sufficient time, a
greenish-yellow fluorescence is produced.—Flückiger, Pharm. Journ.
Trans. (3), vol. xvi. p. 601–602.
Wrewen (Zeit. f. Russland, xxxvi. 723) distinguishes between
hyoscyamine and atropine by obtaining a crystalline precipitate with
Marmé's reagent (10 grims. KI and 5 grnms, CdI, dissolved in 100 c.c.
water). A drop of a solution weakly acidified with sulphuric acid of
either alkaloid tested with a trace of Marmé's reagent develops a
crystalline precipitate. The form of the crystals of the hyoscyamine
compound differs entirely from that of the atropine compound.
The two alkaloids, strychnine and atropine, are not likely to be
often together in the human body, but that it may sometimes occur
is shown by a case recorded by L. Fabris.” A patient in the hospital
at Padua had for some time been treated with daily injections of 3
mgrms. of strychnine nitrate; unfortunately, one day, instead of the
3 mgrms. of strychnine, the same quantity of atropine sulphate was
injected, and the patient died after a few hours, with symptoms of
atropine poisoning.
On chemical treatment of the viscera, a mixture of alkaloids was
obtained which did not give either the reactions of strychnine or of
atropine, To test the possibility of these alkaloids obscuring each
other's reactions, mixtures of 3 per cent, solutions (the strength of the
injections) of atropine sulphate and strychnine nitrate were mixed
together, and strychnine tested for by the dichromate and sulphuric
acid test.
A mixture of equal parts gave the strychnine reaction very clearly,
but the atropine reaction not at all ; 1 strychnine with 3 of atropine
gave strychnine reaction, but not that of atropine; 1 strychnine with
4 atropine gave indistinct reactions for both alkaloids; 1 of strychnine
with 5 of atropine gave a momentary atropine reaction, the violet was,
however, almost immediately replaced by a red colour. Vitali’s reaction
was not clearly shown until the mixture was in the proportion of 9 of
atropine to 1 of Strychnine, but mixtures in the proportion of 3 strych-
mine and 1 atropine will give distinct mydriasis.
In such a case, of course, the strychnine should be separated from the
atropine; this can be effected by precipitating the strychnine as chromate,
filtering and recovering from the filter the atropine by alkalising and
shaking it out with ether.
The atropine may be farther purified by converting it into oxalate,
dissolving the oxalate in as small a quantity of alcohol as possible, and
* Gazzetta, xxii., i. 347–350,
384 POISONS : THEIR EFFECTS AND DETECTION. [$444,
precipitating the oxalate out with ether; the precipitate is collected,
dissolved in as small a quantity of water as possible, the water made
alkaline, and the base shaken out with ether.
The most reliable test for atropine, or one of the mydriatic alkaloids,
is its action on the iris; a solution of atropine, even so weak as
1 : 130,000, causing dilatation.* This action on the iris has been
studied by Ruyter, f Donders, and von Graefe.
The action is local, taking effect when in dilute solution only on the
eye to which it has been applied ; and it has been produced on the eyes
of frogs, not only in the living subject, but after the head has been
severed from the body and deprived of brain. The thinner the cornea,
the quicker the dilatation; therefore the younger the person or animal,
the more suitable for experiment. In frogs, with a solution of 1:250,
dilatation commences in about five minutes; in pigeons, seven minutes;
and in rabbits, ten minutes. In man, a solution of 1 : 120 commences
to act in about six to seven minutes, reaches its highest point in from ten
to fifteen minutes, and persists more or less for six to eight days. A
solution of 1:480 acts first in fifteen to twenty minutes, and reaches its
greatest point in twenty minutes; a solution of 1:48,000 requires from
three-quarters of an hour to an hour to show its effect. Dogs and cats
are far more sensible to its influence than man, and therefore more
suitable for experiment. If the expert chooses, he may essay the proof
upon himself, controlling the dilatation by Calabar bean ; but it is
seldom necessary or advisable to make personal trials of this nature. Î
§ 444. Statistics of Atropine Poisoning.—Since atropine is the active
principle of belladonna and datura plants, and every portion of these—
roots, seeds, leaves, and fruit—has caused toxic symptoms, poisoning by
any part of these plants, or by their pharmaceutical or other preparations,
may be considered with strict propriety as atropine poisoning. Our
English death statistics for the ten years ending 1903 record 95 deaths
(45 males and 50 females) from atropine (for the most part registered
under the head of belladonna); 29 (or 35 per cent.) were suicidal, the
rest accidental.
The greatest number of the accidental cases arise from mistakes in
pharmacy; thus belladonna leaves have been supplied for ash leaves;
the extract of belladonna has been given instead of extract of juniper;
* De Actione Atropa, Belladonnae in Iridem, Traj. ad. Rhen., 1852.
| Arch. Ophthal., ix. 262, 1864.
f A. Ladenburg (Compt. Rend.., xc. 92), having succeeded in reproducing atropine
by heating tropine and tropic acid with hydrochloric acid, by substituting various
organic acids for the tropic acid, has obtained a whole series of compounds to which
he has given the name of tropeines. One of these, hydroxytoluol (amygdalic)
tropeine, he has named homatropine. It dilates the pupil, but is less poisonous
than atropine,
$ 445.] ATROPINE. 385
the alkaloid itself has been dispensed in mistake for theine;” a more
curious and marvellously stupid mistake is one in which it was dispensed
instead of asafoetida (Schauenstein, op. cit., p. 652). Further, valerian-
ate of atropine has been accidentally substituted for quinine valerianate,
and Schauenstein relates a case in which atropine sulphate was adminis-
tered subcutaneously instead of morphine sulphate ; but the result was
not lethal. Many other instances might be cited. The extended use of
atropine as an external application to the eye naturally gives rise to a
few direct and indirect accidents. Serious symptoms have arisen from
the solution reaching the pharynx through the lachrymal duct and nose.
A curious indirect poisoning, caused by the use of atropine as a colly-
rium, is related by Schauenstein.f A person suffered from all the
symptoms of atropine poisoning ; but the channel by which it had
obtained access to the system was a great mystery, until it was traced
to some coffee, and it was then found that the cook had strained this
coffee through a certain piece of linen, which had been used months
before, soaked in atropine solution, as a collyrium, and had been cast
aside as of no value.
§ 445. Accidental and Criminal Poisoning by Atropine.—External
applications of atropine are rapidly absorbed; e.g., if the foot of a rat be
steeped for a little while in a solution of the alkaloid, and the eyes
watched, dilatation of the pupils will soon be observed. If the skin is
broken, enough may be absorbed to cause death. A case is on record
in which 21 grim. of atropine sulphate, applied as an ointment to the
abraded skin, was fatal. Atropine has also been absorbed from the
bowel; in one case, a clyster containing the active principles of 5-2 grms.
(80 grains) of belladonna root was administered to a woman 27
years of age, and caused death. Allowing the root to have been
carefully dried, and to contain 21 per cent. of alkaloid, it would seem
that so little as 10.9 mgrms. (16 grain) may even prove fatal, if left in
contact with the intestinal mucous membrane. Belladonna berries and
stramonium leaves and seeds are eaten occasionally by children. A
remarkable series of poisonings by belladonna berries occurred in London
during the autumn of 1846.
Criminal poisoning by atropine in any form is of excessive rarity in
Europe and America, but in India it has been frightfully prevalent.
In all the Asiatic cases the substance used has been one of the various
species of datura, and mostly the bruised or ground seeds, or a decoction
of the seeds. In 120 cases recorded in papers and works on Indian
toxicology, no less than 63 per cent. of the cases were criminal, 19 per
cent. Suicidal, and 18 per cent. accidental. In noting these figures,
* Hohl, De Effectu Atropini. Diss. Halle, 1863.
† Maschka's Handbuch. † Ploss, Zeitschr. f. Chir., 1863.
25
386 POISONS: THEIR EFFECTS AND DETECTION. [$ 446, 447.
however, it must be borne in mind that known criminal cases are more
certain to be recorded than any other cases. The drug has been known
under the Sanscrit name of dhatoora by the Hindoos from most remote
times. It was largely used by the Thugs, either for the purpose of
stupefying their victim or for killing him; by loose wives to ensure for
a time the fatuity of their husbands; and, lastly, it seems in Indian
history to have played the peculiar rôle of a state agent, and to have
been used to induce the idiocy or insanity of persons of high rank,
whose mental integrity was considered dangerous by the despot in power.
The Hindoos, by centuries of practice, have attained such dexterity in
the use of the “datura” as to raise that kind of poisoning to an art, so
that Dr. Chevers, in his Medical Jurisprudence for India,” declares
that “there appears to be no drug known in the present day which
represents in its effects so close an approach to the system of slow
poisoning, believed by many to have been practised in the Middle Ages,
as does the datura.”
§ 446. Fatal Dose.—It is impossible to state with precision the
exact quantity which may cause death, atropine being one of those
substances whose effect, varying in different cases, seems to depend on
special constitutional tendencies or idiosyncrasies of the individual.
Some persons take a comparatively large amount with impunity, while
others scarcely bear a very moderate dose without exhibiting unpleasant
symptoms. Eight mgrms. (# grain) have been known to produce
poisonous symptoms, and 129 grim. (2 grains) death. We may, there-
fore, infer that about 0648 grim. (1 grain) would, unchecked by
remedies, probably act fatally ; but very large doses have been recovered
from, especially when treatment has been prompt.
Atropine is used in veterinary practice, from 32°4 to 64.8 mgroms.
(# to 1 grain) and more being administered subcutaneously to horses;
but the extent to which this may be done with safety is not yet
established.
§ 447. Action on Animals.-The action of atropine has been
studied on certain beetles, on amphibia (such as the salamander, triton,
frogs, and others), on guinea-pigs, hedgehogs, rats, rabbits, fowls,
pigeons, dogs, and cats. Among the mammalia there is no essential
difference in the symptoms, but great variation in the relative sensi-
bility; man seems the most sensitive of all, next to man come the
carnivora, while the herbivora, and especially the rodents, offer a
considerable resistance. According to Falck the lethal dose for a rabbit
is at least 79 mgrm. per kilo. It is the general opinion that rabbits
may eat sufficient of the belladonna plant to render their flesh poisonous,
and yet the animals themselves may show no disturbance in health ; but
* Dr. Chever's work contains a very good history of datura criminal-poisoning.
§ 448.] ATROPINE. 387
this must not be considered adequately established. Speaking very
generally, the higher the animal organisation the greater the sensibility
to atropine. Frogs are affected in a peculiar manner. According to
the researches of Fraser,” the animal is first paralysed, and some hours
after the administration of the poison lies motionless, the only signs of
life being the existence of a slight movement of the heart and muscular
irritability. After a period of from forty-eight to seventy-two hours,
the fore limbs are seized with tetanic spasms, which develop into a
strychnine-like tetanus.
§ 448. Action on Man.—When atropine is injected subcutaneously,
the symptoms, as is usually the case with drugs administered in this
manner, may come on immediately, the pupil not unfrequently dilating
almost before the injection is finished. This is in no way surprising;
but there are instances in which decoctions of datura seeds have been
administered by the stomach, and the commencement of symptoms has
been as rapid as in poisoning by oxalic or even prussic acid. In a case
tried in India in July 1852, the prosecutor declared that, while a person
was handing him a lota of water, the prisoner snatched it away on pre-
tence of freeing the water from dirt or straws, and then gave it to him.
He then drank only two mouthfuls, and, complaining of the bitter taste,
fell down insensible within forty yards of the spot where he had drunk,
and did not recover his senses until the third day after. In another
case, a man was struck down so suddenly that his feet were scalded by
some hot water which he was carrying.—Chevers.
When the seeds, leaves, or fruit of atropine-holding plants are eaten,
there is, however, a very appreciable period before the symptoms com-
mence, and, as in the case of opium poisoning, no very definite rule can
be laid down, but usually the effects are experienced within half an hour.
The first sensation is dryness of the mouth and throat; this continues
increasing, and may rise to such a degree that the swallowing of liquids
is an impossibility. The difficulty in swallowing does not seem to be
entirely dependent on the dry state of the throat, but is also due to a
spasmodic contraction of the pharyngeal muscles. Tissore i found in
one case such constriction that he could only introduce emetics by pass-
ing a catheter of small diameter. The mucous membrane is reddened,
and the voice hoarse. f The inability to swallow, and the changed voice,
* Transact. of Edin. Roy. Soc., vol. xxv. p. 449. Jowrm. of Anat, and Physiol.,
May 1869, p. 357.
i Gaz, hebd., 1856.
# A friend of the senior author's was given, by a mistake in dispensing, 16 minims
of a solution of atropine sulphate, equivalent to # grain of atropine (or 9.3 mgrms.).
Ten minutes after taking the dose there was dilatation of the pupil, indistinctness of
vision, with great dryness of the throat and difficulty in swallowing ; he attempted to
eat a biscuit, but, after chewing it, he was obliged to spit it out, as it was not
*
388 POISONS : THEIR EFFECTS AND DETECTION. [$ 448.
bear some little resemblance to hydrophobia—a resemblance heightened
to the popular mind by an inclination to bite, which seems to have been
occasionally observed; the pupils are early dilated, and the dilatation
may be marked and extreme; the vision is deranged, letters and figures
often appear duplicated ; the eyeballs are occasionally remarkably
prominent, and generally congested ; the skin is dry, even very small
quantities of atropine arresting the cutaneous secretion; in this respect
atropine and pilocarpine are perfect examples of antagonism. With the
dryness of skin, in a large percentage of cases, occurs a scarlet rash over
most of the body. This is generally the case after large doses, but
Stadler saw the rash produced on a child 3 months old by 3 mgrim. of
atropine sulphate. It appeared three minutes after the dose, lasted
five hours, and was reproduced by a renewed dose.* The temperature
of the body with large doses is raised; with small, somewhat lowered.
The pulse is increased in frequency, and is always above 100—mostly
from 115 to 120, or even 150, in the minute. The breathing is at first
a little slowed, and then very rapid. Womiting is not common ; the
sphincters may be paralysed so that the evacuations are involuntary,
and there may be also spasmodic contractions of the urinary bladder.
The nervous system is profoundly affected; in one case there were clonic
spasms,f in another such muscular rigidity that the patient could with
difficulty be placed on a chair. The lower extremities are often partly
paralysed, there is a want of co-ordination, the person reels like a
drunken man, or there may be general jactitation. The disturbance of
the brain functions is very marked ; in about 4 per cent, only of the
recorded cases there has been no delirium, or very little—in the majority
delirium is present. In adults this generally takes a garrulous, pleasing
form, but every variety has been witnessed. Dr. H. Giraud describes
the delirium from datura (which it may be necessary to again repeat is
atropine delirium) as follows:—“He either vociferates loudly or is
garrulous, and talks incoherently; sometimes he is mirthful, and laughs
wildly, or is sad and moans, as if in great distress; generally he is
observed to be very timid, and, when most troublesome and unruly, can
always be cowed by an angry word, frequently putting up his hands in
a supplicating posture. When approached he suddenly shrinks back as
if apprehensive of being struck, and frequently he moves about as if to
avoid spectra. But the most invariable accompaniment of the final
possible to swallow; the throat was excessively sore, and there was a desire to pass
urine, but only a few drops could be voided. In forty-five minutes he was unable to
stand or walk. There was a bright rash on the chest. In two hours he became
insensible, and was taken to the Middlesex Hospital, recovering under treatment in
about eight hours.
+& jin. Times, 1868. + Lancet, 1881, vol. i. p. 414.
† Ibid., 1876, vol. i. p. 346.
§ 449.] ATROPINE. 389
stage of delirium, and frequently also that of Sopor, is in the incessant
picking at real or imaginary objects. At one time the patient seizes
hold of parts of his clothes or bedding, pulls at his fingers and toes,
takes up dirt and stones from the ground, or as often snatches at
imaginary objects in the air, on his body, or anything near him. Very
frequently he appears as if amusing himself by drawing out imaginary
threads from the ends of his fingers, and occasionally his antics are so
varied and ridiculous, that I have seen his near relatives, although
apprehensive of danger, unable to restrain their laughter.”” This
active delirium passes into a somnolent state with muttering, catching
at the bedclothes, or at floating spectra, and in fatal cases the patient
dies in this stage. As a rule, the sleep is not like opium coma ; there
is complete insensibility in both, but in the one the sleep is deep,
without muttering, in the other, from atropine, it is more like the
stupor of a fever. The course in fatal cases is rapid, death generally
taking place within six hours. If a person live over seven or eight
hours, he usually recovers, however serious the symptoms may appear.
On waking, the patient remembers nothing of his illness; mydriasis
remains some time, and there may be abnormality of speech and weak-
ness of the limbs, but within four days health is re-established. In
cases where the seeds have been swallowed, the symptoms may be much
prolonged, and they seem to continue until all the seeds have been
voided—perhaps this is due to the imperfect but continuous extraction
of atropine by the intestinal juices.
Chronic poisoning by atropine may, from what has been stated, be of
great importance in India. It is probable that its continuous effect
would tend to weaken the intellect, and there is no reason for any
incredulity with regard to its power as a factor of insanity. Rossbach
has ascertained that if dogs are, day after day, dosed with atropine, they
become emaciated ; but a certain tolerance is established, and the dose
has to be raised considerably after a time to produce any marked
physiological effect.
§ 449. Physiological Action of Atropine.—Atropine as well as
muscarine exercises a profound influence on the nervous apparatus of the
heart; the innervation effected may be clearly appreciated by referring
to the accompanying figure, which is a representation of Schmiedeberg's
diagrammatic “schema.” F is the heart muscle; M the vaso-motor
centre; H the brake or skid centre (Hemmungszentrum); B, the
accelerating centre; V the inhibitory nerve (vagus); A the accelerating
nerve (sympathetic); Z the connection between H and the “skid."
* In an English case of belladonna poisoning, the patient, a tailor, sat for four
hours, moving his hands and arms as if sewing, and his lips as if talking, but with-
out uttering a word.
390 POISONS: THEIR EFFECTS AND DETECTION. [$ 450–452.
muscular fibres; H is also connected with B, M, A, and W, but not
directly with the muscular fibres.
Atropine paralyses the end apparatus of H, hence the heart beats are
quickened; if in an animal poisoned by atropime, electrical excitement of
the vagus is tried, the heart's action
is no longer slowed as would be the
case in the normal animal. Atropine
paralyses H, but leaves M intact.
Atropine given to dogs for several
days, first in small doses, 3 mgrms.
per kilo., then increasing up to 110
mgrms., causes pathological changes
in the nervous ganglion cells of the
heart, the protoplasm darkens, the
nucleus is not so sharp in contour,
and the chromatin disappears more
or less—these changes have not been
observed in single fatal doses.
§ 450. Diagnosis.—The diagnosis of atropine poisoning may be very
difficult unless the attention of the medical man be excited by some
suspicious circumstance. A child suffering from belladonna rash, with
hot dry skin, quick pulse, and reddened fauces, looks not unlike one
under an attack of Scarlet fever. Further, as before mentioned, some
cases are similar to rabies; and again, the garrulous delirium and the
hallucinations of an adult are often very similar to those of delirium
tremens, as well as to mania.
§ 451. Post-mortem Appearances.—The post-mortem appearances
do not seem to be characteristic, save in the fact that the pupils remain
dilated. The brain is usually hyperamic, and in one case the absence
of moisture seems to have been remarkable. The stomach and intes.
times may be somewhat irritated if the seeds, leaves, or other parts of
the plant have been eaten ; but the irritation is not constant if the
poisoning has been by pure atropine, and still less is it likely to be
present if atropine has been administered subcutaneously.
§ 452. Treatment.—The great majority of cases recover under
treatment. In 112 cases collected by F. A. Falck, 13 only were fatal
(11.6 per cent.). The greater portion of the deaths in India are those
of children and old people—persons of feeble vitality. The Asiatic
treatment, which has been handed down by tradition, is the application
of cold water to the feet; but the method which has found most favour
in England is treatment by pilocarpine, a fifth of a grain or more being
injected from time to time. Pilocarpine shows as perfect antagonism
as possible; atropine dries, pilocarpine moistens the skin; atropine

§ 453,454.] HYOSCYAMINE. 39 I
accelerates, pilocarpine slows the respiration. Dr. Sydney Ringer and
others have published a remarkable series of cases showing the efficacy
of this treatment, which, of course, is to be combined where necessary
with emetics, the use of the stomach-pump, etc.”
§ 453. Separation of Atropine from Organic Tissues, etc.—From
the contents of the stomach, atropine may be separated by acidulating
strongly with sulphuric acid (15 to 20 c.c. of dilute H2SO, to 100 c.c.),
digesting for some time at a temperature not exceeding 70°, and then re-
ducing any solid matter to a pulp by friction, and filtering, which can
generally be effected by the aid of a filter-pump. The liver, muscles,i
and coagulated blood, etc., may also be treated in a precisely similar way.
The acid liquid thus obtained, is first, to remove impurities, shaken up
with amyl alcohol, and after the separation of the latter in the usual
manner, it is agitated with chloroform, which will take up any of the re-
maining amyl alcohol, ; and also serve to purify further. The chloroform
is then removed by a pipette (or the separating flask before described),
and the fluid made alkaline, and shaken up with ether, which, on re-
moval, is allowed to evaporate spontaneously. The residue will contain
atropine, and this may be farther purified by converting it into oxalate,
as suggested, page 383.
From the urine, Š atropine may be extracted by acidifying with
sulphuric acid, and agitation with the same series of solvents. Atropine
has been separated from putrid matters long after death, nor does it
appear to suffer any decomposition by the ordinary analytical operations
of evaporating solutions to dryness at 100°. In other words, there
seems to be no necessity for operations in vacuo, in attempts at separat-
ing atropine.
2, HYOSCYAMINE.
§ 454. This powerful alkaloid is contained in small quantities in
datura and belladonna, and also is found in the common lettuce (-001
per cent.), and in Scopola carmolica, a solanaceous plant indigenous to
Austria and Hungary'ſ ; but its chief source is the Hyoscyamus niger
* See, for Dr. Ringer's cases, Lancet, 1876, vol. i. p. 346. Refer also to Brit.
Med. Journ., 1881, vol. i. p. 594; ib., p. 659.
f Neither amyl alcohol nor chloroform removes atropine from an acid solution.
# Atropine goes into the blood, and appears to be present in the different organs
in direct proportion to the quantity of blood they contain. Dragendorff has found
in the muscles of rabbits fed upon belladonna sufficient atropine for quantitative esti.
mation.
§ Dragendorff has found atropine in the urine of rabbits fed with belladonna; the
separation by the poison is so rapid that it often can only be recognised in the urine
during the first hour after the poison has been taken.
| T. S. Dymond, Journ. Chem. Soc., Trams., 1892, 90.
T W. R. Dunstan and A. E. Chaston, Pharm. Journ. Trans. (3), xx. 461–464.
§
º

TABLE SHOWING THE ALKALOIDAL CONTENT OF WARIOUS PARTS OF THE HENBANE PLANT.
Plant Destitute of Flowers.
Plant in Flower.
Plant in Fruit.
Hyosc.-Albus.
Hyosc.-Niger.
Hyosc.-Albus.
Hyosc.-Niger.
Hyosc.-Albus.
Hyosc.-Niger.
1868. 1869. 1868. 1869. 1868. 1869. 1868. 1869. 1868. 1869. 1868. 1869.
Seeds, . O' 162 || 0-172 || 0-075 || 0-118
Leaves, . 0.588 || 0:469 || 0-154 || 0-192 || 0.359 || 0.329 || 0-147 || 0-206 || 0:211 || 0-153 0.065 || 0:110
Stalk, 0-012 0.027 | 0-017 || 0-036 || 0-048 || 0-032 || 0-030 || 0.027 | 0-029 || 0:009 || 0-010
Root, 0-128 || 0:176 0-070 || 0-080 || 0-146 || 0-262 || 0°127 || 0-138 || 0-106 || 0-086 || 0:028 || 0-056



§ 455.] HYOSCYAMINE. - 393
and Hyoscyamus albus (black and white henbane): it is also found in the
Duboisia myoporoides. Dunstan and Brown “ have found that Hyoscy-
amus muticus contains only hyoscyamine, and that the plant grown in
Egypt is much richer in the alkaloid than is the European variety;
further, they find that the Datura stramonium grown in Egypt also
contains only hyoscyamine, and is not accompanied by other alkaloids.
The following table gives the percentage of alkaloid (hyoscyamine) found
by them in various plants.
PERCENTAGE OF TOTAL ALKALOID.

Roots. Leaves. Seeds. Stem. #.
Atropa Belladonna . 0°21–0°41 9:30–0 '90 0°16–0'37
Datura Stramonium . 0 15 0°49 * - -
Hyoscyamus niger s e gº & e - e. * - - e s º & © tº
(hiennial) . . 0°15–0°17 || 0-039–069 tº & - e tº e 0-03
(annual) . * * * O'064–0 07 tº 4 º' tº º º tº gº tº
Hyoscyamus muticus tº tº º 0 °46
Hyoscyamine (C17H3s NOs), as separated in the course of analysis,
is a resinoid, sticky, amorphous mass, difficult to dry, and possessing a
tobacco-like odour. It can, however, be obtained in well-marked odour-
less crystals, which melt at 108°–109", a portion subliming unchanged.
It liquefies under boiling water without crystallisation. According to
Thorey,t hyoscyamine crystallises out of chloroform in rhombic tables,
and out of benzene in fine needles; but out of ether or amyl alcohol it
remains amorphous. When perfectly pure, it dissolves with difficulty
in cold, but more readily in hot, water; if impure, it is hygroscopic, and
its solubility is much increased. In any case, it dissolves easily in
alcohol, ether, chloroform, amyl alcohol, benzene, and dilute acids.
Hyoscyamine neutralises acids fully, and forms crystallisable salts, which
assume for the most part the form of needles. It is isomeric with
atropine, and is converted into atropine by heating to 110° without air,
or by allowing to stand in weak alkaline solution. It is the lavo-rotatory
modification of atropine. Dehydrating agents convert it into belladonnine
(atropamine), CnH23NO2. Hyoscyamine saponified with hot water gives
lavo-tropic acid and tropine, but if saponified by acids or alkalies this
lavo-tropic acid is converted into the racemic or inactive form. The
gold salt melts at 159°, and does not melt in boiling water like the
atropine gold salt.
§ 455. Pharmaceutical and other Preparations of Henbane.—The
* Journ. Chem. Soc., 1899, T. 72; 1901, T, 79.
t Pharm. Zeitschr. f. Russl., 1869.
394 POISONS : THEIR EFFECTS AND DETECTION. [$ 455.
leaves are alone officinal in the European pharmacopoeias; but the seeds
and the root, or the flowers, may be met with occasionally, especially
among herbalists. The table * (p. 392) will give an idea of the alkaloidal
content of the different parts of the plant.
In order to ascertain the percentage of the alkaloid in any part of
the plant, the process followed by Thorey has the merit of simplicity.
The substance is first exhausted by petroleum ether, which frees it from
fat ; after drying, it is extracted with 85 per cent. alcohol at a tempera-
ture not exceeding 40°. The alcoholic extracts are then united, the
alcohol distilled off, and the residue filtered. The filtrate is now first
purified by agitation with petroleum ether, then saturated by ammonia,
and shaken up with chloroform. The latter, on evaporation, leaves the
alkaloid only slightly impure, and, after washing with distilled water,
if dissolved in dilute sulphuric acid, a crystalline sulphate may be
readily obtained.
A tincture and an extract of henbane leaves and flowering tops
are officinal in most pharmacopoeias; an extract of the seeds in that of
France.
An oil of hyoscyamus is officinal in all the Continental pharma-
copoeias, but not in the British.
Henbane juice is recognised by the British pharmacopoeia; it is
about the same strength as the tincture.
An ointment, made of one part of the extract to nine of simple
ointment, is officinal in the German pharmacopoeia.
The tincture (after distilling off the spirit) and the extracts (on
proper solution) may be conveniently titrated by Mayer's reagent (p. 264),
which, for this purpose, should be diluted one-half; each c.c. then,
according to Dragendorff, equalling 6'98 mgrms. of hyoscyamine. Kruse
found 0.042 per cent. of hyoscyamine in a Russian tincture, and 0:28
per cent. in a Russian extract. Any preparation made with extract of
henbane will be found to contain nitrate of potash, for Attfield has shown
the extract to be rich in this substance. The ointment will require ex-
traction of the fat by petroleum ether; this accomplished, the determina-
tion of its strength is easy.
The oil of hyoscyamus is poisonous, and contains the alkaloid. An
exact quantitative research is difficult; but if 20 grms. of the oil are
shaken up for some time with water acidified by sulphuric acid, the
fluid separated from the oil, made alkaline, shaken up with chloroform,
and the latter removed and evaporated, sufficient will be obtained to
test successfully for the presence of the alkaloid, by its action on the
pupil of the eye.
* This table, taken from Dragendorff's Chemische Werthbestimmung einiger stark-
wirkenden Droguen, embodies the researches of Thorey.
§ 456–458.] SCOPOLAMINE. 395
§ 456. Dose and Effects.—The dose of the uncrystalline hyoscyamine
is 6 mgrms. (Ho grain). The senior author has seen it extensively
used in asylums to calm violent or troublesome maniacs. Thirty-two
mgrims. (4 grain) begin to act within a quarter of an hour; the face
flushes, the pupils dilate, there is no excitement, all muscular motion
is enfeebled, and the patient remains quiet for many hours, the effects
from a single dose not uncommonly lasting two days. 64.8 mgrms.
(1 grain) would be a very large, and possibly fatal, dose. The absence
of delirium or excitement, with full doses of hyoscyamine, is a striking
contrast to the action of atropine, in every other respect so closely
allied; yet there are cases on record showing that the henbane root
itself has an action similar to that of belladonna, unless indeed one root
has been mistaken for another; e.g., Sonnenschein relates the following
ancient case of poisoning:—In a certain cloister the monks ate by error
the root of henbane. In the night they were all taken with hallucina-
tions, so that the pious convent was like a madhouse. One monk sounded
at midnight the matins, some who thereupon came into chapel could not
read, others read what was not in the book, others sang drinking songs—
in short, there was the greatest disturbance.
§ 457. Separation of Hyoscyamine from Organic Matters.-The
isolation of the alkaloid from organic tissues or fluids, in cases where a
medicinal preparation of henbane, or of the leaves, root, etc., has been
taken, is possible, and should be carried out on the principles already
detailed. Hyoscyamine is mainly identified by its power of dilating the
pupil of the eye. It is said that so small a quantity as 0083 mgrim.
(Tºrg grain) will in fifteen minutes dilate the eye of a rabbit. It is true
that atropine also dilates the pupil; but if sufficient of the substance
should have been isolated to apply other tests, it can be distinguished
from atropine by the fact that the latter gives no immediate precipitate
with platinic chloride, whilst hyoscyamine is precipitated by a small
quantity of platinic chloride, and dissolved by a larger amount, by the
characters of the gold salt, and by the different form of the crystals in
the precipitate by Marmé's reagent (see p. 251).
3. SCOPOLAMINE.
$458. Scopolamine, C17H31NO3. According to Schmidt,” and more lately to
Merck, Ladenburg's t hyoscine Cin BosNOs does not exist, and is nothing but impure
Scopolamine. Scopolamine crystallises with one molecule of water. It is soluble in
alcohol, ether, chloroform, etc., but not very soluble in water. Scopolamine has a
melting-point of 59°, gives an aurochloride crystallising in needles, melting at
212°–214°. The hypobromide has a specific rotation of −25° 41'. It is a tertiary base
* Arch. Pharm., ccxxx. 207–231. + Journ. Soc. Chem. Ind., xvi. 515.
396 POISONS: THEIR EFFECTS AND DETECTION. [$ 459–461.
containing an a-methyl group. Boiled with baryta water it yields tropic acid and
Scopoline.
C17H31NO3 + H2O -> CoH10O3 + CsPI18NO2
Scopolamine. Tropic acid scopoline.
Scopoline forms an aurochloride melting at 223°–225°, and a platinochloride melting
at 228°–230°. By the action of alkalies and alkaline carbonates, scopolamine may be
converted into an inactive crystalline derivative—isoscopolamine, Cºhol NO4+ H2O ;
m. p. 56°. - .
By warming isoscopolamine to 54°–55° an anhydrous isoscopolamine may be
obtained, m.p. 82°–83°. Hesse * has found an inactive alkaloid in commercial
Scopolamine hydrobromide which he called atroscine, C17H31NO3 +2H2O ; m.p. 37°–38°.
Wolffenstein proposes to call these different derivatives i-scopolamine, i-scopolamine
monohydrate and dihydrate. Thus we have
Scopolamine, Ciºłł2, NO3 + H2O, laevorotatory; m.p. 59°.
i-Scopolamine, C17H31NO3, inactive ; m.p. 82°–83°. .
i-Scopolamine monohydrate (or isoscopolamine), C17H31NO3 + H2O, inactive; m.p. 56°.
i-Scopolamine dihydrate (or atroscine), C17H31NO3 +2H2O, inactive ; m.p. 37°–38°.
According to experiments on animals, the heart is first slowed, then quickened ;
the first effect being due to a stimulation of the inhibitory nervous apparatus, the
second to a paralysing action on the same. The temperature is not altered. The
pupils are dilated, the saliva diminished. The irritability of the brain is lessened. †
§ 459. Pseudo-hyoscyamine, C17H23NOs, isolated by Merck * from Duboisia.
myoporoides, crystallises from ether and chloroform in needles, melting at 133°–134°.
Taevorotatory. Soluble in alcohol and chloroform. A little soluble in ether and water.
Saponified with baryta water, it yields tropic acid and a base of the same formula
as, but not identical with, tropine.
Not a very active poison, but causes dilation of the pupil.
§ 460. Atropamine, C17H23NO2, occurs in roots of belladonna, and may be formed
by dehydrating atropine or hyoscyamine with sulphuric acid. On heating it forms
belladonnime.
Crystallises from ether in prisms melting at 60°–62°. Soluble in alcohol, ether,
and chloroform ; a little soluble in water and methyl alcohol. It is optically inactive,
and has no mydriatic action.
On Saponification with baryta it first forms belladonnine, then splits up into
atropic acid and tropine.
§ 460A. Belladonnime, C17H31NO2, is found in the belladonna ; it is a yellow
resinous mass ; a little soluble in water, and readily soluble in alcohol, ether,
chloroform, etc.
4. SOLANINE.
§ 461. Distribution of Solanine.—Solanine is a poisonous nitrogenised glucoside
found in all parts of the plants belonging to the nightshade order. The English
common plants in which solanine occurs are the edible potato plant (Solanum,
tuberosum), the nightshade (Solanum migrum), and the Solanum dulcamara, or
bitter-sweet. The berries of the Solanum nigrwin and those of Solanum dulcamara
contain about 0.3 per cent. Mature healthy potatoes appear to contain no solanine,
but from 150 grns, of diseased potatoes G. Kassner + separated 30 to 50 mgrims.
Albert Hilger and W. Markens (Ber., 1903) have purified crude solanine by
extraction with boiling absolute alcohol, and precipitation with acetic acid, water and
* Liebig’s Amm, der Chemie whd Pharm., ccxxi. 100.
f Parloff, St. Petersburg Med. Chem. Acad. Dissert., No. 9, 1899–90.
# Arch. Pharm. (3), xxv. 402, 403.
§ 462, 463.] - SOLANINE. 397
ammonia. The product is re-crystallised from alcohol ; these observers give the
formula as Cs2H970s N, and state that on hydrolysis with 2 per cent. Sulphuric acid,
croton-aldehyde, dextrose and solanidine are formed according to the reaction—
2C.H,0s N->3C, H2O,4-2C,E,0+2C.H.O.N +22H.O.
This research is criticised by Simon Zeisel and J. Wittman (Ber., 1903), who state
that only methylformaldehyde is formed in small quantity, that the sugar produced
contains a large proportion of rhamnose as well as some other carbohydrate, but that
from the mixture of sugars no crystalline dextrose can be obtained.
§ 462. Properties of Solanine. —The reaction of the crystals is weakly alkaline ;
the taste is somewhat bitter and pungent. Solanine is soluble in 8000 parts of
boiling water, 4000 parts of ether, 500 parts of cold, and 125 of boiling alcohol.
It dissolves well in hot amyl alcohol, but is scarcely soluble in benzene. An
aqueous solution froths on shaking, but not to the degree possessed by saponine
solutions. :
The amyl alcohol solution has the property of gelatinising when cold. It does
this if even so little as 1 part of solanine is dissolved in 2000 of hot amyl alcohol.
The jelly is so firm that the vessel may be inverted without any loss. This
peculiar property is one of the most important tests for the presence of solanine.
The hot ethylic alcohol solution will, on cooling, also gelatinise, but a stronger solution
is required. From very dilute alcoholic solutions (and especially with slow cooling)
solanine may be obtained in crystals. In dilute mineral acids Solanine dissolves
freely, and forms salts, which for the most part have an acid reaction and are soluble
in alcohol and in water, but with difficulty in ether. The compounds with the
acids are not very stable, and several of them are broken up on warming the solution,
solanine separating out from the aqueous solutions of the solanine salts. The
alkaloid may be precipitated by the fixed and volatile alkalies, and by the alkaline
earths. Solanine will stand boiling with strongly alkaline solutions without decom-
position ; but dilute acids, on warming, hydrolyse. By heating solanine in alcoholic
solution with ethyl iodide in closed tubes, and then treating the liquid with ammonia,
ethyl solanine in well-formed crystals can be obtained. Solanine is precipitated by
phosphomolybdic acid, but by very few other substances. It gives, for example, no
precipitate with the following reagents:–Platinic chloride, gold chloride, mercuric
chloride, potassic bichromate, and picric acid. Tannin precipitates it only after a
time. Sodic phosphate gives a crystalline precipitate of solamine phosphate, if
added to a solution of solanine sulphate. Both solamine and solanidine give with
nitric acid at first a colourless solution, which, on gentle warming, passes into blue,
then into light red, and lastly becomes weakly yellow. Solanine, dissolved in strong
sulphuric acid, to which a little Fröhde's reagent is added, at first colours the fluid
light brown ; after standing some time the edges of the drop become reddish-yellow,
and finally the whole a beautiful cherry-red, which gradually passes into dark violet
when violet-coloured flocks separate. -
§ 463. Solanidine.—Solanidine has stronger basic properties than solanine. Its
formula is C39H81 NO2. It is obtained from an alcoholic solution in amorphous
masses interspersed with needles ; m.p. 191°. It dissolves readily in hot alcohol,
with difficulty in ether. With hydrochloric acid it forms a hydrochloride—
3(CºPIsiNO.HCl)HCl + H2O or 1%H2O. This hydrochloride is a slightly yellow
powder, only sparingly soluble in water, and carbonising without melting when
heated to 287°. Solanidine also forms a sulphate, 3(C39H81 NO2H2SO4)H,SO, +8H2O:
this salt is in the form of scaly plates, melting at 247°; it dissolves readily
in water. -
The sugar obtained from the hydrolysis of solanidine is a yellow amorphous
mass dissolving readily in water and wood spirit, and has a specific rotatory power
of [a]be +28°623. With phenylhydrazine hydrochloride and sodium acetate in
\
\
\
398 POISONS: THEIR EFFECTS AND DETECTION. [$ 464–466.
aqueous solution it forms a glucosazone, melting at 199°. It is probably a mixture
of Sugars.
Solaneine is the name that has been given to an amorphous substance accom-
panying solanine; according to Hilger and Merkens (Ber., 1903) it is solanine
minus 5H2O.
§ 464. Poisoning from Solanine.—Poisoning from solamine has been, in all
recorded cases, induced, not by the pure alkaloid (which is scarcely met with out of
the laboratory of the scientific chemist), but by the berries of the different species of
solanum, and has for the most part been confined to children. The symptoms in
about twenty cases,” which may be found detailed in medical literature, have
varied so greatly that the most opposite phenomena have been witnessed as
effects of poisoning by the same substance. The most constant phenomena
are a quick pulse, laboured respiration, great restlessness, and hyperaesthesia
of the skin. Albumen in the urine is common. Nervous symptoms, such as
convulsions, aphasia, delirium, and even catalepsy, have been witnessed. In some
cases there have been the symptoms of irritant poison—-diarrhoea, vomiting,
and pain in the bowels: in many cases dilatation of the pupil has been observed.
Rabbits are killed by doses of 0-1 grm. per kilo. The symptoms commence in
about ten minutes after the administration, and consist of apathy and a low tem-
perature; the breathing is much slowed. Convulsions set in suddenly before death,
and the pupils become dilated. The post-mortem appearances in animals are intense
redness and injection of the meninges of the cerebellum, of the medulla oblongata,
and the spinal cord. Dark red blood is found in the heart, and the kidneys are
hyperaemic. The intestinal mucous membrane is normal.
§ 465. Separation of Solanine from the Tissues of the Body.--Dragendorff has
proved the possibility of separating solanine from animal tissues by extracting it from
a poisoned pig. The best plan seems to be to extract with cold dilute sulphuric acid
water, which is then made alkaline by ammonia, and shaken up with warm amyl
alcohol. This readily dissolves any solanine. The peculiar property possessed by
the alkaloid of gelatinising, and the play of colours with Fröhde's reagent, may then
be essayed on the solanine thus separated.
5. CYTISINE.
§ 466. The Cytisus Laburnum.—The laburnum tree, Cytisus
laburnum, so common in shrubberies, is intensely poisonous. The
flowers, bark, wood, seeds, and the root have all caused serious
symptoms. The active principle is an alkaloid, to which the name of
Cytisine has been given. Cytisine has also been found in many plants
belonging to the Leguminoseae, such as Ulex europaeus, Sophora tomentosa
and speciosa, Baptisia tinctoria, etc. The best source is the seeds of
laburnum. The seeds are powdered and extracted with alcohol con-
taining hydrochloric acid, the alcohol distilled off, the residue treated
with water and filtered through a wet filter to remove any fatty oil,
the filtrate treated with lead acetate; and, after separating the pre-
* See “Death of Three Children by S. nigrum,”; Hirtz., Gaz, Méd. de Stras.
bowrg, 1842; Maury, Gaz. des Hôp., 1864; J. B. Montane, Chim. Med., 1862;
Magne, Gaz, des Hôp., 1869; Manners, Edin. Med. Journ., 1867. Cases of poison-
ing by bittersweet berries are recorded in Lancet, 1856; C. Bourdin, Gaz. des
Hôpitaur, 1864; Bourneville, the berries of S. tuberosum, Brit. Med. ~, 1895.
|
a'
,”
§ 467.] CYTISINE. 399
cipitated colouring matter, made alkaline with caustic potash, and
shaken with amyl alcohol. The amyl alcohol is shaken with dilute
hydrochloric acid, the solution evaporated, the crude crystals of
hydrochloride thus obtained treated with alcohol to remove colouring
matters, and recrystallised several times from water; it then forms
well-developed, colourless, transparent prisms. From the hydrochloride
the free base is readily obtained.
Cytisine, CuFII,N2O.—To cytisine used to be ascribed the formula
Cao H2, NAO, but a study of the salt and new determinations appear to
prove that it is identical with ulexine. Cytisine is in the form of white
radiating crystals, consisting, when deposited from absolute alcohol, of
anhydrous prisms, which melt at from 152” to 153°. Cytisine has a
strong alkaline reaction; it is soluble in water, alcohol, and chloroform,
less so in benzene and amyl alcohol, almost insoluble in cold light
petroleum, and insoluble in pure ether. The specific rotatory power in
solution is [a],17° = – 119:57.
It is capable of sublimation in a current of hydrogen at 154-5°; the
sublimate is in the form of very long needles and small leaflets; at
higher temperatures it melts to a yellow oily fluid, again becoming
crystalline on cooling. Cytisine is a strong base; it precipitates the
earths and oxides of the heavy metals from solutions of the chlorides,
and, even in the cold, expels ammonia from its combinations.
Cytisine forms numerous crystalline salts, among which may be
mentioned two platinochlorides, CuHaN,OH,FtCls +2}H,0 and
(CIIPH14N2O), H2PtCls, crystallising in golden yellow needles, which are
tolerably soluble in water; and the aurochloride, CnH, N,0HAuCl4,
crystallising in short, red-brown, hook-shaped needles; m.p. 212° to 213°,
without evolution of gas. -
Cytisine forms at ordinary temperatures a condensation product
with formaldehyde, viz., methylene dicytisine, CH,(CuHisON.), This
may be crystallised from a solution in toluene; the m.p. of the crystals
is 212” (Freund and Friedmann, Ber., 1901).
$467. Reactions of Cytisine.—Concentrated sulphuric acid dis-
sqlves cytisine without colour; if to the solution is added a drop of
n bric acid, it becomes orange-yellow, and on addition of a crystal of
potassic bichromate, first yellow, then dirty brown, and lastly green.
Concentrated nitric acid dissolves the base in the cold without colour,
but, on warming, it becomes orange-yellow. Picric, tannic, and
phosphomolybdic acids, potassic, mercuric, and potass, cadmium iodides,
and iodine with potassic iodide, all give precipitates. Neither potassic
bichromate nor mercuric chloride precipitates cytisine, even though
the solution be concentrated. The best single test appears to be the
reaction discovered by Magelhaes; this consists in adding thymol
4OO POISONS: THEIR EFFECTS AND DETECTION. [$468, 469.
to a solution of cytisine in concentrated sulphuric acid, when a
yellow colour, finally passing into an intense red, is produced. The
reaction with formalin (formaldehyde) may be useful for purposes
of identification.
$468. Effects on Animals.-W. Marmé found subcutaneous doses
of from 30 to 40 mgrms. fatal to cats; death was from paralysis of the
respiration, and could be avoided by artificial respiration. Cattle are
sometimes accidentally poisoned by laburnum. An instance of this is
recorded in the Veterinarian (vol. lv. p. 92). In Lanark a storm had
blown a large laburnum tree down to the ground; it fell into a field
in which some young heifers were grazing, and they began to feed on
the leaves and pods. Two or three died, and three more were ill for
some time, but ultimately recovered.
The laburnum, however, does not always have this effect, for there
is a case related in the Gardeners' Chronicle, in which five cows browsed
for some time on the branches and pods of an old laburnum tree that
had been thrown aside. Rabbits and hares are said to feed eagerly, and
without injury, on the pods and branches.
§ 469. Effects on Man.—The sweet taste of many portions of
the laburnum tree, as well as its attractive appearance, has been
the cause of many accidents. F. A. Falck has been able to collect
from medical literature no less than 155 cases—120 of which
were those of the accidental poisoning of children: only 4 (or 2-6
per cent.), however, died, so that the poison is not of a very deadly
character.
One of the earliest recorded cases is by Christison.* A servant-
girl of Inverness, in order to excite vomiting in her fellow-servant
(the cook), boiled some laburnum bark in soup; very soon after
partaking of this soup, the cook experienced violent vomiting, which
lasted for thirty-six hours; she had intense pain in the stomach,
much diarrhoea, and great muscular weakness; she appears to have
suffered from gastro-intestinal catarrh for some time, but ultimately
recovered. - \
Wallance f has described the symptoms observed in the poisoning of
fifty-eight boys, who ate the root of an old laburnum tree, being allured
by its sweet taste. All were taken ill with similar symptoms, differing
only in severity; two who had eaten half an ounce (nearly 8 grrms.)
suffered with especial severity. The symptoms were first vomiting, then
narcosis, with convulsive movements of the legs and strange movements
of the arms: the pupils were dilated. This dilatation of the pupil
Sedgwick also saw in the poisoning of two children who ate the root.
On the other hand, when the flower, seeds, or other portions of the
* Ed. Med. Journ., 1843. i Brit. Med. Journ., 1875.
§ 470.] ALKALOIDS OF THE WERATRUMS. 4OI
laburnum have been eaten, the symptoms are mainly referable to the
gastro-intestinal tract, consisting of acute pain in the stomach, vomiting,
and diarrhoea. On these grounds it is therefore more than probable
that there is another active principle in the root, differing from that
which is in those portions of the tree exposed to the influence
of sunlight.*
The post-mortem appearances are, so far as known, in no way
characteristic. -
VII.-The Alkaloids of the Weratrums.
$470. The alkaloids of the veratrums have been investigated
by Dr. Alder Wright, Dr. A. P. Luff, Bozetti, Merck, and other
chemists, f
From the seeds of Veratrum sabadilla, Retz, a white amorphous
powder has been isolated which constitutes the commercial alkaloid
veratrine; it contains at least three alkaloids, viz., Cevadine or crystalline
veratrine, Cs2H16NOo, Veratridine or amorphous veratrine, Cº. Hss NOil,
and Sabadilline or cevadilline, Cs, Has NOs, as well as small quantities of
Sabadine, Cao Hsi NOs, and Sabadinine, C2. His NOs.
From V. album and V. viride a number of active principles have
been isolated.
The method which Wright and Luff adopted to extract and separate
the alkaloids from the root of V. album and V. viride, essentially con-
sisted in exhausting with alcohol, to which a little tartaric acid has
been added, filtering, distilling off the alcohol, dissolving the residue in
water, alkalising with caustic soda, and shaking up with ether. The
ethereal solution was next separated, and then washed with water
containing tartaric acid, so as to obtain a solution of the bases as
tartrates: in this way the same ether could be used over and over again.
Ultimately a rough separation was made by means of the different
solubilities in ether, pseudo-jervine being scarcely soluble in this medium,
whilst jervine, veratralbine, veratrine, and cevadine are very soluble
in it. -
The yield of Wright and Luff's alkaloids was as follows:—
* See also a case related by Dr. Popham, in which ten children ate laburnum
seeds; the pupils were dilated. They all recovered. B. and F. Med. Chir. Review,
Ap. 1863; also a case reported by H. Usher, Med. Times and Gazette, Sept. 15,
1862.
- + “The Alkaloids of the Veratrums,” by C. R. Alder Wright, D.Sc., and A. P.
Luff, Journ. Chem. Soc., July 1879; “The Alkaloids of Veratrum viride,” by C.
R. Alder Wright, D.Sc., ib., 1879. Bozetti, Arch. Pharm., ccxxi. 81; Merck, ibid.,
ccxxix. 104. - -
26
4O2 POISONS : THEIR EFFECTS AND DETECTION. [$470.
TABLE SHOWING THE ALKALOIDS IN THE WERATRUMS.

V. album. W. viride.
Per Kilo, IPer Kilo.
Jervine, . º º º o l'3 grm. ‘2 grim.
Pseudo-jervine, . . . . * '4 , , ‘15 , ,
Rubi-jervine, e e e e “25 , , *02 ,
Weratralbine, e e º • 2'2 , , Traces.
Weratrine, . * & tº º *05 , , Less than ‘004 grm.
Cevadine, . e e º º Absent. 2 3 "4 5 3
From whence it appears that V. album has only a very small quantity
of veratrine, that it is almost absent in V. viride; on the other hand,
V. viride contains a fair quantity of cevadine, an alkaloid absent in
V. album.
Besides the six principles enumerated, G. Salzberger has separated
two other crystalline substances, to which he has given the names of
protoveratrine and protoverałridine, and Pehkschen has also separated a
ninth substance, to which he has given the name of veratroidine.
The formulae of the nine bodies which have been separated from
hellebore root are as follows:—
Melting-point.
1. Veratridine (or amorphous veratrine), Caº Hss NOu, . I81°
2. Cevadine (or crystalline veratrine), C39H16NOo, - . 205°–206°
3. Protoveratrine, Cs2HBINO11, . e º e º . 245°–250°
- - Con H43.N.O. (Wright), . e • . 209°–300°
4. Pseudo-jervine, §§§º * * * * *
5. Weratralbine, Cash43NOs, & * e º & - * *
6. Protoveratridine, C23H48NOs, . & º º º e 26.5°
ſº tº º ConFI43NO2. (Wright and Luff), º e 236°
7. Rubijevine,{ 26++43 º º #) º º . 240°–245°
8. Jervine, C28H37NO32H2O, e º º & 237°–239°
9. Weratroidine, Ca2H53NOe, te e tº e ſº - 149°
Three of these alkaloids possess powerful sternutatory properties, the
least quantity applied to the nostrils exciting sneezing ; the three are
veratridine, cevadine, and protoveratrine.
Protoveratrine, Cash;1NOu, has been obtained by G. Salzberger *
from powdered veratrum root, by the following process:—
The powdered root is first freed from fatty and resinous matters by
treatment with ether, and then the fat-free powder is exhausted with
alcohol. The alcohol is evaporated off in a vacuum, the extract mixed
with much acetic acid water, filtered from the insoluble residue, and
treated with metaphosphoric acid; the voluminous precipitate contains
much amorphous matter, with insoluble compounds of jervine and
* Arch. Pharm., ccxxviii. 462–483,
§ 471.] ALKALOIDS OF THE WERATRUMS. 4O3
rubi-jervine. The precipitate is filtered off, and the filtrate treated
with excess of ammonia and shaken up with ether. On separating
the ether and distilling, protoveratrine crystallises out, and can be
obtained pure by recrystallisation from strong alcohol.
Protoveratrine crystallises in four-sided plates, which melt with
charring at 245° to 250°. The base is insoluble in water, benzene, and
light petroleum ; chloroform and boiling 96 per cent. alcohol dissolve it
somewhat ; cold ether scarcely touches it, boiling ether dissolves it a little.
Concentrated sulphuric acid dissolves the alkaloid slowly with the
production of a greenish colour, which passes to cornflower-blue, and
after some hours becomes violet. Sulphuric acid and sugar gives a
different colour to that produced by commercial veratrine. There is
first a green colour which darkens into olive-green, then becomes dirty
green, and finally dark brown. When warmed with strong sulphuric,
hydrochloric, or phosphoric acids, there is a strong odour of isobutyric
acid developed. Dilute solutions of the salts are precipitated by ammonia,
Nessler's reagent, gold chloride, potassium mercury iodide, cadmium
iodide, phosphotungstic acid, and picric acid ; no precipitate is produced
by tannin, platinum chloride, or mercuric chloride.
$471. Veratridine (Cs1H:ANOu) is an amorphous alkaloid, which is
a powerful irritant of the sensory nerves of the mucous membrane, and
excites violent sneezing. Treated with concentrated sulphuric acid, it
dissolves with a yellow colour, deepening into orange, then into blood-
red, and finally passing into carmine-red. If the freshly-prepared sul-
phuric acid solution is now treated with bromine water, a beautiful
purple colour is produced. Concentrated hydrochloric acid dissolves
veratridine without the production of colour, but, with careful warming,
it becomes beautifully red. This reaction is very delicate, occurring
with 17 mgrim. On Saponification veratridine yields verine, Cash is NOs,
and veratric acid, C, H, O, *
Weratric acid, dimethylether of protocatechuic acid, has the constitu-
tional formula, -
CH,0 °N COOH
CH.0 V
Veratric acid forms colourless needles and four-sided prisms, which have
a marked acid reaction; it melts at 180° to a colourless fluid, and
sublimes without decomposition; it is easily soluble in hot alcohol, but
insoluble in ether. If dissolved in mitric acid, water separates nitro-
veratric acid, Coho(NO2)O4, which crystallises out of alcohol in small
yellow scales. Veratric acid unites with bases forming crystalline salts;
the silver salt has the composition of CoHo AgO, - 37:37 per cent. silver,
4O4 POISONS: THEIR EFFECTS AND DETECTION. [$472-474.
and may assist in identification. It is crystalline, with a melting-point
of 205° to 206°,
Cevadine, or crystalline veratrine, Cash to NOo.—It has powerful
sternutatory properties, and, under the influence of alcoholic potash,
yields tiglic * acid and cevine, Cº. His NOs.
According to Ahrens, angelic acid is first formed, and then converted
into tiglic acid. When the alkaloid is boiled with hydrochloric acid,
tiglic acid is formed, and a ruby red mass. Nitric acid oxidises cevadine
completely; with potassic permanganate it yields acetic and oxalic acids;
with chromic acid it forms acetaldehyde and carbon dioxide,i
The Continental authorities always give to cevadine the name
of veratrine. Cevadine forms a crystalline aurochloride, a crystal-
line mercurochloride, Cs, HºNO,HHgCls, and a crystalline picrate,
Caº HºoVO,O, HANSO. The mercury salt crystallises in small silvery
plates, and melts with decomposition at 172°. The picrate forms stable
crystals blackening at 225°; both of the latter salts are but little soluble
in water, but are soluble in alcohol. Cevadine also unites with bromine,
forming a tetrabromide, an amorphous yellow powder insoluble in water
but readily soluble in alcohol, ether, and chloroform.
$472. Jervine, (C, H, NO,2H2O) (Wright and Luff), CuFI,NO,
(Pehſischen),f crystallises in white needles, and when anhydrous, melts
at 237.7". It is slightly lavorotatory. At 25” one part of the base
dissolves in 1658 benzene, 268 ether, 60 chloroform, and 16-8 absolute
alcohol. It is insoluble in light petroleum, and but slightly soluble in ethyl
acetate, water, or carbon bisulphide. It forms a very insoluble sulphate,
and a sparingly soluble nitrate and hydrochloride. Jervine gives, with
sulphuric acid and sugar, a violet colour, passing to blue. Treated with
strong sulphuric acid it dissolves to a yellow fluid, which becomes succes.
sively dark yellow, brownish-yellow, and then greenish. The green shade
is immediately developed by diluting with water. Jervine does not
produce sneezing.
§ 473. Pseudo-jervine, ConFIANO. (Wright), m.p. 299"; CooligoNOla,
m.p. 25.9° (Pehlschen), may be obtained in a crystalline state. One part
is soluble in 10.9 parts of light petroleum, 372 parts of benzene, 1021
parts of ether, 4 of chloroform, and 185 of absolute alcohol. The pure
base gives no colour with sulphuric, nitric, or hydrochloric acids. It does
not produce sneezing.
§ 474. Protoveratridine, CogPI, NOs, is probably derived from proto-
veratrine. Salzberger § isolated it from powdered veratrum roots by
* Tiglic acid, C.HsO3, is a volatile acid, m.p. 64°, boiling-point 198'5°; it forms
a soluble barium salt, and an insoluble silver salt.
+ Ber., xxiii. 2700–2707. : Jonºrm. Pharm. (5), xxii. 265–269.
§ Arch. Pharm., ccxxviii. 462-483.
§ 475-477.] ALKALOIDS OF THE VERATRUMS. 4O5
treating the powder with barium hydroxide and water, and extracting
with ether. The ether extract was separated and freed from ether in a
current of hydrogen at a low temperature.
From the dark green syrup obtained jervine crystallised out, and from
the mother-liquor ultimately protoveratridine was separated.
Protoveratridine crystallises in colourless four-sided plates, which melt
at 265”. It is almost insoluble in alcohol, chloroform, methyl alcohol,
and acetone, and insoluble in benzene, light petroleum, and ether. Con-
centrated sulphuric acid gives a violet, then a cherry-red colour. Its
solution in concentrated hydrochloric acid becomes light red on warming,
and there is an odour of isobutyric acid. It is readily soluble in dilute
mineral acid, and the solution, on the addition of ammonia, yields the
alkaloid in a crystalline condition. The sulphuric acid solution gives
precipitates with phosphotungstic, picric, and tannic acids, and with
potassium mercury iodide ; but gives no precipitate with platinum
chloride, potassium-cadmium iodide, or with Millon's reagent.
It forms a platinum salt (C26H5NOs), H2PtCl2 + 6H2O, which is pre-
cipitated in large six-sided plates on adding alcohol to a mixed solution
of platinum chloride and a salt of the base.
Protoveratridine is not poisonous, and does not cause sneezing. Its
solutions are very bitter.
$475. Rubijervine, C.His NO, is a crystallisable base wholly dif-
ferent from jervine, yet probably closely allied to it. Melting-point 237°
(Wright and Luff), 240°–246 (Salzberger). It forms a light yellow,
indistinctly crystalline gold salt (C26H13 NO2, HCl, AuCls): it gives a dif-
ferent play of colours from jervine with sulphuric acid. The concentrated
acid dissolves rubi-jervine to a clear yellow fluid, becoming successively
dark yellow, brownish-yellow, and brownish blood-red, changing after
several hours to a brownish-purple. On diluting slightly with water the
brownish-red liquid, it becomes successively crimson, purple, -dark
lavender, dark violet, and ultimately light indigo. Its hydrochloride and
sulphate are both more soluble than either of the corresponding salts of
jervine or pseudo-jervine.
§ 476. Veratralbine, Cash is NOs, an amorphous non-sternutatory
base, gives, when a speck of the substance is dissolved in sulphuric acid,
a play of colours, becoming successively yellow, dark yellow, brownish-
orange, and brownish blood-red, with a strong green fluorescence. It
yields no acid on Saponification.
§ 477. Veratroidine, Cash;s NOo, is another base which has been
separated by C. Pehkschen.” Its melting-point is 149”. One part dis-
solves in 13 of benzene, 59 of chloroform, and 9 of ether. It yield
amorphous salts with the mineral acids, and with oxalic and acetic acids.
* Op. cit.
4O6 POISONS: THEIR EFFECTS AND DETECTION. [$ 478,479.
It is precipitated by most of the group reagents. With 11 per cent.
solution of hydrochloric acid it gives a beautiful rose colour.
§ 478. Commercial Veratrine,—Commercial veratrine is a mixture of
alkaloids, and has usually fairly constant properties, one of which is its
intense irritant action on the nostrils. Placed on moist blue-red litmus
paper it gives a blue spot. It is but little soluble in water, I : 1500; but
readily dissolves in alcohol and chloroform; it is but little soluble in
amyl alcohol, benzene, and carbon disulphide.
When a very small quantity is treated with a drop of sulphuric acid,
the acid in the cold strikes a yellow colour; on warming, the colour
becomes violet, slowly changing to orange and cherry-red. Sensible to
100th of mgrm. If this test is performed in a test tube, a green-yellow
fluorescence is also seen on the sides of the test tube.
Commercial veratrime strikes a pink-red colour with hydrochloric
acid in the cold if a long time is allowed to elapse, but it at once
appears if the acid is warmed, and is permanent. The solution becomes
fluorescent if two drops of acetic acid are added.
If a small quantity of commercial veratrine is added to melted oxalic
acid and the warming continued, a blood-red colour is obtained.
Weratrine, warmed with syrupy phosphoric acid, develops an odour
of butyric acid.
A dark green colour, followed by reddish-purple and blue colours, is
obtained by adding a sprinkling of finely powdered sugar to a solution
of veratrine in sulphuric acid. This is best seen with a solution of
I to 10,000; if in dilution of 1 to 100,000 a grass-green colour is
produced, followed by purple and blue colours, quickly changing to
brown or black.”
When two or three drops of sulphuric acid and furfuraldehyde
(5 drops to 10 c.c. of acid) are added to minute particles of alkaloids, a
more or less characteristic colour makes its appearance; this is parti-
cularly the case with veratrine. A few particles rubbed with a glass
rod, and moistened with the reagent, gives first a yellowish-green, then
an olive-green mixture, the edges afterwards becoming a beautiful blue.
On warming, the mixture gradually acquires a purple-violet colour. The
blue substance obtained in the cold is insoluble in alcohol, ether, or
chloroform. The least amount of water decolorises the solution, and,
on adding much water, a fairly permanent yellow solution is obtained.t
§ 479. Pharmaceutical Preparations.—The alkaloid is officinal in
the English, American, and Continental pharmacopoeias. There is also
an unguémtwº veratrinae—strength about 1.8 per cent. In the London
pharmacopoeia of 1851 there used to be a wine of white veratrum, the
* Flückiger's Reactions, 1893.
+ A. Wender, Chem. Zeitung, xvii. 950, 951.
§ 480–482.] ALKALOIDS OF THE WERATRUMS. 4O7
active principle of 20 parts of the root by weight being contained in
100 parts by measure of the wine. Such a wine would contain about
0.084 per cent. of total alkaloids. Of the green veratrum there is a
tincture (tinctura veratri viridis), to make which four parts by weight
of the root are exhausted by 20 parts by measure of spirits; the strength
varies, but the average is 0:02 per cent. of total alkaloids.
§ 480. Fatal Dose.-The maximum dose of the commercial alkaloid
is laid down as 10 mgrms. ( 15 grain), which can be taken safely in a
single dose, but nothing sufficiently definite is known as to what is a
lethal dose. 1-3 grims. of the powdered rhizome have caused death, and,
on the other hand, ten times that quantity has been taken with impunity,
so that at present it is quite an open question.
§ 481. Effects on Animals—Physiological Action.— Experiments
on animals have proved that the veratrums act on the sensory nerves of
the skin, and those of the mucous membranes of the nose and intestinal
canal; they are first excited, afterwards paralysed. When administered
to frogs, sugar and lactic acid appear in the urinary excretion.* It
exercises a peculiar influence on voluntary muscle; the contractility is
changed, so that, when excited, there is a long-continuing contraction,
and from a single stimulus more heat is disengaged than with healthy
muscle; the motor nerves are also affected. The respiration, at first
quickened, is then slowed, and finally paralysed. The heart's action
is also first quickened, the blood-pressure at the same time is raised, and
the small arteries narrowed in calibre; later follow sinking of the
pressure, slowing of the heart, and dilatation of the vessels, and the
heart becomes finally paralysed.
$482. Effects on Man.—Poisoning by veratrum, sabadilla, or phar-
maceutical preparations containing veratrine, is not common. Plenk
witnessed a case in which the external application of sabadilla powder
to the head caused delirium, and Lentin also relates a case in which an
infant at the breast seems to have died from an external application
made for the purpose of destroying lice. In both instances, however,
there is a possibility that some of the medicament was swallowed.
Blas recorded, in 1861, the case of two children who drank a decoc-
tion of white hellebore, the liquid being intended as an external applica-
tion to an animal. They showed serious symptoms, but ultimately
recovered.
A scientific chemist took 38 grns. (58 grains) of the tincture of
green hellebore for the purpose of experiment. There followed violent
symptoms of gastric irritation, vomiting, and diarrhoea, but he also
recovered.t -
* Zeit. Phys. Chem..., xvi. 453-459.
i Med. Times and Gazette, Jan. 3, 1863.
408 POISONS: THEIR EFFECTS AND DETECTION. [$ 483-485.
Casper relates the poisoning of a whole family by veratrum ; from
the stomach of the mother (who died) and the remains of the repast
(a porridge of lentils) veratrine was separated.
Faber * recorded the poisoning of thirty cows by veratrum; eight
died, and it is noteworthy that violent poisonous symptoms were pro-
duced in animals partaking of their flesh and milk.
§ 483. The symptoms appear soon after the ingestion, and consist of
a feeling of burning in the mouth, spreading downwards to the stomach,
increased secretion of saliva, and difficulty of swallowing; them follow
violent vomiting and diarrhoea, with great pain in the bowels, often
tenesmus; there is also headache, giddiness, a feeling of anxiety, and
the pupils are dilated. The consciousness is ordinarily intact; the pulse
is weak and slow, and the breathing embarrassed ; the skin is benumbed.
There may be also formicating feelings, and twitchings in the muscles
with occasionally the tetanic cramps, which are constantly seen in frogs.
In cases which end fatally, the disturbance of the breathing and circula-
tion increases, and death takes place in collapse.
An important case of slow poisoning is on record,i in which
two brothers, aged 21 and 22 years, died after nine and eleven
weeks of illness, evidently from repeated small doses of the powder
of Veratrum album. They became very weak and thin, suffered
from bloody stools, sleeplessness, disturbance of the intellect, and
delirium.
§ 484. The post-mortem signs do not appear distinctive; even in the
cases just mentioned—in which one would expect to find, at all events,
an extensive catarrh of the intestinal canal—the results seem to have
been negative.
§ 485. Separation from Organic Matters.-The method of Stas (by
which the organic matters, whether the contents of the stomach or the
tissues, are treated with alcohol, weakly acidified by tartaric acid) is to
be recommended. After filtering, the alcoholic extract may be freed
from alcohol by careful distillation, and the extract taken up with water.
By now acidifying gently the watery extract, and shaking it up with
ether and chloroform, fatty matters, resinous substances, and other im-
purities are removed, and it may then be alkalised by soda or potash,
and the veratrine extracted by ether. The residue should be identified
by the hydrochloric acid and by the sulphuric acid and bromine re.
actions; care should also be taken to ascertain whether it excites
sneezing.
A ptomaine, discovered by Brouardel, f was described by him as both
chemically and physiologically analogous to veratrine. A. M. Deleziniereș
* Zeitschr. f. Staatsarzneik., 1862. I Nivet and Geraud, Gaz. Hebdom., 1861.
: Monitewr Scient. (3), x. 1140. § Bull. Soc. Chim, (3), i. 178–180.
§ 486, 487.] PhysosTIGMINE. 4O9
has since investigated this substance. Only when in contact with air
does the analogy to veratrine obtain, and Deleziniere, to ascertain its
reactions, studied it when in an atmosphere of nitrogen. It appears to
be a secondary monamine, CºgPIsiN, and is in the form of a colourless,
oily liquid, with an odour like that of the hawthorn. It is insoluble in
water, but alcohol, ether, toluene, and benzene dissolve it readily. It
oxidises in the presence of air. The salts are deliquescent.
VIII.-Physostigmine.
§ 486. The ordeal bean of Calabar (Physostigma faba) is a large, all
but tasteless, kidney-shaped bean, about an inch in length, and half an
inch thick; its convex edge has a furrow with elevated ridges, and is
pierced by a small hole at one extremity. The integuments are coffee-
brown in colour, thin, hard, and brittle ; they enclose two white coty-
ledons, easily pulverisable, and weighing on an average 398 grns.
(61 grains). The seed contains at least one alkaloid, termed Physostig-
mine (first separated in 1864 by Jobst and Hesse), and possibly a second
according to Harnach and Witkowsky, who have discovered in association
with physostigmine a new alkaloid, which they call Calabariue, and which
differs from physostigmine in being insoluble in ether and soluble in
water, It is also soluble in alcohol; and further, the precipitate pro-
duced by potassium iodo-hydrargyrate in calabarine solutions is insoluble
in alcohol.
§ 487. Physostigmine, or eserine, is not easily obtained in a crystal-
line state, being most frequently extracted as a colourless varnish, drying
into brittle masses. It is, however, quite possible to obtain it in the
form of partially-crystalline crusts, or even rhombic plates, by care being
taken to perform the evaporation, and all the operations, at as low a
temperature as possible, and preferably in a dimly-lit room ; for, if the
temperature rises to 40°, much of the alkaloid will be decomposed.
Hesse recommends that the beans be extracted by alcohol, the alcoholic
solution alkalised by sodic carbonate, and the liquid shaken up with
ether, which will retain the alkaloid. The ether solution is now separated,
and acidified slightly with very dilute sulphuric acid ; the fluid, of course,
separates into two layers, the lower of which contains the alkaloid as a
sulphate, the upper is the ether, which is withdrawn, and the acid fluid
passed through a moist filter. The whole process is then repeated as a
purification.
Again, Vee, who has repeatedly obtained the alkaloid in a crystalline
condition, directs the extraction of the beans by alcohol, the alcoholic
solution to be treated as before with sodic carbonate, and then with ether;
4 IO POISONS : THEIR EFFECTS AND DETECTION. [$ 488.
the ethereal solution to be evaporated to dryness, dissolved in dilute acid,
precipitated by sugar of lead, and the filtrate from this precipitate alkalised
by potassic bicarbonate, and then shaken up with ether. The ethereal
Solution is permitted to evaporate spontaneously, the crystalline crusts
are dissolved in a little dilute acid, and the solution is lastly alkalised
by potassic bicarbonate, when, after a few minutes, crystalline plates are
formed.
The formula ascribed to physostigmine is C18H31N3O3. It is strongly
alkaline, fully neutralising acids, and forming tasteless salts. It crystal-
lises from benzene in large flat prisms which melt at a temperature of
105°-106°. It dissolves easily in alcohol, ether, chloroform, and bisul-
phide of carbon, but is not easily soluble in water. The sp. rotatory
power in chloroform is (a)p = – 82°. The benzoate * crystallises in hard
white prisms melting at 115°-118° ; the majority of the other salts are
very hygroscopic.
If CO2 is passed into water containing the alkaloid in suspension, a
clear solution is obtained ; but the slightest warmth decomposes the
soluble salt and reprecipitates the alkaloid. The hydrarg-hydriodide
(C18H31N3O2HI,2HgI) is a white precipitate, insoluble in water, becoming
yellow on drying, soluble in ether and alcohol, and from such solutions
obtained in crystalline prismatic groups. A heat of 70" melts the
crystals, and they solidify again in the amorphous condition.
It gives a precipitate with gold chloride, reducing the gold; also one
with mercuric chloride, easily soluble in hydrochloric acid. It gives no
precipitate with platinum chloride.
§ 488. Tests.-Da Silva's f test for eserine is as follows:—A minute
fragment of eserine or one of its salts is dissolved in a few drops of
fuming nitric acid; this makes a yellow solution, but evaporated to
complete dryness it is pure green. The green substance, called by others
chloreserine, dissolves to a non-fluorescent green solution ; in water and
also in strong alcohol it shows a band in the red between A670 and A680,
a broader but more nebulous band in the blue and violet between A400
and A418, and a very feeble band in the orange.
J. B. Nagelvoort f has recommended the following tests:–(a) An
amorphous residue of a permanent blue colour is obtained if a trace of
the alkaloid, or one of its salts is evaporated in the presence of an excess
of ammonia; this blue alkaloid dissolves in dilute acids with a red colour;
sensitiveness 0-00001 gm. (1 : 100000). The solution has beautiful red
fluorescence in reflected light ; when evaporated, it leaves a residue that
is green at first, changing to blue afterwards, the blue residue being
* Petit and Polonovsky (J. Pharm., xxix. 55).
+ S. J. Ferreira da Silva, Compt. Rend., czvii. 330, 331.
† Flückiger's Reactions, 1893.
$489, 490.] PHYSOSTIGMINE. 4 II
soluble in water, alcohol, and chloroform, but not in ether. Chloroform
extracts the blue colour from the watery ammoniacal solution only par-
tially. The blue solutions are reddened at first by H.S, and discoloured
afterwards. The blue colour is restored by expelling the H2S on the
water-bath. (b) Eserine and its salts, dissolved in fuming nitric acid,
give a yellow solution which, when warmed on the water-bath, becomes
darker and leaves a green residue. The latter dissolves with a green
colour in water and alcohol; in dilute nitric acid the solution shows
a greenish-yellow fluorescence by transmitted light, and a blood-red by
reflected light. (c) A red fluid is obtained when 0-010 gm, eserine or
its salicylate, 0.050 gm. of slacked lime, and 1 c.c. of water are mixed
together. Warmed in a water-bath, it turns green, and a piece of red
litmus-paper suspended in the test tube turns blue ; a glass rod
moistened with HCl gives off the well-known white clouds character-
istic of an ammonia reaction. The green solution does not lose its
colour by evaporation. Baryta water, added to an eserine solution,
gives a white precipitate that turns red when strongly agitated, sensitive
to 0.01 mgrim. (1 : 100000).
$489. Pharmaceutical Preparations.—The only preparations officinal
in this country are a spirituous extract (Extractum physostigmatis), used
principally for external application, the dose of which is not more than
18.1 mgrums. (28 grain), and gelatine discs for the purpose of the
ophthalmic surgeon, each disc weighing about #5th grain, and containing
rºot, gr. of the alkaloid. -
$490. Effects on Animals.-A large number of experiments have
been made upon animals with physostigmine, most of them with the
impure alkaloid, which is a mixture of calabarine and physostigmine.
Now, the action of calabarine seems to be the opposite to that of physo-
stigmine—that is, it causes tetanus. Hence, these experiments are not
of much value, unless the different proportions of the alkaloids are
known. Harnack and Witkowsky “ made, however, some researches
with pure physostigmine, of which the following are the main results:—
The smallest fatal dose for rabbits is 3 mgrims, per kilo.; cats about the
same ; while dogs take from 4 to 5 mgrms. per kilo. Frogs, under the
influence of the alkaloid, lie paralysed without the power of spontaneous
movement, and the sensibility is diminished ; later, the breathing ceases,
and the reflex irritability becomes extinguished. The activity of the
heart is through 5 mgrim, slowed, but at the same time strengthened.
The warm-blooded animals experimented upon show rapid paralysis
of the respiratory centre, but the animals by artificial respiration can be
saved. Fibrillar muscular twitching of all the muscles of the body are
observed. Death follows in all cases from paralysis of the respiration.
* Arch. f. Pathol. w. Pharm., 1876, Bd. v.
4 I 2 POISONS: THEIR EFFECTS AND DETECTION. [$ 491–493.
Experiments (first by Bexold, then by Fraser and Bartholow, and lastly
by Schroff) have amply shown that atropine is, to a certain extent, an
antidote for physostigmine poisoning. Fraser also maintains an antag-
onism between strychnine and physostigmine, and Bennet that chloral
hydrate is antagonistic to physostigmine.
Effects on Man.—The bean has long been used by the superstitious
tribes of the West Coast of Africa as an ordeal, and is so implicitly
believed in that the innocent, when accused of theft, will swallow it,
in the full conviction that their innocency will protect them, and that
they will vomit up the bean and live. In this way, no doubt, life has
often been sacrifeed. Christison experimented upon himself with the
bean, and nearly lost his life. He took 12 grains, and was then seized
with giddiness and a general feeling of torpor. Being alarmed at the
Symptoms, he took an emetic, which acted. He was giddy, faint, and
seemed to have lost all muscular power; the heart and pulse were
extremely feeble, and beat irregularly. He afterwards fell into a sleep,
and the next day he was quite well.
In August 1864 forty-six children were poisoned at Liverpool by
eating some of the beams, which had been thrown on a rubbish heap,
being part of the cargo of a ship from the West Coast of Africa. A boy,
aged 6, ate six beans, and died. In April of the same year, two
children, aged 6 and 3 years, chewed and ate the broken fragments
of one bean ; the usual symptoms of gastric irritation and muscular
weakness followed, but both recovered. Physostigmine contracts the iris
to a point ; the action is quite local, and is confined to the eye to which
it is applied. When administered internally, according to some, it has
no effect on the eyes, but according to others, it has a weak effect in
contracting the pupil. In any case, the difference of opinion shows that
the effect, when internally administered, is not one of a marked character.
§ 491. Physiological Action.—The physiological action of physostig.
mine is strikingly like that of nicotine, which it resembles in being a
respiratory poison, first exciting, afterwards paralysing the vagus. Like
nicotine, also, it produces a great loss of muscular power; it first excites,
and then paralyses the intra-muscular terminations of the nerves; and
again, like nicotine, it induces a tetanus of the intestine. A difference
between physostigmine and nicotine exists in the constant convulsive
effects of the former, and in the greater influence on the heart of the
latter.
§ 492. Post-mortem Appearances.—But little is known relative to
the post-mortem appearances likely to be found in human poisoning;
redness of the stomach and intestines is probably the chief sign.
§ 493. Separation of Physostigmine.—For the extraction of physo-
stigmine from the fluids of the body, Dragendorff recommends benzene:
§ 494.] PHYSOSTIGMINE. 4 I 3
the alcoholic filtered extract (first acidified) may be agitated with such
solvents as petroleum and benzene, in order to remove colouring matter;
then alkalised and shaken up with benzene, and the latter allowed to
evaporate spontaneously—all the operations being, as before stated,
carried on under 40°. If much coloured, it may be purified according
to the principles before mentioned. In cases where enough of the
extract (or other medicinal preparation) has been taken to destroy life,
the analyst, with proper care, would probably not have much difficulty
in separating a small quantity of the active principle. It is rapidly
eliminated by the saliva and other secretions. In most cases it will be
necessary to identify physostigmine by its physiological activity, as well
as by its chemical characters. For this purpose a small quantity of the
substance should be inserted in the eye of a rabbit; if it contains the
alkaloid in question, in twenty minutes, at the very latest, there will
be a strong contraction of the pupil, and a congested state of the
conjunctival vessels. Further researches may be made with a small
quantity on a bird or frog. The chief symptoms observed will be those
of paralysis of the respiratory and voluntary muscles, followed by death.
If a solution is applied to the web of a frog's foot, the blood-vessels
become dilated. Physostigmine appears, according to Dragendorff and
Pander, to act as an irritant, for they always observed gastro-enteritis
as a result of the poison, even when injected subcutaneously. The
enhanced secretion from all mucous surfaces, and the enlargement of
the blood-vessels, are also very constant symptoms. But of all these
characteristics, the contraction of the pupil is, for the purposes of
identification, the principal. A substance extracted from the tissue or
other organic matters, in the manner mentioned, strongly contracting
the pupil and giving the bromine reaction, would, in the present state
of our knowledge, be indicative of physostigmine, and of that alone.
$494. Fatal Dose of Physostigmine.—One mgrm. (.015 grain) as
sulphate, given by Wee to a woman subcutaneously, caused vomiting, etc.,
after half an hour. A disciple of Gubler's took 2 mgrms, without
apparent effect; but another mgrm., a little time after, caused great
contraction of the pupil and very serious symptoms, which entirely
passed off in four hours. It would thus seem that three times this (i.e.,
6 mgrms.) would be likely to be dangerous, Hence man is far more
sensitive to physostigmine than dogs or cats; and 3 mgrms. per kilo.—
that is, about 205 mgrms. (3 grains)—would be much beyond the least
fatal dose.
4. I4 POISONS: THEIR EFFECTS AND DETECTION. [$495–497.
IX. —Pilocarpine.
§ 495. From the leaves of the jaborandi, Pilocarpus pennatafolius
(Nat. Ord. Rutaceae), four alkaloids have been separated, viz. –
Pilocarpine, CuFileN,02; Isopilocarpine, CuFI18N2O, ; Pilocarpidine,
Cho FL14N2O, ; Jaborine, CuFIGN2O3:
Jaborine (Cu Hign,03) is a strong base, differing from pilocarpine in
its sparing solubility in water, and more ready solubility in ether; its
salts are soluble in water and alcohol, but do not crystallise. P. Ghas-
taing,” by treating pilocarpine with a large quantity of nitric acid,
obtained nitrate of jaborine, and operating in the same way with hydro-
chloric acid, obtained the hydrochlorate of jaborine ; Jowett thinks that
this substance is a mixture of Isopilocarpine, Pilocarpidine, and a little
Pilocarpine.
§ 496. Pilocarpine (Cin Hign,02) is a soft gelatinous mass, but it
forms with the mineral acids crystallisable salts. The solutions are
dextrorotatory, an = + 100:5°.
If the free base is distilled in vacuo, a large portion of the pilo-
carpine is converted into isopilocarpine. By oxidation with potassium
permanganate, ammonia, methylamine, propionic acid, pilopic acid,
Cs H10O, and homopilopic acid, CsPH1904, result. Jowett considers that
Pilocarpine is a stereoisomer of isopilocarpine, and that both may be
represented by the following formula
The nitrate and hydrochloride are at present much used in pharmacy.
Pilocarpine gives a precipitate with phosphomolybdic acid, potassio-
mercuric iodide, and most general alkaloidal reagents, but none that are
very distinctive. When a solution of gold chloride is added to one of
pilocarpine, a salt falls, having the composition CuPIIGN,0, HCl + AuCls.
It is not very soluble in water (about 1 in 4600), and has been utilised
for the estimation of pilocarpine. Pilocarpine dissolves without the
production of colour in sulphuric acid; but, with bichromate of potash
and sulphuric acid, a green colour is produced. It may be extracted
from an aqueous solution made alkaline by ammonia, by shaking up
with chloroform or benzene. - i
§ 497. Tests.--When a little of the alkaloid is mixed with ten times
its weight of calomel, and rubbed, and moistened by the breath, the
* Compt. Rend., vol. xciv. p. 223.
§ 498.] PILOCARPINE. 4I 5
calomel is blackened ; cocaine also acts similarly ; but the two could
not be mistaken for each other. If a solution of mercur-potassium
iodide is added to a solution of the hydrochloride, the amorphous pre-
cipitate becomes, in the course of a day or two, oily drops. “A Solution
of iodine in potassium iodide gives in pilocarpine solutions a brown
precipitate that often crystallises to feathery brown crystals (micro-
scopically), and of serrated form, something like the blade of a scroll-
saw, when the crystallisation is incomplete.”—Flückiger's Reactions.
When boiled with sodium persulphate it gives an ammoniacal
smell, the vapours blacken mercurous nitrate, and turn turmeric paper
blue. Warmed with H.S.O., it gives first a yellow colour, then brownish-
red, blood-red, and finally a brownish-red. Mandeline's reagent gives,
on warming, first a golden-yellow colour, then a clear green, and finally
a blue.* -
§ 498. Effects.-Pilocarpine, given subcutaneously in doses of about
32 mgrms. (; grain), causes within five minutes a profuse perspiration
and salivation, the face becomes flushed, and the whole body sweats;
at the same time, the buccal secretion is so much increased that in a
few hours over a pint may be secreted. The tears, the bronchial
secretion, and the intestinal secretions are also augmented ; there are
generally headache and a frequent desire to pass water; the pulse is
much quickened, and the temperature falls from 14° to 4" : the
symptoms last from two to five hours. Langley has shown that the
over-action of the submaxillary gland is not affected by section either
of the chorda tympani or of the sympathetic supplying the gland.
Although pilocarpine quickens the pulse of man, it slows, according to
Langley,i the heart of the warm-blooded animals, and that of the frog.
With regard to the frog, Dr. S. Ringer's researches are confirmatory.
With large doses the heart stops in diastole. If to the heart thus
slowed, or even when recently stopped, a minute quantity of atropine
be applied, it begins to beat again. There is also a most complete
antagonism between atropine and pilocarpine in other respects, atropiae
stopping the excessive perspiration, and relieving the headache and
pain about the pubes, etc. Pilocarpine, given internally, does not alter
the size of the pupil, but the sight may, with large doses, be affected.
This may be due to the presence of pilocarpidine. If a solution is
applied direct to the eye, then the pupil contracts. No fatal case of
its administration has occurred in man. The probable dangerous dose
would be about 130 mgrms. (2 grains) administered subcutaneously.
Pilocarpine must be classed among the heart poisons.
* E. Barral, Journ. Pharm. Chem..., xix., 1904.
+ “The Action of Jaborandi on the Heart,” by J. N. Langley, B.A., Journ,
Amat. and Physiol., vol. x. p. 187.
416 POISONS: THEIR EFFECTS AND DETECTION. [$499–501.
Isopilocarpine,” CuPIs N2O, is an oily liquid, boiling at 261° at a
pressure of 10 mm. (a) = + 42.8°. The following are the melting-
points of some of the salts of pilocarpine and isopilocarpine:—
& Pilocarpine. Isopilocarpine.
Nitrate, e º tº {- º t . 178° 159°
Hydrochloride, . - º º . 204°-205° 127°
Hydrobromide, . . e tº tº . 185° 147°
Methiodide, . * * º º & . an oil 114°
Pilocarpidine.—CoPI, N,02, a crystalline alkaline mass, soluble in
alcohol and chloroform, and a little soluble in water. The nitrate,
Clo H11N3O2HNO3, gives prismatic crystals, melting at 137°, and
(a) = + 73.2°. The aurochloride melts at 124°–125°. The picrate is
an oil. Pilocarpidine causes dilation of the pupil.
X.—Taxine.
$499. Properties of Taxine.—The leaves and berries, and probably
other portions of the yew tree (Taa:us baccata), are poisonous. The
poison is alkaloidal, and was first separated by Marmé.
Taxine (CºHa2010N).—Taxine has hitherto been obtained as a snow-
white amorphous powder, scarcely soluble in water, but dissolving in
alcohol, in ether, and in chloroform ; insoluble in benzene. It melts
at 82°, gives an intense purple-red, with sulphuric acid, and colours
Frohde's reagent reddish-violet. -
A slightly acid aqueous solution of the alkaloid gives precipitates
with all the group reagents and with picric acid.
The salts are soluble in water; the hydrochloride may be obtained
by passing gaseous HCl into a solution of the alkaloid in anhydrous
ether. The platinochloride forms a yellow micro-crystalline powder,
(Ca, Hºsolo N), H., PtCl6. The salts are generally difficult to crystallise.f
§ 500. Poisoning by Yew.—Falck has been able to collect no less
than 32 cases of poisoning by different parts of the yew—9 were from
the berries, and the rest from the leaves. They were all accidental;
20 persons died, or 62.5 per cent.
§ 501. Effects on Animals—Physiological Action.—From the re-
searches of Marmé-Borchers, it appears that taxine acts upon the
nervous centres—the nervous trunks themselves and the muscles re-
maining with their excitability unimpaired, even some time after
death. Taxine kills through paralysis of the respiration, the heart
beating after the breathing has stopped. The leaves contain much
.* Jowett, Journ. Chem. Soc., lxxvii. 473.
| A. Hilger and F. Brande, Ber., xxiii. 464–468,
§ 502, 503.] TAXINE. 4 I 7
formic acid, and their irritant action on the intestine is referred to this
C3,UISé.
§ 502. Effects on Man.—Several deaths from yew have resulted in
lunatic asylums from the patients chewing the leaves. For example,
some years ago, at the Cheshire County Asylum, a female, aged 41, was
suddenly taken ill, apparently fainting, her face pale, her eyes shut, and
pulse almost imperceptible. Upon the administration of stimulants,
she somewhat revived, but in a little while became quite unconscious.
The pupils were contracted, and there were epileptiform convulsions,
succeeded by stertorous breathing. These convulsions returned from
time to time, the action of the heart became weaker, and there was a
remarkable slowing of the respirations, with long intervals between the
breathing. The woman died within an hour from the time when her
illness was first observed, and within two hours of eating the leaves.
Yew leaves were found in her stomach. In another case that occurred
at the Parkside Asylum,” the patient died suddenly in a sort of epileptic
fit. Yew leaves were again found in the stomach. In a case quoted by
Taylor, in which a decoction of the leaves was drunk by a girl, aged 15,
for the purpose of exciting menstruation, she took the decoction on four
successive mornings. Severe vomiting followed, and she died eight
hours after taking the last dose. In another case there were also no
symptoms except vomiting, followed by rapid death. Mr. Hurt, of
Mansfield, has recorded a case of poisoning by the berries. The child
died in convulsions before it was seen by any medical man.
From these and other recorded cases, the symptoms seem generally
to be a quick pulse, fainting or collapse, nausea, vomiting, convulsions,
slow respiration, and death, as a rule sudden and unexpected. We may
suppose that the sudden death is really due to a rapid paralysis of the
respiration, and suffocation. -
§ 503. Post-mortem. Appearances.—In the case of the girl who
drank the decoction, nothing unusual was observed in the stomach or
organs of the body; but when the leaves have been eaten, usually more
or less congestion of the mucous membrane of the stomach as well as of
the bowels is apparent. In the case of the child who ate the berries
(Hurt's case), the stomach was filled with mucous and half-digested pulp
of the berries and seeds. The mucous membrane was red in patches and
softened, and the small intestines were also inflamed.
* Pharm. Journ. (3), No. 294.
27
418 POISONS : THEIR EFFECTS AND DETECTION. [$ 504.
XI.-Curare alkaloids.
§ 504. Commercial curare is a black, shining, resinoid mass, about
83 per cent. of which is soluble in water, and 79 in weak spirit. It is a
complicated mixture of vegetable extracts, from various plants. Tube-
curare, which, according to Pictet, is the commercial variety, has been
shown by Boehm to contain two alkaloids, tubo-curarine, Ciołł21NO, a
reddish powder with a bitter taste, and curine, CisłIlo NOs, which crystal-
lises in colourless prisms and melts at 212°. s
Calabash-curare, from Strychnos toacifera, is said to contain a substance,
curarine, Clo Hoa NO2, which is amorphous and very bitter. It must be
remembered that the name curarine has also been applied to the mixed
alkaloids from commercial curare. i
Pot-curare,from Strychnos castelnaca, contains protocurine, CooHosNOs,
a slightly toxic crystalline substance, melting at 306”; protocuridine,
Clo H21NO3, a non-toxic crystalline substance, melting at 274°-276°; and
Protocurarine, Clo HosNO2, a toxic substance. These substances have not
been fully investigated.
Curare is an arrow poison * prepared by different tribes of Indians
in South America, between the Amazon and the Orinoco ; therefore,
samples are found to vary much in their poisoning properties, although
it is noticeable that qualitatively they are the same, and produce closely
analogous symptoms. It is now known that some of the curare is
derived from different species of strychnos, and like the South American
strychnines paralyse, and do not tetanise. It is not unlikely that the
active principles of curare (or woorari) may be methyl compounds similar
to those which have been artificially prepared, such as methylstrychnine
* A constituent of the Borneo arrow poison is “derrid,” a toxic principle obtained
from a leguminous plant, the Derris elliptica ; it is a resinous substance, which has
not yet been obtained in the pure state. It is said not to be a glucoside, nor to contain
any nitrogen (Greshoff, Ber., xxiii. 3537–3550).
The Comalis on the east coast of Africa prepare an arrow poison from the aqueous
extract of the root of Oubaion, a tree closely related to Carissa Schimperii.
Oubain is prepared by treating the aqueous extract with lead acetate, getting
rid of excess of lead by SH2, and concentrating in a vacuum. The syrup is boiled
with six times its volume of alcohol of 85°, and allowed to cool in shallow vessels :
crystals are obtained which are recrystallised, first from alcohol, and afterwards
from water.
Oubain, Cao H16O12, forms thin white nacreous lamellae. It is tasteless, odourless,
and neutral, almost insoluble in cold water, and soluble in boiling water ; it dissolves
readily in moderately concentrated alcohol, is almost insoluble in absolute alcohol,
and insoluble in ether and chloroform. Its melting-point is 200°. The solution of
oubain in water is laevorotatory [a]D=-340. It is a glucoside, yielding on boiling
with dilute acids a sugar. It is very poisonous; 2 mgrms. will kill a dog of 12 kilos.
weight in a few minutes, if subcutaneously injected ; but, taken by the stomach, it
produces no effect.—Arnaud, Compt. Rend, cvi. 1011–1014,
§ 505.] CURARE ALKALOIDS. 4 IQ
and methyl brucine, both of which have a curare-like action. And
methoxyl groups have been found in tubo-curarine and curine.
The mixed alkaloids of curare were first separated by Preyer in a
crystalline form in 1865. He extracted curare with boiling alcohol, to
which a few drops of soda solution had been added, evaporated off the
alcohol, took up the extract with water, and, after filtration, precipitated
by phosphomolybdic acid, which had been acidified with nitric acid. The
precipitate was dried up with baryta water, exhausted with boiling
alcohol, and the alkaloids precipitated from the alcoholic solution by
anhydrous ether. It may also be obtained by precipitating with
mercuric chloride solution, and throwing out the mercury afterwards
by means of hydric sulphide, etc.
The alkaloids so isolated form colourless, four-sided, very hygroscopic
prisms of bitter taste, and weakly alkaline reaction; soluble in water
and alcohol in all proportions, but with difficulty soluble in amyl alcohol
and chloroform, and not at all in anhydrous ether, bisulphide of carbon,
or benzene. The bases form crystallisable salts with hydrochloric,
nitric, and acetic acids. The alkaloids strike a purple colour with strong
nitric acid. Concentrated solutions mixed with dilute glycerin give an
amorphous precipitate with potassic bichromate, and the precipitate
treated with sulphuric acid strikes a beautiful blue colour. The chromate
is distinguished from strychnine chromate by its amorphous character,
and by its comparatively easy solubility. If the chromates of strychnine
and curare alkaloids be mixed, and the mixed chromates be treated
with ammonia, strychnine will be precipitated and curare alkaloids pass
into solution, thus forming a ready method of separating them.
§ 505. Physiological Effects.-According to Voisin and Liouville's
experiments, subcutaneous injections of curare on man cause, in small
doses, strong irritation at the place of application, swelling, and pain.
The temperature of the body is raised from 1° to 2°, and the number of
respirations increased from 4 to 8 per minute. The pulse becomes
somewhat stronger and more powerful. The urine is increased, and
contains sugar. Large doses administered to warm-blooded animals
cause, after a short time, complete paralysis of voluntary motion and of
reflex excitability, and the animal dies in asphyxia, the heart continuing
to beat.
This state is best produced, for the purpose of experiment, on frogs,
and, indeed, is the best test for the poison. A very minute dose
injected beneath the skin of a frog soon paralyses both the voluntary
and respiratory muscles; the animal continues to breathe by the skin;
the heart beats normally, or, perhaps, a little weakly, and the frog may
remain in this motionless condition for days and yet recover. Only
curare and its congeners have this effect. By tying the femoral artery
42O POISONS: THEIR EFFECTS AND DETECTION. [$ 506.
of one of the frog's legs before administering the poison, an insight into
the true action of the drug is obtained. It is then found that the
reflex excitability and power of motion in the leg are retained, although
all the rest of the body is paralysed. The only explanation of this is
that curare does not act centrally, but paralyses the intramuscular ends
of the motor nerves. The experiments of Overend Hofman (“Studien
über den Tetanus,” Pfluger's Archiv, Bd. xciii.), also show that curare
has a special action on the muscular fibre itself, decreasing in a marked
degree its power. Curare is eliminated partly through the liver and
partly through the kidneys. Dragendorff found it in the faeces, while
a striking proof that it is excreted by the kidneys is given by the
experiment of Bidder,” in which the urine of a frog poisoned by curare
was made to poison a second, and the urine of the second, a third. The
easy excretion of curare through the kidneys furnishes an explanation
of the relatively large dose of curare which can be taken by the stomach
without injury. A dose which, given by subcutaneous injection, would
produce violent symptoms, perhaps death, may yet be swallowed, and no
ill effects follow. It is hence presumed that, in the first case, the poison
is, comparatively speaking, slowly absorbed, and almost as fast separated,
and put, as it were, outside the body by going into the urine ; while, in
the other case, the whole dose is thrown suddenly into the circulation.
§ 506. Separation of Gurarine.—It is hardly probable that the
toxicologist will have to look for curarine, unless it has entered the
body by means of a wound or by subcutaneous injection ; so that in all
cases the absorbed poison alone must be sought for. The seat of entry,
the liver, the kidneys, and the urine are the only parts likely to be of
any use. Dragendorff recommends the extraction of the tissues with
water feebly acidulated with a mineral acid, to precipitate albuminous
matters, etc., by strong alcohol, and the separation, by means of benzene,
of fatty matters. The liquid is then made alkaline, and shaken up with
petroleum ether, which removes certain alkaloidal matters. It is now
evaporated to dryness, mixed with finely-powdered glass, and extracted
with absolute alcohol. The alcohol is evaporated to dryness, and any
curarine extracted from this residue with water. By very careful
drying up of this last extract, and taking it up in alcohol, the alkaloid
is said to be obtained so pure as to respond to chemical tests. The
identification may be by the colour reaction of sulphuric acid described
ante, in all cases supplemented by its physiological action on frogs.f
* Arch. f. Amat. w. Physiol., 1879, p. 598.
+ It is known that curare may cause slight symptoms of excitation before the
paralysis comes on. M. Couty has succeeded in isolating these symptoms by
employing feeble extracts of Strychnos triplinervia, or small doses of certain native
preparations. By these means, in dogs, a new phase of intoxication may be present
for ten or even twenty minutes. In the first instance the animal is agitated, jump-
§ 507, 508.] COLCHICINE. 42 I
XII. —Colchicine.
§ 507. The whole of the Colchicum autumnale, or common meadow-
saffron, is poisonous, owing to the presence of an alkaloid (discovered by
Pelletier and Caventou) called Colchicine.
According to Johannson's experiments, the dried colchicum seeds
contain 1:15 per cent. of colchicine; the leaves, 1.459 per cent. ; the
bulbs, from 1:4 to 1:58 per cent. ; and the roots, 0-634 per cent. The
frequent poisoning of cattle in the autumn by colchicum, its use in
quack pills for rheumatism, and its supposed occasional presence in
beer, give it an analytical importance. .
§ 508. Colchicine (C23H, NOs) may be extracted from the seeds, etc.,
in the manner recommended by Hübler —The seeds are treated, without
crushing, by hot 90 per cent. alcohol, and the alcoholic solution evapo-
rated to a syrup, which is diluted with twenty times its bulk of water
and filtered ; the liquid is next treated with acetate of lead, again filtered,
and the lead thrown out by phosphate of soda. Colchicine is now pre-
cipitated as a tannate.* The precipitation is best fractional, the first
and last portions being rejected as containing impurities. The tan-
nate is decomposed in the usual way with litharge and extracted by
alcohol.
A simpler method is, however, extraction by chloroform from an
aqueous solution, feebly acidified, as recommended by Dragendorff.
ing, scratching, barking, as if in a state of general hyperaesthesia. Then it presents
half choreic shocks or tremors; the pupils dilate, and are alternately dilated and
contracted. The heart's action is increased or diminished in frequency; sometimes
there is vomiting, micturition, or defecation ; and there is always salivation. Finally,
the central and peripheral temperatures are raised, and the excitability of the muscles
and nerves becomes highly increased. With the native preparation of curare, it is
impossible to prolong this stage, and symptoms of paralysis soon become associated
with those of excitement. The choreic shocks were found to be arrested by section
of the sciatic nerve. Other experiments proved that the spasms originated from the
spinal cord, and were influenced by its preceding functional condition. If the cord
was tied in the mid-dorsal region, and the curare injected, the spasms were still pro-
duced in the hind legs; but if, after the operation, the excitability of the posterior
segment became lowered, the spasm was no longer produced in the hind legs. This
dependence on a perfect functional activity is a point of difference of these spasms
from those produced by strychnine, and by asphyxia. The action of small doses of
curare is not, however, limited to the spinal cord. The diminished frequency of the
heart continues after section of the pneumogastrics, and will even occur if the
pneumogastrics have been previously divided. From these facts M. Couty considers
that curare must not be regarded as entirely destitute of a “convulsant’ action,
nor of an action on the central nervous system.
* The purest tannic acid must be used. The commercial tannin may be purified
by evaporating to dryness with litharge, exhausting the tannate of lead repeatedly
with boiling alcohol and water, and, lastly, suspending in water, and separating the
lead by SH3.
422 POIsons: THEIR EFFECTS AND DETECTION. [$ 509, 5 IO.
The parts of the plant are digested in very dilute acid water, and the
resulting solution concentrated and shaken up with chloroform, which is
best done in a separating tube.
Colchicine contains four methoxyl groups, and its constitutional
formula is considered to be C.H.INH(CH3CO)](COOCHA)(OCH3)s.
Its melting-point is 143°–147°. It is usually a white, gummy mass.
It is easily soluble in cold water, in alcohol, and in chloroform. The
solutions are lavorotatory. It is hardly soluble in ether. Boiling with
dilute acids or alkalies in closed tubes yields colchiceine, Cal HosnO6.
Colchiceine contains three methoxyl groups. It crystallises with one
molecule of water and melts at 140”; when anhydrous it melts at 172".
It dissolves but little in cold, copiously in boiling water. Colchiceine is
a monobasic acid, forming salts with the alkalies, and colchicine is its
methyl ester.
Zeisel” has formed acetotrimethylcolchicinamide (NHAcC15H2(OMe),
CONH2) by heating colchicine with alcoholic ammonia in closed tubes
for four hours at 100°. The amide is crystallised from hot alcohol; it is
readily soluble in dilute HCl, almost insoluble in water; when a strong
hydrochloric acid solution of the amide is treated with a small amount of
potassium nitrite a splendid violet colour is produced.
§ 509. Tests.—Ferric chloride, if added to an alcoholic solution of
the alkaloid, strikes a garnet-red; if to an aqueous solution a green or
brownish-green ; nitric acid added to the solid substance gives a violet
colour. Erdmann's reagent (nitrosulphuric acid) gives in succession
green, dark blue, and violet colours, ultimately turning yellow, changed,
on addition of an alkali, to raspberry-red. Mandelin's reagent (1 grm.
of ammonium vanadate in 200 grns. of sulphuric acid) gives a green
colour.
§ 510. Pharmaceutical Preparations.—Colchicine itself is officinal in
Austria—the wine in the British, French, and Dutch, and the seeds
themselves in all the pharmacopoeias. The wine of colchicum, officinal
in nearly all the pharmacopoeias, is made with very different proportions
of seeds or bulbs.
The tincture of colchicum is officinal in our own and in all the
Continental pharmacopoeias; in the British, one part of seeds is exhausted
by eight parts of proof spirit.
A tincture of colchicum seeds, examined by Johannson, contained
‘18 per cent. of colchicine, and a tincture prepared from the bulbs 14
per cent.
Colchicum vinegar is not officinal in Britain, but one containing 5-4.
per cent. of acetic acid is so in the Netherlands, Germany, and France;
the strength appears to be about 095 per cent. of colchicine.
* Momalsh., ix. 1–30.
§ 51 1, 512.] - COLCHICINE. 423
An extract of colchicum is officinal in Britain and France; and an
acetic extract in Britain. The latter is the most active of all the
pharmaceutical preparations of colchicum. .
Lastly, an oxymel of colchicum is in use in Germany, France, and
the Netherlands,
Quack and Patent Medicines.—In all specifics for gout the analyst
will naturally search for colchicum. Most gout pills contain the extracts;
and liquids, such as “Reynolds’ gout specific,” the wine or the tincture,
variously flavoured and disguised.
The strength of the different pharmaceutical preparations may be
ascertained by dissolving in chloroform, evaporating off the chloroform,
dissolving in water (which is finally acidified by from 7 to 10 per cent.
of sulphuric acid), and titrating with Mayer's reagent (see p. 264). If
the solution is diluted so that there is about 1 part of colchicine in
600 of the solution, then each c.c. of Mayer's reagent equals 31.7 mgrms.
colohicine.
§ 511. Fatal Dose.—In Taylor's Principles of Medical Jurisprudence
is mentioned an instance in which 3% drachms of colchicum wine, taken
in divided doses, caused death on the fourth day. The quantity of
the active principle in the colchicum wine, as found by Johannson
(Dragendorff), being 0-18 per cent., it follows that 24.4 mgrims. (.378
grain) were fatal, though not given as one dose, so that this quantity may
be considered as the least fatal one. Casper puts the lethal dose of
colchicine at from 25 to 30 mgrms. (.385 to 463 grain). It is, however,
incontestable that there are cases of recovery from as much as 70 mgroms.
(1-08 grain). The lethal dose of the pharmaceutical preparations of
colchicum may, on these grounds, be predicted from their alkaloidal con-
tents, and, since the latter is not constant, in any medico-legal inquiry,
it may be necessary, where facility is given, to ascertain the strength of
the preparation administered. -
§ 512. Effects of Colchicine on Animals. – The researches of
Rossbach show that the carnivorae are more sensitive to colchicine
than any other order of mammals. Frogs show a transitory excite-
ment of the nervous system, then there is loss of sensation, paralysis
of motion, and of the respiratory apparatus; the heart beats after
the respiration has ceased. Death follows from paralysis of the
respiration. The mucous membrane of the intestine is much congested
and swollen.
The senior author has seen cattle die from the effects of eating the
meadow-saffron; the animals rapidly lose condition, suffer great abdominal
pain, and are generally purged. The farmers, in certain parts of the
country, have had extensive losses from want of care and knowledge
with regard to colchicum poisoning.
424 Poisons: THEIR EFFECTS AND DETECTION. [$ 513.
§ 513. Effects of Colchicine on Man.-Colchicine poisoning in man*
is not very common: 2 deaths (accidental) are recorded in England and
Wales during the ten years ending 1892, and a single death is also
recorded in the Registrar-General's returns for 1896. F. A. Falck was
able to collect from medical literature, prior to 1880, 55 cases, and he
gives the following analysis of the cases:–In 2, colchicum was taken
for suicidal purposes; of the unintentional poisonings, 5 were from too
large a medicinal dose of colchicum wine, syrup, or extract, given in
cases of rheumatism ; in 13 cases, colchicum was used as a purgative ;
42 cases were owing to mistaking different preparations for drinks, or
cordials—the tincture in 5, and the wine in 14, being taken instead of
orange tincture, quinine wine, Schnapps or Madeira; in 1 case the corms
were added to mulled wine, in another, the leaves consumed with salad ,
in 16 cases (all children), the seeds of colchicum were eaten. Forty-six
of the 55 died—that is, 83-7 per cent.
In the remarkable trial at the Central Criminal Court, in 1862, of
Margaret Wilson (Reg. v. Marg. Wilson), who was convicted of the
murder of a Mrs. Somers, the evidence given rendered it fairly probable
that the prisoner had destroyed four people at different dates by colchi-
cum. The symptoms in all four cases were—burning pain in the throat
and stomach, intense thirst, violent vomiting and purging, coldness and
clamminess of the skin, excessive depression, and great weakness. One
victim died on the second day, another on the fifth, a third on the eighth,
and the fourth on the fourteenth day. Schroff witnessed a case in which
a man took 2 grims. (nearly 31 grains) of the corms; in one and a half
hours he experienced general malaise; on the next day there were flying
muscular pains, which at length were concentrated in the diaphragm,
and the breathing became oppressed; there was also pain in the neigh-
bourhood of the duodenum, the abdomen was inflated with gas; there
was a sickly feeling and faintness. Then came on a sleepy condition,
lasting several hours, followed by fever, with excessive pain in the head,
noises in the ears, and delirium ; there was complete recovery, but the
abdomen continued painful until the fifth day.
In another instance, a gentleman, aged 50,i had taken twenty-eight
of Blair's gout-pills in four and a half days for the relief of a rheumatic
affection. He suffered from nausea, griping pains in the belly, consider-
able diarrhoea, vomiting, and hiccough ; towards the end there was
stupor, convulsive twitchings of the muscles, paralysis, and death. The
fatal illness lasted fourteen days; he was seen by three medical men at
different dates—the first seems to have considered the case one of
* For the curious epidemic of diarrhoea which broke out in the Rhone Gorge in
1785, and was referred to colchicine, see “Foods,” p. 248, 5th edition.
+ Sce Lancel, 1881, vol. i. p. 368.
§ 514, 515.] - COLCHICINE. 425
diarrhoea, the second one of suppressed gout ; but Dr. C. Budd was
struck with the similarity of the symptoms to those from an acrid
poison, and discovered the fact that the pills had been taken. These
pills were examined by the senior author; they were excessively hard,
and practically consisted of nothing else than the finely-ground colchicum
corms; six pills yielded 8 mgrms. of colchicine, so that the whole twenty-
eight would contain 39 mgrms. (# grain). Dr. Budd considered that the
whole of the pills, which were of a stony hardness, remained in the
bowels for some time undigested, so that the ultimate result was the
same as if the whole had been taken in one dose.
§ 514. The general symptoms produced by colchicum are—more or
less burning pain in the whole intestinal tract, vomiting, diarrhoea, with
not unfrequently bloody stools; but sometimes diarrhoea is absent. In
single cases tenesmus, dysuria, and, in one case, haematuria have been
noted. The respiration is usually troubled, the heart's action slowed,
the pulse small and weak, and the temperature sinks. In a few cases
there have been pains in the limbs; cerebral disturbance is rare; but in
two cases (one described ante) there was stupor. Muscular weakness
has been observed generally. In a few cases there have been cramps in
the calves and in the foot, with early collapse and death.
Post-mortem. Appearances.—Schroff found in rabbits poisoned with
from 0-1 to 1-0 grnm. of colchicine, tolerably constantly enteritis and
gastritis, and always a thick, pitch-like blood in the heart and veins.
Casper has carefully recorded the post-mortem appearances in four
labourers, ages ranging from fifteen to forty years, who, finding a bottle
of colchicum-wine, and supposing it to be some kind of brandy, each
drank a wine-glassful. They all died from its effects. In all four there
was great hyperamia of the brain membranes and of the kidneys. The
large veins were filled with thick, dark, cherry-red blood, very similar to
that seen in sulphuric acid poisoning. There was an acid reaction of
the contents of the stomach. The lungs were moderately congested.
The mucous membrane of the stomach of the one who died first was
swollen and scarlet with congestion ; with the second there was some
filling of the vessels at the small curvature; while the stomachs of the
third and fourth were quite normal. In 5 cases described by Roux
there was also hyperamia of the brain and kidneys, but no gastritis or
enteritis. It is, therefore, evident that there are in man no constant
pathological changes from colchicine poisoning.
§ 515. Separation of Colchicine from Organic Matters.—W.
Obolonski “ has recommended the following process:–The finely divided
viscera are triturated with powdered glass and digested for twelve
hours with alcohol. The liquid is squeezed out and the dry residue
* Zeit. amal. Chem..., xxix. 493.
426 POISONS : THEIR EFFECTS AND DETECTION. [$ 516.
washed with alcohol. The extract is concentrated at a temperature not
exceeding 80°, and the cooled residue made up to the original volume
with alcohol. The filtered liquid is evaporated as before, and this opera-
tion repeated until no more clots separate on addition of water. The
residue is then dissolved in water, the solution purified by shaking with
light petroleum, and the colchicine finally extracted with chloroform.
In cases of poisoning by colchicum at Berlin, Wittstock used the
following process:–The contents of the stomach were mixed with a
large amount of alcohol, a few drops of HCl added, and the whole
well shaken ; the fluid was then filtered, and the filtrate evaporated to
a syrupy consistence at 37°. The resulting residue was dissolved in
distilled water, the fat, etc., filtered off, and the liquid carefully evapo-
rated. From the extract foreign matter was again separated by treatment
with alcohol and filtration, and the last filtrate was evaporated to a syrupy
consistence. The syrupy fluid was taken up by distilled water, filtered,
evaporated to 30 grns., and 2 grns. of calcined magnesia, with 90 grms.
of ether were added. After a time, the ether was removed, and allowed
to evaporate spontaneously. The residue was once more taken up with
water, filtered from fat, etc., and evaporated. This final residue gave
all the reactions of colchicine. In medico-legal researches, it must be
remembered that colchicine is absorbed but slowly, a not insignificant
portion remaining in the bowels, with the faeces.
XIII.-Muscarine and the Active Principles of Certain Fungi.
§ 516. The Amanita Muscaria, or fly-blown agaric, is a very con-
spicuous fungus, common in fir-plantations, about the size and shape of
the common mushroom ; but the external surface of the pileus is of a
bright red, or sometimes of a yellowish cast, and studded over with
warts. The common name of the fungus denotes that it was used in
former times as a popular insecticide ; the fungus was bruised, steeped
in milk, and the milk exposed, in the same way as we now expose
arsenical fly-papers. .
Some peculiar properties of the agaric have long been known to the
natives of Kamschatka, and of the north-eastern part of Asia generally.
They collect the fungi in the hottest months, and hang them up to dry.
The fungus is then rolled up in a kind of bolus, and swallowed without
chewing. One large, or two small, fungi will produce a kind of intoxi-
cation, which lasts a whole day. It comes on in about two hours' time,
and is very similar to that of alcohol. There is a giddy feeling, the
spirits are exalted, the countenance becomes flushed, involuntary actions
§ 517, 518.] MUSCARINE. 427
and words follow, and sometimes loss of consciousness. It renders some
persons remarkably active, and proves highly stimulant to muscular exer-
tion; by too large a dose violent spasmodic effects are produced. “So
very exciting to the nervous system in many individuals is this fungus,
that the effects are often very ludicrous. If a person under its influence
wishes to step over a straw or small stick, he takes a stride or a jump
sufficient to clear the trunk of a tree. A talkative person cannot keep
silence or secrets, and one fond of music is perpetually singing. The
most singular effect of the amanita is the influence which it has over the
urine. It is said that from time immemorial the inhabitants have known
that the fungus imparts an intoxicating quality to that secretion, which
continues for a considerable time after taking it. For instance, a man
moderately intoxicated to-day will, by the next morning, have slept
himself sober, but (as is the custom) by taking a teacup of his urine
he will be more powerfully intoxicated than he was the preceding day.
It is, therefore, not uncommon for confirmed drunkards to preserve their
urine as a precious liquor against a scarcity of the fungus. The intoxi-
cating property of the urine is capable of being propagated ; for every
one who partakes of it has his urine similarly affected. Thus, with a
very few amanitas, a party of drunkards may keep up their debauch for
a week. Dr. Langsdorf mentions that by means of the second person
taking the urine of the first, the third of the second, and so on, the
intoxication may be propagated through five individuals.””
§ 517. A few cases of poisoning by the fly-blown agaric from time to
time have occurred in Europe, where it has been eaten in mistake for the
edible fungi, or taken by children allured by the bright attractive colours.
In these cases the poisonous symptoms noticed have been those of gastro-
intestinal irritation, as shown by vomiting and diarrhoea, dilated f pupils,
delirium, tetanic convulsions, slow pulse, stertorous breathing, collapse,
and death. In a few cases epileptic attacks and trismus have been
observed. The course is usually a rapid one, the death occurring within
twelve hours. In cases of recovery, convalescence has been prolonged.
The post-mortem characteristics are not distinctive, a fluid con-
dition of the blood, hyperamia of the brain, liver, and kidneys have been
noticed.
§ 518. Muscarine. —These effects are partly due to an undiscovered,
toxic substance—which seems to be destroyed at the temperature of
boiling water, and is probably of rather easy destructibility—and of a
very definite poisonous alkaloid (muscarine) first separated by a complex
* Lindley’s Vegetable Kingdom.
+ This is the more curious, for muscarine strongly contracts the pupil. It, how-
ever, tends to prove what is stated in the text—viz., that there is more than one
poisonous substance in Amanita.
428 POISONS : THEIR EFFECTS AND DETECTION. [$ 519.
process by Schmiedeberg and Koppe in 1869.” It is a trimethyl-
ammonium base. Fischer has prepared a base very similar, but not
identical, with muscarine; the base on oxidation yielded betaine.
Schmiedeberg and Harmack,t by oxidation of choline with nitric
acid, obtained a base also very similar, but not identical, with natural
muscarine :—
/CH, —CH2 – OH CH, -CH(OH),
+ O—-(CH.). EN
NoH >(CH3)3 NoH
Choline. Muscarine (?).
(CH3)4=N
The true constitution of muscarine has not yet been determined.
Muscarine is a colourless, strongly alkaline, syrupy fluid, which, if
allowed to stand over sulphuric acid, becomes gradually crystalline, but
liquefies again on exposure to the atmosphere. It dissolves in water in
every proportion, and also in alcohol, but is very little soluble in chloro-
form, and insoluble in ether. It is not precipitated by tannin: it forms
Salts with acids, and gives precipitates with auric chloride, phospho-
tungstic, and phosphomolybdic acids, and also with potassio-mercuric
iodide. The last precipitate is at first amorphous, but it gradually
becomes crystalline. This was the compound used by the discoverers
to separate the base. With many other general alkaloidal reagents
muscarine forms no compound that is insoluble, and therefore gives no
precipitate, such, e.g., as iodine with potassic iodide, picric acid, and
platinic chloride. Muscarine is a stronger base than ammonia, and
precipitates copper and iron oxides from solutions of their salts. Mus-
carine is very poisonous; 2 to 4 mgrms. are sufficient in subcutaneous
injection to kill cats in from two to twelve hours—larger doses in a
few minutes; but with rabbits the action is less intense. Cats become
salivated, their pupils contract, they vomit, and are purged, the breathing
becomes frequent, and there is marked dyspnoea. At a later stage the
respirations are slower, and there are convulsions, and death.
The alkaloid has also been tried on man. Doses of from 3 to 5
mgrms., injected subcutaneously, cause, after a few minutes' profuse
salivation, increased frequency of the pulse, nausea, giddiness, confusion
of thought and myosis, but no vomiting, and no diarrhoea. Small
quantities applied to the eye cause, after a few minutes, a derangement
of the accommodation, but no change in the size, of the pupil; larger
quantities cause also myosis, which depends upon an excitement of the
sphincter iridis, or of the oculomotorius.
§ 519. The actions of muscarine and atropine are to a great extent
antagonistic. This is especially and beautifully demonstrated by the
* Das Muscarin, das giftige Alkaloid des Fliegempilzes. Leipzig, 1869.
| Arch. f. exper. Path., Bd. iv. u. v.
§ 52O, 52 I.] MUSCARINE. - - 429
effects of the two substances on the frog's heart. The action of muscarine
upon the heart is to excite the inhibitory nerve apparatus, while the
action of atropine is to paralyse the same system. One mgrm. of mus-
carine, injected subcutaneously into a frog, arrests the heart in diastole,
but if a suitable dose of atropine is applied to the heart thus arrested,
it begins to beat again; or, if atropine is first given, and then muscarine,
the heart does not stop. The muscarine heart, when it has ceased to
beat, may be successfully stimulated by galvanism. Muscarine at first
excites the respiratory centre, and then paralyses it.
§ 520. Detection of Muscarine in the Body.—Muscarine itself is
not likely to be taken as a poison or administered ; but if it is sought
for in the fly-blown agaric, or in the tissues or organs of persons who
have been poisoned by the fungus, the process of Brieger appears the
best. The process depends upon the fact that muscarine gives a soluble
mercuric chloride compound, and is not precipitated by chloride of
platinum, whilst most other substances accompanying it give more or
less insoluble precipitates. The substances are treated with water
acidulated with hydrochloric acid, and the acidulated extract concentrated
(best in a vacuum) to a syrup. The syrupy residue is now treated with
water, and the solution precipitated by means of mercuric chloride
solution and any precipitate filtered off; the filtrate is freed from
mercury by SH2, and evaporated to a syrup; the syrup is repeatedly
extracted with alcohol, and the alcoholic solution precipitated with
platinum chloride and any precipitate filtered off. The filtrate is freed
from alcohol, and all the platinum thrown out of solution by SH, ; the
aqueous filtrate is now concentrated to a small volume, and again
platinum chloride added, any precipitate which forms is filtered off, and
the final filtrate allowed to crystallise. If muscarine be present, a
crystalline compound of muscarine platinum chloride will form.
The crystals are usually octahedral in form, and have the composition
(C.H.I.N.O.,Cl), PtCl, ; the percentage of platinum is 30-41.
It would probably be necessary to identify farther, by the action of
the poison on a frog.
§ 521. The Agaricus phalloides, a common autumn fungus, has been
several times mistaken for mushrooms, and has proved fatal; of some
53 cases collected by Falck, no less than 40, or 75 per cent., were
fatal; the real mortality is much lower than this, for it is only such
cases that are pronounced and severe which are likely to be recorded.
The fungus contains a toxalbumin which has been named “phallin.”
The action of this toxalbumin is to dissolve the blood corpuscles; ac-
cording to Kobert, even one 250,000th dilution produces “polycholie”
with all its consequences, such as the escape of haemoglobin and its
decomposition products in the blood and urine, multiple blood coagula-
43O POISONs: THEIR EFFECTS AND DETECTION. [$ 522, 523.
tion through the fibrin ferment becoming free, and serious cerebral
disturbance. If into a dog, cat, or rabbit, only 0.5 mgrm. of phallin be
injected intravenously, within from twenty to thirty minutes blood
from a vein shows that the serum has a red colour.
The symptoms in man first appear in from three to forty-eight hours;
there is mostly diarrhoea, violent vomiting, with cramp in the legs,
cyanosis, and collapse. There are also nervous phenomena, convulsions,
trismus, and, in a few cases, tetanic spasms. The pulse, in seven cases
described by Maschka, was very small, thready, and quick, but in others,
again, small and slow. The pupils have in some cases been dilated, in
others unchanged. Death is generally rapid. In two of Maschka's
cases from sixty to sixty-eight hours after the investigation, but in the
rest from twelve to eighteen hours. Life may, however, be prolonged
for several days. In a case recorded by Plowright,” in which a boy
had eaten a piece of the pileus, death occurred on the fourth day.
§ 522. The post-mortem appearances observed in Maschka's seven
cases were—absence of cadaveric rigidity, dilatation of the pupil, a dark
red fluid condition of the blood, numerous ecchymoses in the pleura, in
the substance of the lungs, the pericardium, the substance of the heart,
the liver, kidneys, and spleen. The mucous membrane of the digestive
canal presented nothing characteristic. In two cases there were a few
ecchymoses, and in one the mucous membrane of the stomach was
softened, red, and easily detached. In one case only were any remnants
of the fungus found, by which the nature of the substance eaten could
be determined. The bladder in each case Was full. In three cases a
fatty degeneration of the liver had commenced. The same appearance
was met with in some of the older cases related by Orfila.
§ 523. The Agaricus pantherinus is said to be poisonous, although
Hertwig found it to have no action when given to dogs.
The Agaricus ruber, a bright-hued fungus, growing profusely on
the Hampshire coast, of a purple-red colour—the colouring-matter
not only covering the pileus, but also extending down the stipe—is
poisonous, and has been chemically investigated by Phipson,t who has
identified a colouring-matter ruberine, and an alkaloid agarythrine.
Agarythrine is separated by macerating the fungus (from which the
skin containing the colouring-matter has been removed) as completely as
possible in water acidulated with 8 per cent. of hydrochloric acid. The
filtered solution is neutralised by sodic carbonate, and the alkaloid
shaken np with ether. On evaporation the ether leaves a white, some-
what greasy-looking substance, having a bitter burning taste, and easily
fusible into yellow globules, giving forth an odour like quinoleine; it
is soluble in alcohol and ether. From Phipson's observations it would
* Lancet, 1879. f Chem. News, p. 199, 1882.
§ 524–526.] - DIGITALIS GROUP. 43 I
appear probable that the red colouring-matter is derived from a decom-
position of this alkaloidal substance. A rose-red colour is produced by
the action of nitric acid, and chlorinated lime first reddens and then
bleaches it. Buchwald” has recorded three cases of poisoning by this
fungus; the patients were labourers, who, after eating the fungus,
suffered from vomiting, thirst, a “drunken” condition, cramp, albu-
minuria, and disturbance of the sensory functions. The fungus causes
in cats myosis, but is said not to affect rabbits.
§ 524. The Boletus Satanas, or luridus (Lenz), is poisonous; very
small quantities of the uncooked fungus caused in Lenz, who experi-
mented upon its properties, violent vomiting. In cases in which this
fungus has been eaten accidentally, the symptoms have been very similar
to cholera.
§ 525. The Common Morelle seems under certain conditions to be
poisonous. From six to ten hours after ingestion there have appeared
depression, nausea, jaundice, dilated pupils, and in the worst cases at the
end of the first day, delirium, somnolence, and muscular cramps, followed
by collapse and death. In a case observed by Kromholz, the post-
mortem appearances were jaundice, a dark fluid state of the blood, and
hyperamia of the brain and liver. Boström fed a dog with 100 grims.
of the fresh young morelle; the animal died on the third day, and the
canaliculi of the kidney were found filled with the haemoglobin, partly
amorphous, and partly crystalline.t
DIVISION II.-GLUCOSIDES.
I.—Digitalis Group.
§ 526. The Digitalis purpurea, or foxglove, is a plant extremely
common in most parts of England, and poisoning may occur from the
accidental use of the root, leaves, or seeds. The seeds are very small
and pitted ; they weigh 1126 to a grain (Guy), are of a light brown
colour, and in form somewhat egg-shaped. The leaves are large, ovate,
crenate, narrowed at the base, rugous, veined, and downy, especially on
the under surface. Their colour is a dull green, and they have a faint
odour and a bitter, nauseous taste. The leaf is best examined in section.
* Industr. Bl., 1876.
t See Casper's Viertelj., 1844; Keber, Preuss. Vereinszeitg., 1846; Boström,
Ber, d. Phys. Med. Soc., Erlangen, 1880; Schauenstein, “Giftige Schwämme” in
Maschka's Handbuch, etc.
432 POISONS: THEIR EFFECTS AND DETECTION. [$ 527–530.
Its epidermis, when fresh, is seen to consist of transparent, hexagonal,
colourless cells, beneath which, either singly or in groups, there are
round cells of a magenta tint, and beneath these again a layer of
columnar cells, and near the lower surface a loose parenchyma. The
hairs are simple, appearing scantily on the upper, but profusely on the
lower, surface; each is composed of from four to five joints or cells, and
has at its base a magenta-coloured cell. The small leaves just below the
seed-case, and the latter itself, are studded with glandular hairs. The
root consists of numerous long slender fibres.
§ 527. Chemical Composition.—It is now generally accepted that
there exist in the foxglove, at least, four distinct principles—digitalin,
digitonin, digitoxin, and digitalein. Besides these there are several
others of more or less definite composition, which are are all closely
related, and may be derived from a complex glucoside by successive
removals of hydrogen in the form of water. -
§ 528. Digitalein is a colourless, amorphous body, probably a mixture easily
soluble in water and in cold absolute alcohol. It may be precipitated from an
alcoholic solution by the addition of much ether. It is with difficulty soluble in
chloroform, and insoluble in ether. It is precipitated from a watery solution by
tannin, or by basic lead acetate ; Saponification by dilute acids splits it up into
glucose and digitaleretin. It has a sharp, acrid taste, and the watery solution froths
on shaking.
§ 529. Digitonin may be obtained in crystals by treating German digitalin with
water, adding alcohol to the solution, and then shaking with ether; after a time
crystals separate, CºsłII,014+ H2O ; the crystals are easily soluble in hot water or
alcohol; with warm concentrated HCl it forms a yellow solution which quickly
becomes green ; it is precipitated by tannic acid, lead acetate, and ammonia, but not
by magnesic nor ammonium sulphate. Schmiedeberg's amorphous and Kiliani's
crsytalline digitonin are, according to Cloetta,” different substances; on the other
hand, Kiliani (Arch. Pharm., 1905, coxliii.) thinks Cloetta's compound is a mixture,
and that it cannot be represented by such a simple formula as Cºsłła,014.
Digitogenin is insoluble in water and aqueous alkalies; it is somewhat
soluble in alcohol, chloroform, and glacial acetic acid; it forms a crystal-
line compound with alcoholic potash, which is strongly alkaline, and not
very soluble in alcohol. -
$ 530. Digitalin, Cash;6014, when perfectly pure, forms fine, white,
glittering, hygroscopic needles, or groups of crystalline tufts; it is
without smell, but possesses a bitter taste, which is at once of slow
development and of long endurance. On warming, it becomes soft
under 100°, and, above that temperature, is readily decomposed with
evolution of white vapours. It is insoluble in water, in dilute soda
solution, in ether, and in benzene. It is soluble in chloroform, especially
in chloroform and alcohol, and dissolves easily in warm acetic acid;
twelve parts of cold and six of boiling alcohol of 90 per cent, dissolve
* Cloetta, Max, Arch. fr. eaſp. Pharm., 1901. -
§ 531–532A] DIGITALIS GROUP. 433
one of digitalin. On hydrolysis it yields digitalose * C.H.I.O.. Con-
centrated sulphuric acid dissolves it with the production of a green
colour, which by bromine passes into violet-red, but on the addition
of water becomes green again. Hydrochloric acid dissolves it with the
production of a greyish-yellow colour, passing gradually into emerald
green; water precipitates from this solution a resinous mass.
§ 531. Digitaletin.—A substance obtained by Walz on treating his digitalin by
dilute acids. It is crystalline, and its watery solution tastes bitter. It melts at
175°, and decomposes, evolving an acid vapour at about 206°. It dissolves in 848
parts of cold, and 222 of boiling, water; in 3-5 parts of cold, and in from 2 to 4 of
boiling, alcohol. It is with difficulty soluble in ether. It dissolves in concentrated
sulphuric acid, developing a red-brown colour, which, on the addition of water,
changes to olive-green. On boiling with dilute acids, it splits up into sugar and
digitaleretin.
§ 532. Digitoxin, Cs1H:0016 (according to H. Kiliani, C.H. On),
is considered the most active poisonous constituent of digitalis leaves;
although the experiments of Hans Ziegenbein (Arch. Pharm., 1902), on
the heart of a frog, with extracts from dried leaves in which the con-
tent of digitoxin was ascertained, show that such extracts are far more
toxic than could be predicated from the amount of digitoxin found.
Similar facts may be shown as to muscarine and other extracts containing
alkaloids; associated glucosides or, possibly, unknown toxines heightening
the toxic effect.
§ 532A. Separation of Digitoxin from Organic Matters.--Digitoxin
may be estimated by Keller'st method, which is as follows:—Twenty grims.
of the powdered leaves are exhausted by percolation with 300 c.c. of 70 per
cent. alcohol, and the alcohol got rid of by evaporating down in a porcelain
dish on the water-bath to about 25 grns. ; the residue is taken up with
water until the weight is brought up to 222 grims. To the turbid
solution 25 grms. of lead acetate are added, which produce a copious
precipitate. The thick liquid is transferred to a filter 10 c.m. diameter,
and 132 grms. filtered through. To the clear filtrate, 5 grims. of sodium
hyposulphite dissolved in 7 grns. of water are added to precipitate the
excess of lead. The lead precipitate is separated by filtration, 2 c.c. of
10 per cent. ammonia solution added, and the liquid transferred to a
separating funnel and shaken out four or five times with chloroform. The
chloroformic extract is filtered through a double filter previously soaked
by chloroform, and obtained in this way clear. On distilling the chloro-
form, the digitoxin is obtained as a yellow varnish. It is dissolved in
3 grns, of chloroform, and precipitated in flocks by 7 grms. of ether
and 50 grims, petroleum ether. The precipitate is collected in a small
filter, and washed with petroleum ether. The residue, still moist, is
dissolved in hot absolute alcohol, the alcoholic solution evaporated, the
* H. Kiliani, Ber. 1898, xxxi. i Zeit. f. Amal. Chem., 1900, 257.
28
434 POISONS: THEIR EFFECTS AND DETECTION. [$ 533–536.
residue treated with 5 c.c. of ether and allowed to evaporate in the
water-bath; it now becomes partly crystalline and may be completely
dried and then weighed. -
Dioscoride Vitali (Chem. Centr., 1900) isolates digitoxin from the
tissues by extracting with dilute alcohol, evaporating the alcoholic
extract to a small bulk; the residual liquid is treated with lead acetate,
and then with sodic sulphate to get rid of the excess of lead; after
filtration the filtrate is alkalised as in the previous process with ammonia,
and shaken with chloroform ; the chloroform extract may be treated as
in Keller's process.
On hydrolising with alcoholic soda digitoxin breaks up into digi-
toxegenin, Cog HsiO4H, and digitoxose, CoFilsog, thus:—
Cs1H500,0=CoHisO3 + C23H3304.
§ 533. Digitaleretin, a decomposition product of digitalin, is a yellowish-white
amorphous powder, possessing no bitter taste, melting at 60°, soluble in ether or in
alcohol, but insoluble in water.
Paradigitaletin is very similar to the above, but it melts at 100°, and is insoluble
in ether.
§ 534. Several other derivatives have been obtained and described,
such as the inert digitim, digitalacrin, digitalein, and others, but their
properties are, as yet, insufficiently studied.
§ 535. Reactions of the Digitalins.—0-01 grm. of digitonin dissolved
in 5 c.c. of HCl (sp. gr. 1:19) and heated on the water-bath gives a
liquid, at first yellow, then deep red and finally dark blue. This re-
action thus serves to distinguish digitonin from the three other con-
stituents, as well as from saponin ; but digitalin gives somewhat similar
reactions.
Sulphuric and gallic acids colour the glucosides of digitalin, digitalein,
and digitonin, red, but not digitoxin, which can be identified in this
way.
Sulphuric acid and bromine give with digitalin a red, and with digi-
talein a violet coloration, which, on the addition of water, change re-
spectively into emerald and light green. This, the most important
chemical test we possess, is sometimes called Grandeau's test ; it is not
of great delicacy, the limit being about 0.1 mgrm.
§ 536. Pharmaceutical Preparations of Digitalin.—Digitalin itself
is officinal in the French, Belgium, Portuguese, Russian, Spanish, and
Austrian pharmacopoeias. It is prepared in our own by making a strong
tinctºre of the leaves at 120° F.; the spirit is then evaporated off, and
the extract heated with acetic acid, decolorised by animal charcoal,
and filtered. After neutralisation with ammonia, the digitalin is pre-
cipitated with tannin, and the tannate of digitalin resolved into tannate
of lead and free digitalin, by rubbing it with oxide of lead and spirit.
§ 537.] DIGITALIS GROUP. 435
Digitalis leaf is officinal in most of the pharmacopoeias.
Tincture of digitalis is officinal in our own and all the Continental
pharmacopoeias, and an ethereal tincture is used in France and
Germany.
An Acetum digitalis is officinal in the Netherlands and Germany ;
an extract and infusion are also used to Some extent,
With regard to the nature of the active principle in these different
preparations, according to Dragendorff, digitonin and digitalein are
most plentiful in the acetic and aqueous preparations; whilst in the
alcoholic, digitalin, digitoxin, and digitalein are present.
According to Schmiedeberg, commercial digitalin contains, in
addition to digitoxin ; digitonin, digitalin, and digitalein; of these,
digitonin is greatest in amount.*
§ 537. Fatal Dose.—The circumstance of commercial digitalin con-
sisting of varying mixtures of digitoxin, digitalin, and digitalein, renders
it difficult to be dogmatic about the dose likely to destroy life. Besides,
with all heart-poisons, surprises take place; and very minute quantities
have a fatal result when administered to persons with disease of the
heart, or to such as, owing to some constitutional peculiarity, have a
heart easily affected by toxic agents. Digitoxin, according to Kopp'st
experiments, is from six to ten times stronger than digitalin or digitalein.
Two mgrms. caused intense poisonous symptoms. Digitoxin is con-
tained in larger proportions in Nativelle's digitalin than in Homolle's, or
in the German digitalin. The digitalin of Homolle is prescribed in
1 mgrm. (0.015 grain) doses, and it is thought dangerous to exceed 6
mgrms.
Lemaistre has, indeed, seen dangerous symptoms arise from 2 mgrms.
(0.03 grain), when administered to a boy fifteen years old. It may be
predicated from recorded cases and from experiment, that digitoxin
would probably be fatal to an adult man in doses of 4 mgrms. (Tº grain),
and digitalin, or digitalein, in doses of 20 mgrms. (0.3 grain). With
regard to commercial digitalin, as much as from 10 to 12 mgrms. (0.15
to 0-13 grain) have been taken without a fatal result ; on the other
hand, 2 mgrms. gave rise to poisonous symptoms in a woman (Battaille).
Such discrepancies are to be explained on the grounds already men-
tioned. It is, however, probable that 4 mgrims. (or ſº grain) of ordinary
commercial digitalin would be very dangerous to an adult.
It must also, in considering the dose of digitalin, be ever remembered
that it is a cumulative poison, and that the same dose, harmless, if taken
once, yet frequently repeated, becomes deadly : this peculiarity is
shared by all poisons affecting the heart. When it is desired to settle
* H. Kiliani, Ber., xxiii.
+ Archiv f. exp. Pathol. w. Pharm., vol. iii. p. 284, 1875.
436 POISONS: THEIR EFFECTS AND DETECTION. [$ 538, 539.
the maximum safe dose for the various tinctures, extracts, and infusions
of digitalis used in pharmacy, there is still greater difficulty—a difficulty
not arising merely from the varying strength of the preparations, but
also from the fact of the vomiting almost invariably excited by large
doses. Individuals swallow quantities without death resulting, simply
because the poison is rapidly expelled; whereas, if the oesophagus was
ligatured (as in the experiments on the lower animals formerly favoured
by the French school of toxicologists), death must rapidly ensue. The
following table is a guide to the maximum single dose, and also the
amount safe to administer in the twenty-four hours in divided doses.
As a general rule, it may be laid down that double the maximum dose is
likely to be dangerous:—
TABLE SHOWING THE MAXIMUM SINGLE DOSE, AND MAXIMUM
QUANTITY OF THE DIFFERENT PREPARATIONS OF DIGITALIS,
WHICH CAN BE ADMINISTERED IN A DAY.
Single Dose. Per Day.
Grains Or Grammes Grains or Grammes
Minins. Or C.C.'s. Minins. or c.c's.
Powdered Leaves, 4% grns. ‘3 grm. 15°4 grns. 1-0 grim.
Infusion, 480 m. 28'3 C. c. 1440 m. 84 °9 C. C.
Tincture, . 45 m. 3 c.c. 135 m. 9 c.c.
Digitalin, . * '03 grn. '002 grm. '09 grn. ‘006 grim.
Extract, . e - 3.0 , , •2 3 5 12-0 , , e 3 3
§ 538. Statistics.-The main knowledge which we possess of the
action of digitalis is derived from experiments on animals, and from
occasional accidents in the taking of medicines; but in comparison with
certain toxic agents more commonly known, the number of cases of
death from digitalis is very insignificant. Of 42 cases of digitalis-
poisoning collected by Husemann, 1 was criminal (murder); I the
result of mistaking the leaves for those of borage; 42 were caused in
medicinal use—in 33 of these last too large a dose had been given, in 3
the drug was used as a domestic remedy, il, 2 of the cases the prescrip-
tion was wrongly read, and in 1 digitalis was used as a secret remedy.
Twenty-two per cent. of the 45 were fatal.
§ 539. Effects on Man.—It was first distinctly pointed out by Tar-
dieu that toxic doses of digitalis, or its active principles, produced not
only symptoms referable to an action on the heart, but also, in no small
degree, gastric and intestinal irritation, similar to that produced by
arsenic. Tardieu also attempted to distinguish the symptoms produced
by the pharmaceutical preparations of digitalis (the tincture, extract,
§ 539.] DIGITALIS GROUP. 437
etc.), and the glucoside digitalin ; but there does not appear a sufficient
basis for this distinction. The symptoms vary in a considerable degree
in different persons, and are more or less tardy or rapid in their develop-
ment, according to the dose. Moderate doses continued for some time
(as, for example, in the persistent use of a digitalis medicine) may pro-
duce their first toxic effects even at the end of many days; but when a
single large dose is taken, the symptoms are rarely delayed more than
three hours. They may commence, indeed, in half an hour, but have
been known to be retarded for more than twenty-four hours, and the
longer periods may be expected if digitalis is given in hard, not easily
soluble pills. There is commonly a feeling of general malaise, and then
violent retching and vomiting. The pulse at first may be accelerated,
but it soon is remarkably slowed—it sinks commonly down to 50, to
40, and has even been known as low as 25. To these symptoms, refer-
able to the heart and to the digestive tract, are added nervous troubles;
there are noises in the ears, and disturbances of vision. In a case re-
lated by Taylor, a red-coal fire seemed to the patient to be of a blue
colour; in another, related by Lersch,” there was blindness for eighteen
hours, and for some time a confusion in the discrimination in colours;
quiet delirium has also been noticed. As the case proceeds, the gastric
symptoms also increase in severity ; the tongue Christison, in one case,
moticed to be enormously swollen, and the breath foetid. Diarrhoea is
commonly present, although also sometimes absent. The action of the
kidneys is suppressed. Hiccough and convulsions close the scene.
In the cumulative form, the symptoms may suddenly burst out, and
the person pass into death in a fainting-fit without any warning. As a
rare effect, hemiplegia may be mentioned.
This brief résumé of the symptoms may be further illustrated by the
following typical cases:—A recruit, aged 22, desiring to escape from
military service, went to a so-called “Freimacher,” who gave him 100
pills, of which he was to take eight in two doses daily, Eleven days
after the use of the pills, he became ill, and was received into hospital,
where he suddenly died after three weeks' treatment. His malady was
at first ascribed to gastric catarrh; for he suffered from loss of appetite,
nausea, and constipation. He complained of pain in the head, and
giddiness. His breath smelled badly, and the region of the stomach
was painful on pressure. The pulse was slow (56), the temperature of
the body normal. Towards the end, the pulse sank to 52; he suffered
from vomiting, noise in the ears, troubles of vision, great weakness, and
later, hiccough and swelling in the neck. The mere act of standing up
in order to show his throat caused him to faint ; on the same day on
which this occurrence took place, he suddenly died on the way to the
* Rhen. West, Corr. Bl., 15, 1848; Husemann in Maschka's Handbuch.
438 POISONS : THEIR EFFECTS AND DETECTION. [$ 539.
nightstool. Thirteen of the pills were found in the patient's clothes,
and from a chemical and microscopical examination it was found that
they contained digitalis leaf in fine powder. The quantity which the
unfortunate man took in the four weeks was estimated at 13-7 grms.
(= about 211 grains).
Two of his comrades had also been to the “Freimacher,” and had
suffered from the same symptoms, but they had left off the use of the
medicine before any very serious effect was produced.* f
An instructive case of poisoning by digitoxin occurred in the person
of Dr. Koppe, in the course of some experiments on the drug. He had
taken 1.5 mgrim. in alcohol without result; on the following day (May 14)
he took 1 mgrm. at 9 A.M., but again without appreciable symptoms,
Four days later he took 2 mgrms. in alcoholic solution, and an hour
afterwards felt faint and ill, with a feeling of giddiness; the pulse was
irregular, of normal frequency, 80 to 84. About three hours after
taking the digitoxin, Dr. Koppe attempted to take a walk, but the
nausea, accompanied with a feeling of weakness, became so intense that
he was obliged to return to the house. Five hours after the dose, his
pulse was 58, intermittent after about every 30 to 50 beats. Vomiting
set in, the matters he threw up were of a dark green colour; after
vomiting he felt better for a quarter of an hour, then he again vomited
much bilious matter; the pulse sank to 40, and was very intermittent,
stopping after every 2 or 3 beats. Every time there was an intermission,
he felt a feeling of constriction and uneasiness in the chest. Six and a
quarter hours after the dose there was again violent vomiting and
retching, with paleness of the face. The muscular weakness was so
great that he could not go to bed without assistance. He had a disorder
of vision, so that the traits of persons well-known to him were changed,
and objects had a yellow tint. He had a sleepless night, the nausea
and vomiting continuing. During the following day the symptoms
were very similar, and the pulse intermittent, 54 per minute. He
passed another restless might, his short sleep being disturbed by terrible
dreams. On the third day he was somewhat better, the pulse was 60,
* Köhnhorn, Vierteljhrsschr, f. ger. Med., 1876, n. F. xxiv. p. 402.
+ There is an interesting case on record, in which a woman died from the ex-
pressed juice of digitalis. She was twenty-seven years of age, and took a large
unknown quantity of the freshly expressed juice for the purpose of relieving a swell-
ing of the limbs. The symptoms came on almost immediately : she was very sick,
and was attacked by a memorrhagia. These symptoms continued for several days
with increasing severity, but it was not until the fifth day that she obtained medical
assistance. She was then found semi-comatose, the face pale, pulse slow, epigastrium
painful on pressure, diarrhoea and hiccough were frequent. She died on the twelfth
day. The post-mortem appearances showed nothing referable to digitalis save a few
spots of inflammation on the stomach.-Caussé, Bull. de Thérapeutique, vol. lvi.
p. 100; Brit, and For. Med. Chir. Review, vol. xxvi., 1860, p. 523.
§ 540.] DIGITALIS GROUP. * 439
but irregular and still intermittent; the nausea was also a little abated.
The night was similar in its disturbed sleep to the preceding. He did
not regain his full health for several days.”
A third case may be quoted, which differs very markedly from the
preceding, and shows what a protean aspect digitalin poisoning may
assume. A woman, twenty-three years old, took on June 26th, at 7 A.M.,
for the purpose of suicide, 16 granules of digitalin. Two hours later
there was shivering and giddiness, so that she was obliged to go to bed.
In the course of the day she had hallucinations. In the evening at
8 P.M., after eating a little food, she had a shivering fit so violent that
her teeth chattered ; there was cold sweat, and difficulty in breathing ;
she became gradually again warm, but could not sleep. At 1 A.M. the
difficulty of breathing was so great that she dragged herself to the
window, and there remained until 3 A.M., when she again went back to
bed, slept until 7 A.M., and woke tolerably well. Since this attempt of
self-destruction had failed, she took 40 granules. After one hour she
became giddy, had hallucinations, chilliness, cold sweats, copious vomit-
ing, and colicky pains; there was great muscular weakness, but no
diarrhoea. Towards evening the vomiting became worse. There was
no action of the bowels, nor was any urine passed; she felt as if her
eyes were prominent and large. The sufferings described lasted during
the whole might until five o'clock the following day, when the vomiting
ceased, whilst the hallucinations, chilliness, and cold sweat continued;
and the thirst, sick feeling, and weakness increased. The next morning,
a physician found her motionless in bed, with pale face, notable double
exophthalmus, dilated pupils, and cold skin, covered with sweat ; the
pulse was small and intermittent, sometimes scarcely to be felt (46 to
48 per minute); the epigastrium was painful on pressure. She passed
this second night without sleep, and in the morning the pulse had risen
from 56 to 58 beats, but was not quite so intermittent. There was
some action of the bowels, but no urine was passed, nor had any been
voided from the commencement ; the bladder was not distended. The
following (third) day some red-coloured, offensive urine was passed; the
skin was warmer, and the pulse from 60 to 64, still somewhat inter-
mittent—from this time she began to improve, and made a good
recovery.f
§ 540. Physiological Action of the Digitalins. – Whatever other
physiological action this group may have, its effect on the heart's action
is so prominent and decided, that the digitalins stand as a type of heart
poisons. The group of heart poisons has been much extended of late
* Arch. f. exp. Path. w. Pharm., vol. iii. p. 289, 1875.
† Related by Ducroix : De l'Empoisonnement par la Digitale et la Digitaline.
Paris, 1864.
44O POISONS: THEIR EFFECTS AND DETECTION. [$ 541, 542.
years, and has been found to include the following:—Antiarin, an arrow
poison ; helleborin, a glucoside contained in the hellebore family; a
glucoside found in the Apocynaceae, Thevatia neriifolia, and Thevatia
decotli ; the poisonous principle of the Nerium oleander and N. odorum ;
the glucoside of Tamghinia venemifera ; convallamarin, derived from the
species of Convallaria ; scillotoxin, from the squill; superbin, from the
Indian lily; strophantin, from the seeds of Strophanthus hºspidus;
euonymotoxin, from Euonymus atro-purpureus; urecthin and urechi-
toxin, from Urechitis Suberecta; and the alkaloid erythrophlein from
the Erythrophlaeum judiciale (see p. 447 et seq.). This list is yearly
increasing.
§ 541. Local Action.—The digitalins have an exciting or stimulating
action if applied to mucous membranes—e.g. if laid upon the nasal
mucous surface, sneezing is excited ; if applied to the eye, there is red-
ness of the conjunctivae with smarting; if to the tongue, there is much
irritation and a bitter taste. The leaves, the extract, and the tincture
all have this directly irritating action, for they all redden and inflame
mucous membranes. -
§ 542. Action on the Heart.—The earlier experimenters on the
influence of digitalis on the heart were Stannius and Traube. Stannius *
experimented on cats, and found strong irregularity, and, lastly, cessation
in diastole, in which state it responded no longer to stimuli. Rabbits
and birds—especially those birds which lived on plants—were not so
susceptible, nor were frogs.
Traube i made his researches on dogs, using an extract, and adminis-
tering doses which corresponded to from 0-5 to 4:0 grms. He divided
the symptoms witnessed into four stages:—
1st Stage.——The pulse frequently diminishes, while the pressure of
the blood rises.
2nd Stage.—Not seen when large doses are employed; pulse
frequency, as well as blood pressure, abnormally low.
3rd Stage.—Pressure low, pulse beats above the normal frequency.
The curves in accompanying figure illustrate one of Traube's experi-
ments on blood pressure and pulse frequency in a dog treated by
intravenous injections of digitalis infusion, and illustrates the three
stages just described. -
The slowing of the heart # is attributed to the stimulus of the inhibi-
* Arch. f. Physiol., 1852.
+ Amm, d. Charité-Krankenhauses, vol. ii. p. 785.
+ Slowing of the pulse was mentioned first by Withering (An Account of the
Foºglove, Lond., 1785). Beddoes afterwards observed that digitalis increased the
force of the circulation, the slowing of the pulse not being always observed ; accord-
ing to Ackermann, if the inhibitory apparatus is affected by atropine, or if the patient
is under deep narcosis, the slowing is absent.
§ 542.] DIGITALIS GROUP. 44. I
tory nerves, but the later condition of frequency to their paralysis.
After the section of the vagi the slow pulse frequently remains, and this
O 5 10 15 20 25 30 35 40 45 50 55 60 minutes.
250
200
|50
| OO
50
0 5 10 |5 20 25 30 35 40 45 50 55 60 minutes.
Curve showing changes in the pulse, and arterial tension produced by
intravenous injection of infusion of Digitalis in a dog.
is explained by the inhibitory action of the cardiac centre. The Vagus,
in point of time, is paralysed earlier than the muscular substance of the
heart,
The increased blood pressure Traube attributed to increased energy

442 POISONS: THEIR EFFECTS AND DETECTION. [$ 543–545.
of the heart's contraction, through the motor centre being stimulated
later ; the commencing paralysis explains the abnormally low pressure.
There is, however, also an influence on vaso-motor nerves. What
Dr. Johnson has described as the “stop-cock” action of the small arteries
comes into play, the small arteries contract and attempt, as it were, to
limit the supply of poisoned blood. Ackermann,” indeed, witnessed this
phenomenon in a rabbit's mesentery, distinctly seeing the arteries
contract, and the blood pressure rise after section of the spinal cord.
This observation, therefore, of Ackermann's (together with experiments
of Böhm f and L. Brunton i) somewhat modifies Traube's explanation,
and the views generally accepted respecting the cause of the increased
blood pressure may be stated thus:—The pressure is due to prolongation
of the systolic stroke of the cardiac pump, and to the “stop-cock” action
of the arteries; in other words, there is an increase of force from behind
(vis a tergo), and an increased resistance in front (vis a fronte).
§ 543. Action of the Digitalins on the Muco-Intestinal Tract and
other Organs.—In addition to that on the heart, there are other actions
of the digitalins; for example, by whatever channel the poison is intro-
duced, vomiting has been observed. Even in frogs this, in a rudimentary
manner, occurs. The diuretic action which has been noticed in man
is wanting in animals, nor has a lessened diminution of urea been
confirmed.
Ackermann found the temperature during the period of increased
blood pressure raised superficially, but lowered internally. According
to Boeck Ś there is no increase in the decomposition of the albuminoids,
§ 544. The Action of Digitalin on the Common Blow-fly.—The senior author has
studied the effects of digitalin, made up into a thin paste with water, and applied to
the head of the common blow-fly. There are at once great signs of irritation, the
sucker is extruded to its full length, and the fly works its fore feet, attempting to
brush or remove the irritating agent. The next symptom is a difficulty in walking
up a perpendicular glass surface. This difficulty increases, but it is distinctly
observed that weakness and paralysis occur in the legs before they are seen in the
wings. Within an hour the wings become paralysed also, and the fly, if jerked from
its support, falls like a stone. The insect becomes dull and motionless, and ulti-
mately dies in from ten to twenty-four hours. A dose, in itself insufficient to destroy
life, does so on repetition at intervals of a couple of hours. The observation is not
without interest, inasmuch as it shows that the digitalins are toxic substances to
the muscular substance of even those life-forms which do not possess a heart.
§ 545. Action of the Digitalins on the Frog's Heart.—The general
action of the digitalins is best studied on the heart of the frog. Drs.
Fagge and Stevenson have shown || that, under the influence of digitalin,
* Deutsch. Arch. f. klin. Med., vol. xix. p. 125.
† Archiv f. d. Ges. Phys., vol. v. p. 153.
+ On Digitalis, with some Observations on the Urine, Lond., 1868.
§ Intoxication, p. 404. | Guy's Hospl. Reports, 3rd ser, vol. xii. p. 37.
§ 546.] - DIGITALIS GROUP. 443
there is a peculiar form of irregularity in the beats of the heart of the
frog; the ventricle ultimately stops in the white contracted state, the
voluntary power being retained for fifteen to twenty minutes after-
wards; in very large doses there is, however, at once paralysis. Lauder
Brunton * considers the action on the heart to essentially consist in the
prolongation of the systole.
Atropine or curare have no influence on the heart thus poisoned. If
the animal under the influence of digitalin be treated with muscarine,
it stops in diastole instead of systole. On the other hand, the heart
poisoned by muscarine is relieved by digitalin, and a similar influence
appears to be exercised by atropine. The systolic stillness of the heart
is also removed by substances which paralyse the heart, as delphinin,
Saponin, and apomorphin.
Large doses of digitalin, thrown suddenly on the circulation by intra-
venous injection, cause convulsions and sudden death, from quick palsy
of the heart. With frogs under these circumstances there are no con-
vulsions, but a reflex depression, which, according to Weil f and
Meihuizen, ; disappears on decapitation. The central cerebral symptoms
are without doubt partly due to the disturbance of the circulation, and
there is good ground for attributing them also to a toxic action on the
nervous substance. The arteries are affected as well as the heart, and
are reduced in calibre ; the blood pressure is also increased.S This is
essentially due to the firm, strong contraction of the heart, and also to
the “stop-cock” action of the small arteries. ||
§ 546. Post-mortem. Appearances.—In the case of the recruit
poisoned by digitalis leaf (p. 437), the blood was found dark and fluid ;
the right ventricle and auricle of the heart were filled with blood; the
left empty; the brain and its membranes were anaemic ; the stomach
and mucous membrane of the intestines were in parts ecchymosed, and
there were patches of injection. In the case of the widow De Pauw,
poisoned with digitalin by the homoeopath (Conty de la Pommerais),
the only abnormality discovered was a few hyperaemic points in the
* On Digitalis, with some Observations on the Urine, Lond., 1868.
t Archiv f. Amat. w. Physiol., 1871, p. 282.
# Archiv f. d. Ges. Physiol., vol. vii. p. 201.
§ The following is a brief summary of observations on the blood pressure; four
stages may be noticed—(1) Rise of normal blood pressure, not necessarily accom-
panied with a diminution of pulse frequency; (2) continuation of heightened blood
pressure, the pulse being raised beyond the normal rate ; (3) continued high pressure,
with great irregularity of the heart and intermittent pulse ; (4) quick depression of
pressure, sudden stopping of the heart, and death.
| According to Boehm (Arch. f. d. Ges. Physiol., Bd. V. S. 189) and to Williams
(Arch. f. exper. Pathol., Bd. xiii. S. 2), the rise of pressure is due entirely to the
heart, and not to the contractions of the small arteries; but it is difficult to see how
the small arteries can contract, and yet not heighten the pressure.
444 POISONS : THEIR EFFECTS AND DETECTION. [$ 547.
mucous membrane of the stomach and small intestines. It is then
certain that although more or less redness of the liming membrane of
the intestine track may be present, yet, on the other hand, the active
principle of the digitalis may destroy life, and leave no appreciable
sign. - -
§ 547. Separation of the Digitalins from Animal Tissues, etc.—
It is best to make an alcoholic extract after the method of Vitali, already
detailed, the alcohol being feebly acidulated, if necessary, by acetic acid,
and all operations being carried on at a temperature below 60°. The
alcoholic extract is dissolved in water feebly acidulated by acetic acid,
and shaken up, first with petroleum ether to remove impurities (the
ether will not dissolve any of the digitalins), then with benzene, and,
lastly, with chloroform. The benzene dissolves digitalein, and the
chloroform, digitalin and digitoxin. On allowing these solvents to
evaporate spontaneously, residues are obtained which will give the
reactions already detailed. Neither the bromine nor any other chemical
test is sufficient to identify the digitalins; it is absolutely necessary to
have recourse to physiological experiment. The method used by Tardieu
in the classical Pommerais case may serve as a model, more especially
the experiments on frogs. Three frogs were properly secured, the hearts
exposed, and the beats counted. The number of beats was found to be
fairly equal. Frog No. 1 was placed under such conditions that the
heart was constantly moist. Frog No. 2 was poisoned by injecting into
the pleura 6 drops of a solution in which 10 mgrms. of digitalin were
dissolved in 5 c.c. of water. The third frog was poisoned by a solution
of the suspected extract. The number of beats per minute were now
counted at definite intervals of time as follows:—
TABLE SHOWING THE ACTION OF DIGITALIN ON THE
FROGPS HEART.
Frog No. 1 Frog No. 2. Frog No. 3.
ū; led Poisoned by a known Poisoned by the suspected
npolSOne(1. quantity of digitalin. extract.
No. of beats per minute. No. of beats per minute. - No. of beats per minute.
After 6 minutes, 42 20 26
,, 10 , , 40 16 irregular. 24 irregular.
,, 20 3 3 40 15 . 22.
,, 28 , 38 0 12 very irregular.
,, 31 3 5 36 0 0
In operating in this way—which is strictly comparative, and, with
care, has few sources of error—if the heart of the frog poisoned with
§ 548–5 5O.] POISONOUS GLUCOSIDES. 445
the unknown extract behaves in the number and irregularity of its
contractions similarly to that of the digitalin-poisoned heart, it is a fair
inference that, at all events, a “heart-poison’ has been separated ; but
it is, of course, open to question whether this is a digitalin or one of the
numerous groups of glucosides acting in the same way. If sufficient
quantity has been separated, chemical reactions, especially the bromine
test (Grandeau's test), may decide; but with the larger number (yearly
increasing) of substances acting similarly on the heart, great caution in
giving an opinion will be necessary.
II.-0ther Poisonous Glucosides Acting on the Heart.
§ 548. Several members of these glucosides have been studied by
Schmiedeberg,” and his convenient divisions will be followed here :-
1. CRYSTALLISABLE GLUCOSIDES.
Antiarin (C27H12O10+ 4H2O).--Antiarin is an arrow poison obtained from the
milky juice of the Antiaris toa;icaria (upas tree) growing in Java. Antiarin is ob-
tained in crystals, by first treating the inspissated milky juice with petroleum ether
to remove fatty and other matters, and then dissolving the active principle out with
absolute alcohol. The alcoholic extract is taken up with water, precipitated with lead
acetate, filtered, and from the filtrate antiarin obtained by freeing the solution from
lead, and then evaporating. De Vry and Ludwig obtained about 4 per cent. from
the juice. Antiarin is crystalline, the crystals containing 4 atoms of water. Its
melting-point is given as 220-0 ; the crystals are soluble in water (254 parts cold, 27 °4
parts boiling), they are not soluble in benzene, and with difficulty in ether ; 1 part
of antiarin requiring 2792 parts of ether.
The watery solution is not precipitated by metallic salts. On hydrolysing with
dilute alcoholic hydrochloric acid it splits up into antiarigenin and antiarose. Antiari-
genin, Cal H3005, is a crystalline substance, m.p. above 100°. Antiarose is isomeric with
Thamnose, it is oxidised with bromine and water to antiaronic acid, C;HitQ,COOH
(Heinrich Kiliani, Arch. Pharm., 1896). Concentrated sulphuric acid gives with
antiarin a yellow-brown solution, hydrochloric and nitric acids strike no distinctive
colours. -
§ 549. Effects.--Antiarin is essentially a muscular and a heart poison. When
given in a sufficient dose it kills a frog in from half an hour to an hour. Its most
marked effect is on the cardiac muscle, the heart beats more and more slowly, and at
last stops, the ventricle being firmly contracted. As with digitalin, there is a very
marked prolongation of the systole, and as with digitalin, after the beats have ceased,
a forcible dilatation of the ventricle will restore them (Schmiedeberg). It is doubtful
whether by physiological experiment antiarin could be differentiated from digitalin.
§ 550. Separation of Antiarin.—In any case of poisoning by antiarin, it would be
best to extract with alcohol, evaporate, dissolve the alcoholic extract in water, pre-
cipitate with lead acetate, filter, free the filtrate from lead, and then, after alkalising
with ammonia, shake the filtrate successively with petroleum ether, benzene, and a
small quantity of ether in the manner recommended at page 255 et seq. The liquid,
* Beiträge zur Kentniss pharmakol, der Gruppe;des Digitalins,
446 POISONS: THEIR EFFECTS AND DETECTION. [$ 551, 552.
now freed from all fatty, resinous, and alkaloidal bodies, is neutralised and evaporated
to dryness in a vacuum, and the dry residue taken up with absolute alcohol, filtered,
the alcohol evaporated at a very low temperature, and finally the extract dissolved in
a small quantity of water, and submitted to physiological tests.
§ 551. The Active Principles of the Hellebores.—The Christmas
rose (Helleborus niger), as well as H. viridis, H. foetidus, and, in short,
all the species of hellebore, are poisonous, and if the root is treated with
alcohol, from the alcoholic extract may be separatcd two glucosides,
helleborin and helleboyein.
Helleborin is in the form of white, glittering needles, insoluble in
water, but soluble in ether, which, if placed on the tongue, are almost
tasteless, but if dissolved in alcohol, and then tasted, give a burning,
numbing sensation. By boiling with zinc chloride, helleborin splits up
into sugar and a resin–helleboresin. Concentrated sulphuric acid
dissolves the crystals with the production of a beautiful red colour;
on standing, the solution after a while becomes colourless, and a white
powder separates. K. Thaeter (Arch. Pharm., 1897) separates it from
an ethereal extract of the plant, by heating the extract first with light
petroleum to remove fat, next with acetone to remove tarry and colour-
ing matters, and crystallises the residual impure helleborin from a
mixture of alcohol and ether.
Helleborein forms colourless crystals mostly consisting of fine
needles; they have a bitter taste, excite sneezing, and are very
hygroscopic. The crystals easily dissolve in water and dilute alcohol,
but are with difficulty soluble in absolute alcohol, and not soluble in
ether. They dissolve in fatty oils. Helleborein splits by the action of
mineral acids into sugar and amorphous helleboretin.
Helleboretin is in the moist condition of a beautiful violet-blue
colour, becoming, when dried at 100°, dirty green. Concentrated
sulphuric acid dissolves it with the production of a brown-yellow colour,
which on standing passes into violet and then into brown.
Marmé separated from H. faitidus, in addition, a white, intensely
odorous substance, but too small in quantity to thoroughly investigate
its properties.
§ 552. There is little doubt that hellebore owes its properties to the
glucosides just described. There are several instances of poisoning by
hellebore root,” and by the pharmaceutical preparations, but none of
poisoning by the pure active principles. Morgagni mentions a case in
which 2 grims. (nearly 31 grains) of the watery extract of H. niger
caused death within eight hours; and Ferrari saw, after the use of the
* There used to be a tincture officinal in our pharmacopoeia; the root of H.
viridis is officinal in the German pharmacopoeia, maximum single dose, 3 grim. ;
maximum total quantity in twenty-four hours, 1-2 grim. The tincture is also
officinal on the Continent.
§ 553–555.] POISONOUS GLUCOSIDES. 447
wine in which the root had been boiled, two persons poisoned with a
like result. A more recent case was recorded by Felletar, in 1875, in
which a person died from an infusion of hellebore; there was, however,
old standing heart disease, so that there may be a doubt as to the real
cause of death in this instance. Schauenstein mentions a case in which
the roots of hellebore were accidentally used in soup, but the bitter
taste prevented any quantity being eaten. The physiological action,
especially of helleborein, is that of an intense heart poison, and the
symptoms produced by the hellebores are so strikingly like those of
the digitalins that it might be difficult to distinguish clinically between
them. In any case of poisoning, the active principle must be separated
in the form of an alcoholic extract, and identified as a heart poison by
physiological experiment.
§ 553. Euonymin is found in a resin obtained from the Euonymus atropur-
pureus; it is crystalline, crystallising in colourless, cauliflower-like masses consisting
of groups of stellate needles, which are soluble in water, but with difficulty in
alcohol. It is a glucoside, and a powerful heart poison, 1 mgrin. causing the heart
of a frog to cease in diastole.”
§ 554. Thevetin (CºHisO3). —A glucoside which has been separated from the
Thevetia meriifolia, and perhaps also from the Cerbera Odallam. It is soluble in
124 parts of water at 14°, and is easily soluble in spirit, but not in ether. It is
coloured by sulphuric acid red-brown, passing into cherry-red, and then, in a few
hours, into violet. On boiling with diluted acids, it splits up into sugar and
theveresin. Both the vetin and theveresin are powerful heart poisons. T
2. SUBSTANCES PARTLY CRYSTALLISABLE BUT WHICH ARE
NOT GLUCOSIDES.
§ 555. Strophantin (Cºl HisO2) (a)p = + 30 is a very poisonous substance which
belongs physiologically to this group, but does not seem to be a glucoside. It is
soluble in water and in alcohol, less so in ether and chloroform. It is found in
the kombé, mangamja, imee, or omaje, a West African poison derived from the
Strophanthus hispidus of the family of Apocynaceae. The poison has been investi-
gated by several observers.;
Dr. Fraser considers, from his experiments, (1) That strophantin acts primarily
on the heart, producing, as an end result, heart paralysis, with permanence of the
ventricular systole. (2) He found the pulmonary respiration to continue in cold.
blooded animals many minutes after the heart was paralysed. (3) The striped
muscles of the body are affected, and twitches occur in them ; their tomicity is
exaggerated, and finally their functional activity is destroyed. This change is
referred to an action on the muscular structure itself, independent of that upon the
heart, and also independent of the cerebro-spinal nervous system. (4) The reflex
action of the spinal cord is suspended after the heart is paralysed, but the motor
conductivity of the spinal cord and of the nerve trunks continue after the striped
muscles of the body are paralysed. (5) The lymph-hearts of the frog continue to
contract for many minutes after the blood-heart has been paralysed.
* Schmiedeberg, op. cit., from unpublished researches of Professor H. Meyer,
Dorpat.
+ Husemann, Archiv f. exper. Path. w. Pharmakol., Bd. v., S. 228, 1876.
# Digitoxim (see ante, p. 433) belongs to this group.
448 POISONS: THEIR EFFECTS AND DETECTION. [$ 556–559.
3. NON-CRYSTALLISABLE GLUCOSIDES ALMOST INSOLUBLE
IN WATER.
§ 556. Scillain, or Scillitin, a glucoside which has been separated from the
bulbs of the common squill. It is insoluble or nearly so in water, but easily dis-
solves in alcohol. It is little soluble in ether. It acts upon the heart, and is
poisonous.
§ 557. Adonidin, a very similar substance, has been separated from the root of
the Adonis vernalis (Nat. Ord. Ramwmculaceae), to which the name of adonidin has been
given.” It is an amorphous, colourless substance, without odour ; soluble in alcohol,
but with difficulty soluble in ether and water. It is precipitated by tannin, and on
Saponification by mineral acids, splits up into sugar and a substance soluble in ether.
The effects on animals are identical with those of digitalin. The root has been used
recently in medicine, and found to slow the heart and increase the urinary secretion ;
in this also it is like digitalis.
§ 558. Oleandrin.—Oleander leaves contain two chemically-different, nitrogen-
free substances. The one is probably identical with digitalein ; but as this is not
certain, Schmiedeberg proposes to call it provisionally meriin. The other active
substance is essentially the same as the oleandrin of Lukomsket and Betelli.f
Oleandrin has basic properties, and is separated in the form of an amorphous mass,
soluble in alcohol, ether, and chloroform, and slightly soluble in water. Schmiede-
berg obtained a third product from African leaves, which he calls merianthim. This,
on treatment with sulphuric acid and bromine, gives a beautiful colour peculiar to
oleander leaves. It is very similar in physiological and chemical properties to
digitalin, and is probably derived by decomposition from one of the principles already
described. There is also a product similar to digitaliresin.
The active principles of the oleander are separated by digestion of the leaves with
alcohol of 50 per cent., and precipitating the alcoholic extract with lead acetate and
ammonia. The first precipitate is yellow, and is probably composed of a tannin-like
substance; the next precipitate is white, consisting of the lead compound of neriin.
The precipitates are filtered off, and the filtrate concentrated ; merianthin, after a
while, separates in light flocks, and the filtrate from this contains some of the other
products.
§ 559. Neriin or Oleander Digitalin.—Neriin is, in the presence of much free
mineral acid, precipitated by potass-bismuth iodide, a reaction first pointed out by
Marmé, S as useful in the isolation of the helleborins; or it may be precipitated by
tannin, and them the precipitate decomposed by dissolving in alcohol, and evaporating
it to dryness with zinc oxide on the water-bath. It is next extracted by absolute
alcohol, and precipitated by the addition of much ether. The further purification
consists of re-solution in alcohol, and fractional precipitation by ether. If, however,
the potass-bismuth iodide process is used, the liquid must be acidified strongly with
sulphuric acid, and the precipitate washed with diluted sulphuric acid. The pre-
cipitate may be decomposed by baryta, filtered, and the filtrate freed from baryta by
carbon dioxide ; the filtrate from this contains meriin with baric iodide ; it is there-
fore treated with silver sulphate, then again with baryta, next with carbon dioxide,
and also with SH2 to get rid of the last trace of silver.
The filtrate will also contain some oleandrin which, by evaporating slowly in
a vacuum, separates gradually in the form of a clear, resinous mass. It can be filtered
* Cervello, Archiv für cap. Path. Pharm., 1882, p. 338.
+ Repert. de Chimie de Wavrtz et Barreswil, t. iii. p. 77, 1861.
† Bull. Med. di Bologna, t. xix. p. 321, 1865.
§ Zeitsch'. f. rat. Med. (3 R.), Bd. xxvi. S. 1, 1866.
§ 560-562.] POISONOUS GLUCOSIDES. 449
off, and the neriin then may be precipitated pure by fractional precipitation. Its
physiological action is the same as that of digitalein.
§ 560. The Nerium, oleander has several times caused grave symptoms of poison-
ing, and they have usually fairly agreed with those produced by foxglove. For
example, Maschka" relates the case of a boy, 2 years old, who ate two handfuls
of the Nerium oleander. The effects commenced in ten minutes, the child was
uneasy, and vomited. In six hours a sleepy condition came on ; the face was pale,
the skin cold, the pupils contracted, and the pulse slow and irregular. After the
sickness the boy woke up, but again fell asleep, and this occurred frequently ;
coffee was given, which appeared to do good. The pulse was intermittent. On
the following day the child was still ill, with an intermittent pulse, frequent
vomiting, feebleness, sleeplessness, and dilatation of the pupil; there was no
diarrhoea, on the contrary, the bowels were confined. On the third day recovery
followed.
In an Indian case,f the symptoms were altogether peculiar, and belonged
rather to the convulsive order. A woodcutter, aged 35, near Kholapore,
took, for the purpose of suicide, a little over an ounce of the expressed juice
of the oleander. The symptoms began so rapidly that he had not time to walk
five yards before he fell insensible; he was brought to the hospital in this state ;
the face on his arrival was noticed to be flushed, the breathing stertorous, there
were violent spasmodic contractions of the whole body, more marked on the
left than on the right side. The effect of this was remarkable. During the
intervals of the spasm, the patient lay evenly on his back, and when the con-
vulsions commenced the superior contraction of the left side threw him on to
the right, in which position he remained during the paroxysm, after the subsidence
of which he fell back into his old position. The evacuations were involuntary
and watery ; the man was insensible, with frequent convulsions of the kind
described, for two days, but on the third day became conscious, and made a good
recovery.
In any case of poisoning, the methods by which neriin and oleandrin are separated
from the plant can be applied to separate them from the tissues with more or less
success. Here, as in all the other digitalin-like glucosides, physiological tests are
alone of value in the final identification. -
§ 561. The Madagascar Ordeal Poison.—To this group may also belong the
poison of the Tamghinia venemifera, a tree in the Island of Madagascar, the fruit of
which is used as an ordeal poison. It may be obtained in crystals; it is insoluble
in water, and very poisonous. The upas of Singapore is also said to contain with
strychnine a glucoside similar to antiarin.
4. SUBSTANCES WHICH BEHAVE LIKE THE DIGITALINS.
§ 562. Apocynin, which with apocynein (a glucoside) occurs in Apocynum
cannabimum onabam, an East Indian arrow poison ; echujin, a north-west African
arrow poison ; wrecthin and wrechitoa in from Urechitis suberecta; Kovallamarin,
a glucoside from May-flowers; koronillin, a glucoside from Coronilla scorpioides ;
cheiranthim, a glucoside from Cheiranthus cheir ; are all substances which have a
similar action to digitalis on the heart. Erythrophlein is an alkaloid, not a gluco-
side, and is obtained from the bark of the Erythrophlaeum gwineense (West Africa).
It acts on the heart like digitalis, and has also effects similar to picrotoxin.
* Vierteljahrsschrift f. gericht. Med., Bd. ii. No. 17, 1860. Brit, and For. Med.
Chir. Review, vol. xxvi. p. 523, 1860.
+ Transac. of Med, and Phys. Soc. of Bombay, 1854,
29
450 POISONS: THEIR EFFECTS AND DETECTION. [$ 563, 564.
III.-Saponin—Saponin Substances.
§ 563. The term “saponin’ of late years has been applied to a class
of glucosides which possess the common property of being poisonous,
and, when dissolved in water, forming solutions which froth on shaking
like soapsuds.
The substances which have these properties are not all of the same
series chemically, but those of the general formula, C, Han-s010, are
most numerous, and the following is a list:—
Name. Formula.
Saponin, Senegin,
Quillaja-Sapotoxin,
Sapindus-sapotoxin, º ſº & & tº g Chºhodolo.
Gypsophila-Sapotoxin,
Agrostemma-Sapotoxin,
Saponin II., digitonin, Saporubrin, assamin, º e s CishesC10.
Saponin III., quillajic acid, polygalic acid,
Herniari-saponin, p ! . . . CigH3000.
Cyclamin, Sarsaparilla-Saponin, . g º g # e C20H82O10.
Sarsa-Saponin, . te e º g & * * C22H26O10.
Parillin, e & & e t tº sº ſº CogFIA4010.
Melanthin, e e & º g & § g C28HB0019.
Possibly also dulcamarin, C22H84010, and syringin, C17H26Olo, may
belong to this series.
There are some 150 distinct plants which thus yield saponins; a
few of these plants are as follows:–Saponaria officinalis, Gypsophila
Struthium, AgroStemma githago (corn cockle), Polygala Senega, Monimia
polystachia, the bark of Quillaja Saponaria, and Chrysophyllum gly-
cyphleum.
The saponin separated from Saponaria and from the corn cockle
will be here described.
§ 564. Properties.—Saponin is a white amorphous powder, very
soluble in water, to which it gives the curious property of frothing just
like soap solution. To obtain this effect there must be at least 1 mgrum.
in 1 c.c. of liquid. Saponin is neutral in reaction, it has no odour, but
causes sneezing if applied to the mucous membrane of the nose ; the
taste is at first sweet, and then sharp and acrid. It is almost entirely
insoluble in absolute alcohol, but dissolves in hot alcohol of 83° to
separate again nearly completely on cooling. It is precipitated by basic
lead acetate, and also by baryta water, but in each case it is advisable
to operate on concentrated solutions. Picric acid, mercuric chloride,
and alkaloidal “group reagents” give no precipitate. When a little of
the solid substance is treated with “Nessler” reagent, there is a
§ 565.] SAPONIN. 45 I
greenish or yellow colour produced. A drop of strong sulphuric acid,
mixed with a minute quantity of saponin, strikes slowly a bright red
colour, which, on heating, deepens to maroon-brown. Nordhausen
sulphuric acid shows this better and more rapidly. If Saponin is boiled
with dilute acid it breaks up into sapogenin and sugar, and therefore
the liquid after neutralisation reduces “Fehling.”
Sapogenin may be separated by evaporating the neutralised liquid to
dryness, treating the dry residue with ether, which dissolves out the
sapogenin, and finally recovering the substance from the ethereal
solution, and crystallising it from hot alcohol. Crystals are readily
obtained if the alcoholic solution is allowed to evaporate spontaneously.
A solution of saponin exposed to the air gets turbid, and develops
carbon dioxide; not unfrequently the solution becomes mouldy.
W. von Schulz” has shown that saporubin, the active principle of
Saponaria rubra, when treated with dilute sulphuric acid, gives glucose
and various Sapogenins according to the temperature and having the
formulae Car PI3506, C1s H2O6, Cisłł2404, C14H22O2, this last melting at
248"–250°. The sugar formed has (a) = + 23-67 and is not fermentable
by yeast, the osazone melts at 165°–170°.
§ 565. Effects.-Pelikant has studied the effects of various saponins
on frogs. One to two drops of a saturated watery solution of saponin
applied subcutaneously to the leg, caused, in from five to six minutes,
great weakness, accompanied by a loss of sensibility; but strong
mechanical, chemical, or electrical stimuli applied to the foot excited
reflex action, for the ischiatic nerve still retained its functions. Never-
theless, from the commencement, the excitability of the poisoned muscles
was much weakened, and just before death quite disappeared. Section
of the ischiatic nerve delayed the phenomena. Curarine did not seem
to have any effect on the poisomous action. A concentrated solution
applied to the heart of a frog soon arrests its beats, but weaker doses
first excite, and then retard. }
The senior author has studied the general action of saponin on kittens,
insects, and infusoria. Small doses, such as from 13 to 32 mgrms. (# to
# grain), were injected beneath the loose skin of the back of the neck of
a kitten, when there were immediate symptoms of local pain. In from
ãve to ten minutes the respiration notably quickened, and the animal
fell into a lethargic state, with signs of general muscular weakness; just
before death the breathing became very rapid, and there were all the signs
of asphyxia. The pathological appearances after death were fulness in
the right side of the heart, and intense congestion of the intestinal canal,
the stomach generally being perfectly normal in appearance, and the
* Chem. Centr., 1897, 302. f Berl. klin. Wochschr., 36, 186.
+ J. Hoppe, Nervenwirkung der Heilmittel, H, 4, 37,
452 POISONS: THEIR EFFECTS AND DETECTION. [$ 566, 567.
kidneys and other organs healthy. The least fatal dose for a kitten
seems to be 13 mgrms., or '04 grim. to a kilogramme.*
§ 566. Action on Man.—The effects of saponin on man have been but
little studied; it has been administered by the mouth in doses of from
‘1 to 2 grm., and in those doses seems to have distinct physiological
effects. There is increased mucous secretion, and a feeling of nausea ;
but neither diaphoresis nor diuresis has been observed. From the fore-
going study it may be predicated that 2:6 grims. (40 grains), if adminis-
tered subcutaneously to an adult, would endanger life. The symptoms
would be great muscular prostration, weakness of the heart's action, and
probably diarrhoea. In fatal cases, some signs of an irritant or inflam-
matory action on the mucous membranes of the stomach and intestines
would be probable.
§ 567. Separation of Saponin.-Saponin is separated from bread,
flour, and similar substances by the process given at p. 153, “Foods.”
The process essentially consists in extracting with hot spirit, allowing the
saponin to separate as the spirit cools, collecting the precipitate on a
filter, drying, dissolving in cold water, and precipitating with absolute
alcohol. In operating on animal tissues, a more elaborate process is
necessary. The senior author has successfully proceeded as follows:—The
finely divided organ is digested in alcohol of 80 to 90 per cent. strength,
and boiled for a quarter of an hour ; the alcohol is filtered hot and
allowed to cool, when a deposit forms, consisting of fatty matters, and
containing any Saponin present. The deposit is filtered off, dried, and
treated with ether to remove fat. The insoluble saponin remaining
is dissolved in the least possible quantity of water, and precipitated with
absolute alcohol. It is also open to the analyst to purify it by precipi-
tating with baryta water, the baryta compound being subsequently
decomposed by carbon dioxide. Basic lead acetate may also be used as
a precipitant, the lead compound being, as usual, decomposed by hydric
sulphide; lastly, a watery solution may be shaken up with chloroform,
which will extract Saponin. By some one of these methods, selected
according to the exigencies of the case, there will be no difficulty in
separating the glucoside in a fairly pure state. The organ best to ex.
amine for saponin is the kidney. In one of the experiments, in a cat
poisoned with a subcutaneous dose of Saponin (2 grnm.), evidence of the
glucoside was obtained from the kidney alone. The time after death at
which it is probable that Saponin could be detected is unknown ; it is a
* The action of Saponin when applied in concentrated solution to flies is that of
an intense irritant. There is protrusion of the sucker, and progressive paralysis.
The common infusoria live for some time in dilute solutions of saponin—this is also
true of some of the higher forms; for example, a Cyclops quadricornis seemed in no
way affected by a 2 per cent. Solution.
§ 568-570.] SANTONIN. 453
substance easily decomposed, and, therefore, success in separating it from
highly putrid matters is not probable.
§ 568. Identification of Saponin.—An amorphous white powder,
very soluble in water, insoluble in cold alcohol or ether, having gluco-
sidal reactions, striking a red colour with sulphuric acid, imparting a
soap-like condition to water, and poisonous to animals, is most probably
a Saponin.
DIVISION III.—WARIOUS VEGETABLE POISONOUS PRIN-
CIPLES NOT READILY ADMITTING OF CLASSIFICA-
TION IN THE PREVIOUS DIVISION.
I.—Santonin.
§ 569. Santonin (C15HisO3) is a lactone extracted from the
unexpanded heads of various species of Artemisia (Nat. Ord. Compositae).
The seeds contain, according to Dragendorff, 2-03 to 2-13 per cent. of
santonin, and about 2:25 per cent. of volatile oil, with 3 per cent. of fat
and resin. Santonin forms brilliant, white, four-sided, flat prisms, in
taste feebly bitter, m.p. 170°. Santonin in a concentration of 2 per
cent. in 80 per cent. alcohol turns the plane of polarised light to the
left, [a], at 15° =–176'5"; in chloroform, -171.5°. Santonin dissolves
in alkalies, changing into santonic acid, C, H20, ; this may be retrans-
formed into Santonin and water by heating at 120°.
Santonin contains a ketone group and its phenyl-hydrazone melts
at 220°. It is believed to be a derivative of hexa-hydro-dimethyl-
naphthalin. The crystals become yellow through age and exposure
to light; they are scarcely soluble in cold water, but dissolve in 250
parts of boiling water, freely in alkaline water, in 3 parts of boiling
alcohol, and in 42 parts of boiling ether. Sodic santonate (C15H16NaO,
+ 3}H2O) is officinal on the Continent; it forms colourless rhombic
crystals, soluble in 3 parts of cold water.
§ 570. Poisoning by Santonin.-Eighteen cases of poisoning, either
by Santonin or Santonin-holding substances, which F. A. Falck has been
able to collect, were mearly all occasioned by its use as a remedy for
worms. A few were poisonings of children who had swallowed it by
accident. With one exception those poisoned were children of from
2 to 12 years of age ; in five the flower heads, and in thirteen
santonin itself was taken. Of the eighteen cases, two only died (about
11 per cent.).
454 POISONs: THEIR EFFECTS AND DETECTION. [$ 571-573.
§ 571. Fatal Dose.—So small a number of children have died
from Santonin, that data are not present for fixing the minimum
fatal dose. 12 grn. of Santonin killed a boy of 5% years of age
in fifteen hours; a girl, 10 years old, died from a quantity of
flower heads equal to 2 grnm. of santonin. The maximum, dose for
children is from 65 to 194 mgrms. (1 to 3 grains), and twice the
quantity for adults.
§ 572. Effects on Animals.-Experiments on animals with Santonin
have been numerous. It has first an exciting action on the centres of
nerves from the second to the seventh pairs, and then follows decrease
of excitability. The medulla is later affected. There are tetanic con-
vulsions, and death follows through asphyxia. Artificial respiration
lessens the number and activity of the convulsions, and chloroform,
chloral hydrate, or ether also either prevent or shorten the
attacks.
§ 573. Effects on Man.—One of the most constant effects of
Santonin is a peculiar aberration of the colour-sense, first observed by
Hufeland in 1806. All things seem yellow, and this may last for
twenty-four hours, seldom longer. According to Rose, this apparent
yellowness is often preceded by a violet hue over all objects. If the
lids are closed while the “yellow sight” is present, the whole field is
momentarily violet. De Martiny,” in a few cases, found the “yellow
sight ° intermit and pass into other colours, e.g., after 3 grn. there was
first the yellow perception, then giving the same individual 6 grim., all
objects seemed coloured red, after half an hour orange, and then again
yellow. In another patient the effect of the drug was to give “green
vision,” and in a third blue.
Hufner and Helmholtz explain this curious effect as a direct action
on the nervous elements of the retina, causing them to give the per-
ception of violet; they are first excited, then exhausted, and the eye is
“violet blind.” On the other hand, it has been suggested that
Santonin either colours the media of the eye yellow, or that there
is an increase in the pigment of the macula lutea. The two last
theories do not, however, account for the intermittency and the play
of colours observed in a few cases. To the affections of vision are
also often added hallucinations of taste and smell; there is headache
and giddiness, and in fourteen out of thirty of Rose's observations
vomiting occurred. The urinary secretion is increased. In large and
fatal doses there are shivering of the body, clonic, and often tetanic
convulsions; the consciousness is lost, the skin is cool, but covered with
sweat, the pupils dilated, the breathing becomes stertorous, the heart's
action weak and slow, and death occurs in collapse—in the case observed
* Gaz. des Hôpit., 1860.
$574, 575.] SANTONIN. 45.5
by Grimm in fifteen hours, in one observed by Linstow in forty-
eight hours. In those patients who have recovered, there have
also been noticed convulsions and loss of consciousness. Sieveking *
has recorded the case of a child who took 12 grm. (17 grain)
Santonin; an eruption of nettle rash showed itself, but disappeared
within an hour.
§ 574. Post-mortem. Appearances.—The post-mortem appearances
are not characteristic.
§ 575. Separation of Santonin from the Contents of the Stomach,
etc.—It is specially important to analyse the faeces, for it has been
observed that some portion goes unchanged into the intestinal canal.
The urine, also, of persons who have taken Santonin, possesses some
important peculiarities. It becomes of a peculiar yellow-green, the
colour appearing soon after the ingestion of the drug, and lasting even
sixty hours. The colour may be imitated, and therefore confused with
that which is produced by the bile acids; a similar colour is also seen
after persons have been taking rhubarb. Alkalies added to urine
coloured by santonin or rhubarb strike a red colour. If the urine thus
reddened is digested on zinc dust, Santonin urine fades, rhubarb urine
remains red. Further, if the reddened urine is precipitated by excess
of milk of lime or baryta water and filtered, the filtrate from the urine
reddened by rhubarb is colourless, in that reddened by Santonin the
colour remains. Santonin may be isolated by treating substances con-
taining it with warm alkaline water. The water may now be acidified
and shaken up with chloroform, which will dissolve out any Santonin.
On driving off the chloroform, the residue should be again alkalised,
dissolved in water, and acidified with hydrochloric acid, and shaken up
with chloroform. In this way, by operating several times, it may be
obtained very pure. Santonin may be identified by its dissolving in
alcoholic potash to a transitory carmine-red, but the best reaction is to
dissolve it in concentrated sulphuric acid, to which a very little water
has been added, to warm on the water-bath, and then to add a few drops
of ferric chloride solution to the warm acid; a ring of a beautiful red
colour passing into purple surrounds each drop, and after a little time,
on continuing the heat, the purple passes into brown. A distinctive
reaction is also the production of “iso-santonin ’’; this substance is
produced by warming Santonin on the water-bath with sulphuric acid
for a few hours, and then diluting with water; iso-Santonin is pre-
cipitated, and may be crystallised from boiling alcohol. Iso-Santonin
melts at 138”; it has the same composition as Santonin. It is dis-
tinguished from Santonin by giving no red colour when treated with
sulphuric or phosphoric acids.
* Brit. Med. Journ., 1871.
456 POISONS: THEIR EFFECTS AND DETECTION. [$ 576-578.
II.-Mezereon.
§ 576. The Daphne Mezereum (L.). —Mezereon, an indigenous shrub belonging
to the Thymeleaceae, is rather rare in the wild state, but very frequent in gardens.
The flowers are purple and the berries red. Buckheim isolated by means of ether an
acrid resin, which was converted by saponifying agents into mezereic acid ; the acrid
resin is the anhydride of the acid. The resin is presumed to be the active poisonous
constituent of the plant, but the subject awaits further investigation. There are a
few cases of poisoning on record, and they have been mostly from the berries. Thus,
Linné has recorded an instance in which a little girl died after eating twelve berries.
The symptoms observed in the recorded cases have been burning in the mouth,
gastroenteritis, vomiting, giddiness, narcosis, and convulsions, ending in death.
The lethal dose for a horse is about 30 grns, of powdered bark; for a dog, the
Cesophagus being tied, 12 grims. ; but smaller doses of the fresh leaves may be deadly.
III.-Ergot of Rye.
§ 577. Ergot is a peculiar fungus attacking the rye and other grami-
naceous plants; * it has received various names, Claviceps purpurea
(Tulasne), Spermodia clavus (Fries), Sclerotium clavus (D.C.), etc. The
peculiar train of symptoms arising from the eating of ergotised grain
(culminating occasionally in gangrene of the lower limbs), its powerful
action on the pregnant uterus, and its styptic effects, are well known.
The very general use of the drug by accoucheurs has, so to speak,
popularised a knowledge of its action among all classes of society, and
its criminal employment as an abortive is not infrequent.f
The healthy grain of rye, if examined microscopically in thin sections,
is seen to be composed of the seed-coating, made up of two layers,
beneath which are the gluten-cells, whilst the great bulk of the seed
is composed of cells containing starch. In the ergotised grain, dark
(almost black) cells replace the seed-coat and the gluten-cells, whilst
the large starch-containing cells are filled with the small cells of the
fungus and numerous drops of oil.
§ 578. The chemical constituents of ergot are a fixed oil, trimethyl-
amine, certain active principles, and colouring-matters.
The fixed oil is of a brownish-yellow colour, of aromatic flavour and
acrid taste; its specific gravity is 0.924, and it consists chiefly of
palmitin and olein; it has no physiological action.
Trimethylamine is always present ready formed in ergot; it can also
be produced by the action of potash on ergot.
With regard to the active principles of ergot considerable confusion
still exists, and no one has hitherto isolated any single substance in such
* Some of the Cyperaceae are also attacked.
+ The Russian peasantry use the drug for the same purpose. Vide Mackenzie
Wallace’s “Russia,” i. p. 117.
§ 578.] ERGOT OF RYE, 457
a state of purity as to inspire confidence as to its formula or other
chemical characters. They may, however, be briefly described.
C. Tanret * has separated an alkaloid, which appears identical with
Wenzel’s ergot; nine. To obtain this the ergot is extracted by alcohol of
86°, the spirit removed by distillation, and the residue cooled; a resin
(which is deposited) and a fatty layer (which floats on the surface) are
separated from the extractive liquor and washed with ether; the ethereal
solution is filtered and shaken with dilute sulphuric acid, which takes
up the alkaloid; the aqueous solution of the substance is then filtered,
rendered alkaline by KHO, and agitated with chloroform. The
ergotinine is now obtained by evaporating the chloroform solution, care
being taken to protect it from contact with the air. It gives precipitates
with chloride of gold, potassium iodohydrargyrate, phosphomolybdic
acid, tannin, bromine water, and the chlorides of gold and platinum.
With moderately concentrated SO, H2, it gives a yellowish-red coloration,
changing to an intense violet, a reaction which does not occur if the
alkaloid has been exposed to the air. The composition of the base is
represented by the formula CroH to N4O13, and a crystalline sulphate and
lactate have been obtained. i
Wenzel's Ecboline is prepared by precipitating the cold watery
extract of ergot with sugar of lead, throwing out the lead in the usual
way by hydric sulphide, concentrating the liquid, and adding mercuric
chloride, which precipitates the echoline only. The mercury salt is now
decomposed with hydric sulphide, and after the mercury precipitate
has been filtered off, the filtrate is treated with freshly precipitated
phosphate of silver, and refiltered; lastly, the liquid is shaken up with
milk of lime, again filtered, and the lime thrown out by CO2. The last
filtrate contains echoline only, and is obtained by evaporation at a gentle
heat. It is an amorphous, feebly bitter substance, with an alkaline
reaction, forming only amorphous salts.
A research by Dragendorff on ergot tends to show that Wenzel’s
alkaloids, ergotinine and echoline, are inactive. Dragendorff describes
also (a) Scleromucin, a slimy substance which goes into solution upon
extraction of the ergot with water, and which is again precipitated by
40 to 45 per cent. alcohol. It is colloidal and soluble with difficulty
in water. It contains nitrogen, but gives no albuminoid reaction, nor
any reaction of an alkaloidal or glucosidal body; it yields to analysis—
8'26 per cent. Water.
26.8 35 Ash.
39-0 5 ) Carbon.
6°44 5 5 Hydrogen.
6-41 5 y Nitrogen.
* Compt. Rendus, vol. xxxi. p. 896. t Ibid., April 1878.
458 POISONS : THEIR EFFECTS AND DETECTION. [$ 578.
(b) Sclerotic acid.—A feebly-acid substance, easily soluble in water
and dilute and moderately concentrated alcohol. It passes, in associa-
tion with other constituents of the ergot extract, into the diffusate, when
the extract is submitted to dialysis; but after its separation in a pure
state it is, like scleromucin, colloidal. It is precipitated by 85 to 90 per
cent. alcohol, together with lime, potash, soda, silica, and manganese ;
but after maceration with hydrochloric acid, the greater part of the ash
constituents can be separated by a fresh precipitation with absolute
alcohol. The sample gave 400 per cent. of carbon, 5.2 per cent. hydro-
gem, 42 per cent. nitrogen, 50.6 per cent. Oxygen, with 3.4 per cent. of
ash. Sclerotic acid forms with lime a compound that is not decomposed
by carbonic acid, and which upon combustion leaves from 19 to 20 per
cent. of calcium carbonate. Both these substances are active, although
evidently impure. Sclerotic acid is sold in commerce, and has been
employed subcutaneously in midwifery practice in Russia and Germany
for some time.
The active principle of ergot has been recently called Sphacelo-toxin,
but has not been separated in a pure form. According to Jacobi (Pharm.
Centr., H. xxxviii. 58, and Arch. eaſpt. Path. Pharm., xxxix. 85–143)
there are three substances, all possessing similar therapeutic powers,
which may be obtained from ergot, viz., Sphacelo-toxin, as yet only
obtained as a tarry substance containing no nitrogen; secalin-toxin, a
compound of sphacelo-toxin with the inactive secalin ; and chryso-toxin,
a compound of sphacelo-toxin with the inactive ergo-chrysin, Cai H2,09.
Of these, by far the most definite is Chryso-towin, which has the same
effects as ergot ; chryso-toxin can be precipitated from the ethereal
extract of ergot by light petroleum—by redissolving this product in
ether and again precipitating and repeating the process many times; it
may ultimately be obtained as a yellow, tasteless, odourless powder;
crystallising from an ethereal saturated solution in needles. It is
soluble in most organic solvents, but insoluble in light petroleum and
dilute acids. It is slightly soluble in alkalies and ammonia, and from
such solutions is precipitated by carbon dioxide.
Secalin-toxin, Clah, N,02, is apparently a nitrogenous substance;
possibly, as Jacobi suggests, a compound ; in any case it seems to be
identical with the so-called alkaloid, “Cornutin.” It is obtained from
the ethereal extract by shaking it with acetic acid, and precipitating the
acid extract with sodium carbonate. It is very easily soluble in alcohol,
ethylic acetate, benzene, and chloroform. It is not very soluble in ether,
very slightly soluble in water, and insoluble in petroleum ether. The
oxalate may be prepared by precipitating its ethereal solution with
an alcoholic solution of oxalic acid.
The cornutin of Kobert is obtained by thoroughly exhausting ergot
§ 578.] ERGOT OF RYE. - 459
by petroleum ether, drying the ergot thus freed from fat, and
exhausting with ether; the ethereal solution is shaken up several times
with dilute hydrochloric acid (0.5 per cent.); the acid solution is now
Saturated with ammonia, and the cornutin extracted by shaking the
ammoniacal liquid up with ether.
The ethereal solution on evaporation leaves the alkaloid, which,
when it becomes crystalline, is with difficulty soluble in ether, but
dissolves easily in chloroform and alcohol. It is insoluble in petroleum
ether, and may be precipitated from an ethereal solution by that reagent
in white flocks. The alcoholic solution shows a blue-violet fluorescence;
from the alcoholic solution the alkaloid can be precipitated by the
addition of water. The salts are obtained best by adding to the
chloroform solution an ethereal solution of an acid, in the dark, for the
salts are sensitive to light; in this way the hydrochloride, tartrate, and
citrate can be obtained, the salts separating out.
The alkaloid gives precipitates immediately, or after a little time, with
picric acid, iodine in iodide of potassium solution, bromine water,
ferridcyanide of potassium, Mayer's reagent, and tannic acid ; a few
mgrms. of the acid dissolved in 1 c.c. of strong sulphuric acid becomes in
a few hours of a beautiful violet-blue colour, which only after several
days bleaches out. If to the solution in sulphuric acid a small drop of
ferric chloride solution is added, the mixture becomes first of an orange-
red colour, passing into a deep red colour; this reaction succeeds best
with from 2–3 mgrms. ; larger quantities do not give the reaction so
neatly (Keller, Zeit. f. anal. Chemie, 1895).
The inert principles of ergot are—(1) A red colouring-matter,
Sclererythrin, insoluble in water, but soluble in dilute and strong
alcohol, ether, chloroform, dilute solutions of potash, ammonia, etc. It
can be obtained by dissolving in an alkali, neutralising with an acid,
and shaking up with ether. Alcoholic solution of sclererythrin gives
with aluminium sulphate, and with zinc chloride, a splendid red
mixture ; with salts of calcium, barium, and many of the heavy metals
it gives a blue precipitate; the yield is only 1 to 05 in a thousand
parts.
(2) Another colouring-matter, dissolving in concentrated sulphuric
acid with the production of a fine blue-violet colour, the discoverer has
named Scleroidin. This is not soluble in alcohol, ether, chloroform, or
water, but dissolves in alkaline solutions, potash producing a splendid
violet colour; yield about 1 per 1000.
(3, 4) Two crystalline substances, which may be obtained from ergot
powder, first treated with an aqueous solution of tartaric acid, and the
colouring-matters extracted by ether. One Dragendorff names Sclero-
crystallin (CoH10O.); it is in colourless needles, insoluble in alcohol and
46O POISONS: THEIR EFFECTS AND DETECTION. [$ 579–581.
water, with difficulty soluble in ether, but dissolving in ammonia and
potash solutions. The other crystalline substance is thought to be
merely a hydrated compound of sclerocrystallin. Both are without
physiological action. -
§ 579. Detection of Ergot in Flour (see “Foods,” 5th edition,
p. 155).-The best process is to exhaust the flour with boiling alcohol.
The alcoholic solution is acidified with dilute sulphuric acid, and the
coloured liquid examined by the spectroscope in thicker or thinner
layers, according to the depth of colour. A similar alcoholic solution of
ergot should be made, and the spectrum compared. If the flour is
ergotised, the solution will be more or less red, and show two absorp-
tion bands, one in the green, and a broader and stronger one in the
blue. On mixing the original solution with twice its volume of water,
and shaking successive portions of this liquid with ether, amyl alcohol,
benzene, and chloroform, the red colour, if derived from ergot, will
impart its colour to each and all of these solvents. Ludwig Medicus
and Kober [Zeit. Nahr. Genussm., 1902] detect ergot in flour by treating
10 grims, with 20 c.c. of ether and 10 drops of sulphuric acid [1 : 5].
The ethereal extract on shaking up with 10 drops of sodium hydrogen
carbonate gives a violet coloration if ergot is present.
§ 580. Pharmaceutical Preparations.—Ergot itself is officinal in all
the pharmacopoeias, and occurs in grains from 3 to 1 inch in length, and
about the same breadth, triangular, curved, obtuse at the ends, of a
purple colour, covered with a bloom, and brittle, exhibiting a pinkish
interior, and the microscopical appearances already detailed. Ergot may
also occur as a brown powder, possessing the unmistakable odour of the
drug. A liquid extract of the B.P. is prepared by digesting 16 parts
of ergot in 80 parts of water for twelve hours, the infusion is decanted or
filtered off, and the digestion repeated with 40 parts of water; this is
also filtered off, and the residue pressed, and the whole filtrate united
and evaporated down to 11 parts; when cold, 6 parts of rectified spirit
are added, and, after standing, the liquid is filtered and made up to
measure 16. A tincture and an infusion are also officinal ; the latter is
very frequently used, but seldom sold, for it is preferable to prepare it
on the spot. The tincture experience has shown to be far inferior in
power to the extract, and it is not much used. Ergotin is a purified
extract of uncertain strength; it is used for hypodermic injection ; it
should be about five times more active than the liquid extract.
§ 581. Dose.—The main difficulties in the statement of the medicinal
dose, and of the minimum quantity which will destroy life, are the
extreme variability of different samples of ergot, and its readiness to
decompose. A full medicinal dose of ergot itself, as given to a woman
in labour, is 4 grns. (61.7 grains), repeated every half-hour. In this
§ 582, 583.] ERGOT OF RYE. 46 I
way enormous doses may be given in some cases without much effect.
On the other hand, single doses of from 1 to 4 grns. have caused serious
poisonous symptoms. The extract and the tincture are seldom given in
larger doses than that of a drachm as a first dose, to excite uterine con-
traction. In fact, the medical practitioner has in many cases to experi-
ment on his patient with the drug, in order to discover, not only the
individual susceptibility, but the activity of the particular preparation
used. From the experiments of Nikitin, it is probable that the least
fatal dose of sclerotic acid for an adult man is 20 mgrims. per kilogrºm.
§ 582. Ergotism.—Ergotised cereals have played a great part in
various epidemics, probably from very early times, but the only accurate
records respecting them date from the sixteenth century. According to
Dr Tissot,” the first recorded epidemic was in 1596, when a strange,
spasmodic, convulsive disease broke out in Hessia and the neighbouring
regions. It was probably due to spurred rye. In Voigtlander, the same
disease appeared in 1648, 1649, and 1675; in 1702 the whole of Freiberg
was attacked In Germany and in France successive epidemics are
described throughout the eighteenth century. In France, in 1710, Ch.
Noel, physician at the Hôtel Dieu, had no less than fifty cases under
treatment at the same time.
It is generally said that in 1630, Thuillier, in describing an ergot
epidemic which broke out in Cologne, first referred the cause of the
disease to spurred rye.
It is interesting to inquire into the mortality from this disease. In
1770, in an epidemic described by Taube, in which 600 were affected,
16 per cent. died. In a nineteenth-century epidemic (1855), in which,
according to Husemann, 30 were ill, 23.3 per cent. died. In other
epidemics, according to Heusinger, out of 102, 12 per cent. died ;
according to Griepenkerl, out of 155, 25, or 16 per cent, died ; and,
according to Meyer, of 283 cases, 6 per cent. died.
There are two forms of chronic poisoning by ergot—one a spasmodic
form, the other the gangrenous form.
§ 583. The convulsive form of ergotism mostly begins with some
cerebral disturbance. There are sparks before the eyes, giddiness, noises
in the ears, and a creeping feeling about the body. There is also very
commonly anaesthesia of the fingers and toes, and later of the extremities,
of the back, and even of the tongue. Diarrhoea, vomiting, colic, and
other signs of intestinal irritation seldom fail to be present ; there are
also tetanic spasms of the muscles, rising in some cases to well-marked
tetanus ; epilepsy, faintings, aberrations of vision, amaurosis, and ambly-
opia are frequent ; the skin becomes of a yellow or earthy colour, and is
* Dr. Tissot in Phil. Trams., vol. lv. p. 106, 1765. This is a Latin letter by Dr.
Baker, and gives a good history of the various epidemics of ergotism,
462 POISONS : THEIR EFFECTS AND DETECTION. [$ 584.
covered with a cold sweat; boils and other eruptions may break out;
blebs, like those caused by burns or scalds, have in a few cases been
noticed. Death may occur in from four to twelve weeks after the eating
of the spurred grain from exhaustion. In those individuals who recover,
there remain for some time weakness, contractions of groups of muscles,
anaemia, or affections of vision.
§ 584. The Gangrenous Form of Ergotism.—In this form there is
generally acute pain in the limb or limbs which are about to mortify; and
there may be prodromata, similar to those already described. The limb
swells, is covered with an erysipelatous blush, but at the same time feels
icy cold; the gangrene is generally dry, occasionally moist; the mummi-
fied parts separate from the healthy by a moist, ulcerative process;
and in this way the toes, fingers, legs, and even the nose, may be lost.
During the process of separation there is some fever, and pyaemia may
occur with a fatal result.
Fontenelle described a case in which a rustic lost all the toes of one
foot, then those of the other; after that the remnant of the first foot,
and lastly the leg. But probably the most extraordinary case of gangrene
caused by the use of ergot is that which occurred at Wattisham, Suffolk,
in the family of a labouring man named John Downing. He had a wife
and six children of various ages, from 15 years to 4 months. On
Monday, January 10, 1762, the eldest girl complained of a pain in the
calf of her left leg; in the evening her sister, aged 10, also experienced
the same symptoms. On the following Monday, the mother and another
child, and on Tuesday, all the rest of the family except the father, became
affected. The pain was very violent. The baby at the breast lived a few
weeks, and died of mortification of the extremities. The limbs of the
family now began to slough off, and the following are the notes on their
condition made by an observer, Dr. C. Wollaston, F.R.S., on April
13:—
“The mother, aged 40. Right foot off at the ankle, the left leg
mortified; a mere bone left, but not off.
“Elizabeth, aged 13. Both legs off below the knees.
“Sarah, aged 10. One foot off at the ankle.
“Robert, aged 8. Both legs off below the knees.
“Richard, aged 4. Both feet off at the ankle.
“Infant, 4 months old, dead.” -
The father was also attacked a fortnight after the rest of the family,
and in a slighter degree—the pain being confined to the fingers of his
right hand, which turned a blackish colour, and were withered for some
time, but ultimately got better.
As a remarkable fact, it is specially noted that the family were in
other respects well. They ate heartily, and slept soundly when the pain
$ 585, 586.] ERGOT OF RYE. 463
began to abate. The mother looked emaciated. “The poor boy in
particular looked as healthy and florid as possible, and was sitting on
the bed quite jolly, drumming with his stumps.” They lived as the
country people at the time usually lived, on dried peas, pickled pork,
bread and cheese, milk, and small beer. Dr. Wollaston strictly ex-
amined the corn with which they made the bread, and he found it
“very bad ; it was wheat that had been cut in a rainy season, and had
lain in the ground till many of the grains were black and totally
decayed.””
$ 585. Symptoms of Acute Poisoning by Ergot.—In a fatal case
of poisoning by ergot of rye, recorded by Dr. Davidson,t in which a
hospital nurse, aged 28, took ergot, the symptoms were mainly vomiting
of blood, the passing of bloody urine, intense jaundice, and stupor. But
in other cases, jaundice and vomiting of blood have not been recorded,
and the general course of acute poisoning shows, on the one hand, symp-
toms of intense gastro-intestinal irritation, as vomiting, colicky pains
and diarrhoea ; and, on the other, of a secondary affection of the nervous
system, weakness of the limbs, aberrations of vision, delirium, retention
of urine, coma, and death.
§ 586. Physiological Action as shown by Experiments on Animals.
—In spite of numerous experiments on animals and man, the action of
the ergot principles remains obscure. It has been found in medicine to
exert a specific action on the uterus, causing powerful contractions of
that organ, especially in labour. It is also a haemostatic, and is used to
check bleeding from the lungs and other internal organs of the body.
This haemostatic action, as well as the extraordinary property possessed
by ergot, of producing an arrest or disturbance of the circulation
inducing gangrene, has naturally led to the belief that ergot causes
a narrowing in the calibre of the small arteries, but this has not
received the necessary experimental sanction. Holmes,S Eberty,
* In the Phil. Trams, for 1762 there are two strictly concordant accounts of this
case; and in the parish church of Wattisham, there is said to be a memorial
tablet, which runs as follows:–“This inscription serves to authenticate the truth
of a singular calamity which suddenly happened to a poor family in this parish,
of which six persons lost their feet by a mortification not to be accounted for. A
full narrative of their case is recorded in the Parish Register and Philosophical
Transactions for 1762.”
f Lancet, Sept. 30, 1882.
# In a case in which the senior author was engaged, a dabbler in drugs, having
seduced a young woman, administered to her a dose of ergot which produced a
miscarriage, and for this offence he was convicted. The defence raised was that ergot
is a common medicine used by physicians in the treatment of amenorrhoea, and
other uterine affections. Although in itself this statement was perfectly true, as a
defence it was invalidated by the large dose given, the fact of the seduction, and the
other circumstances of the case.
Ś Archiv d. Physiol. Norm. u. Pathol., iii. p. 384.
464 POISONS : THEIR EFFECTS AND DETECTION. [$ 586.
Köhler,” and Wernick f all observed a contraction in the part to which
the ergot was applied, both in frogs and in warm-blooded animals;
but L. Hermann, ; although he made many experiments, and used
Various preparations, never succeeded in observing a contraction. It
would also seem reasonable to expect that with a narrowing of the
vessels, which means a peripheral obstruction, the blood-pressure would
rise, but on the contrary the pressure sinks, a fact on which there is no
division of opinion.
Nikitin has made some researches with pure sclerotic acid, which
certainly possesses the most prominent therapeutic effects of ergot; but
since it is not the only toxic substance, it may not represent the
collective action of the drug, just in the same way that morphine is not
equivalent in action to opium. Cold-blooded animals are very sensitive
to Sclerotic acid ; of the warm-blooded the carnivora are more sensitive
than the herbivora. The toxic action is specially directed to the
central nervous system—with frogs, the reflex excitability is diminished
to full paralysis; with warm-blooded animals reflex excitability is only
diminished, and continues to exist even to death.
The temperature falls, the breathing is slowed, and the respiration
stops before the heart ceases to beat ; the peristaltic action of the intes-
times is quickened, and the uterus (even of non-pregnant animals) is
thrown into contraction. The terminations of the sensory nerves are
paralysed by the direct action of Sclerotic acid, but they remain intact
with general poisoning. The heart of frogs is slowed by sclerotic acid.
Eberty observed that this slowing of the heart (he used ergotin) was
produced even after destruction of the spinal cord; he therefore con-
sidered it as acting on the inhibitory nerve apparatus of the heart itself.
Rossbach, using Wenzeln's echolin, has also studied its action on the
heart of the frog, and observed that the slowing affected the ventricles
rather than the auricles, so that for one ventricle-systole there were two
contractions of the auricles; besides which, the contractions themselves
were peculiar and abnormal in character. The cause of death from
sclerotic acid seems to be paralysis of the respiration. It is said not to
affect animal foetal life. With regard to the effects produced by feeding
animals with ergotised grain, experiments made during the last century
have proved that it produces a gangrenous disease—e.g., C. Salerné mixed
one part of spurred rye with two of good barley, and fed pigs with the
mixture; a few days afterwards the pigs perished with dilated, hard,
and black bellies, and offensively ulcerated legs; another pig, fed entirely
on the rye, lost its four feet and both ears.
* Ueber die Wirkwngen des Secale Cornutum, Dissert. Halle, 1873.
+ Arch. f. pathol. Amat., lvi. p. 505.
| Lehrbuch der eaper. Toricologie, Berlin, 1874, p. 386.
§ 587, 588.] PICROTOXIN. 465
Kobert * has investigated the effects produced on animals by “spha-
celic acid,” and by “cornutin.” Sphacelic acid appears to cause gangrene-
like ergot, and Kobert believes that in “sphacelic acid” is to be found
the gangrene-producing substance. In cases of death putrefaction is
rapid, the mucous membrane of the intestine is swollen, and the spleen
enlarged. If the mucous membrane of the intestine is examined micro-
scopically, a large quantity of micro-organisms are found in the vessels,
in the villi, between the muscular bundles, and in the deeper layers of
the intestinal walls; this is evidence that the protective epithelial cells
have been destroyed. The mesentery of cats, pigs, and fowls contains
numerous small extravasations of blood. The organs generally, and
especially the subcutaneous cellular tissue, are tinged with the colouring
matters of the bile; this Kobert considers as evidence of weakened vitality
of the red blood corpuscles. The walls of the blood-vessels show hyaline
degeneration, and give with iodine a quasi-amyloid reaction. The vessels
are often partly filled with a hyaline mass, in which, at a later date, a fine
black pigment appears. These pigmented hyaline masses probably
occlude the vessels, and hence cause gangrene.
Cornutin, according to Kobert, first excites the vagus; consequently
there is slow pulse and heightened blood-pressure; then it paralyses the
vaSO-motor centre, and the pulse is accelerated. Severe convulsions,
preceded by formication, follow. Paralysis of the extensor muscles, with
permanent deformity, may result. Cornutin stimulates the uterus to
contraction, but it does not act so well in this respect alone as when
given with Sphacelic acid. In animals poisoned with cornutin, no special
pathological changes of a distinctive nature have been described.
§ 587. Separation of the Active Principles of Ergot from Animal
Tissues.—There has been no experience in the separation of the constitu-
ents of ergot from the organs of the body; an attempt might be made
on the principles detailed on page 254, but success is doubtful.
II.-Picrotoxin, the Active Principle of the Cocculus
indicus (Indian Berry, Levant Nut).
§ 588. The berries of the Menispermum cocculus comprise at least
three definite crystalline principles: menispermine,f paramenispermine
* Lehrbuch der Intoxicationem, by Dr. Rudolph Kobert, Stuttgart, 1893.
f Menispermine (CsII2.N2O, ), discovered in 1834 by Pelletier and Courbe, is
associated with a second named paramenispermine. The powdered berries are
extracted by alcohol of 36° ; the picrotoxin removed by hot water from the alcoholic
extract ; the menispermine and paramenispermine dissolved out together by acidu-
lated water, and from this solution precipitated by ammonia. The brown precipitate
3O
466 POISONS: THEIR EFFECTS AND DETECTION. [$ 589.
(nitrogen containing bases), and picrotoxin, which possesses some of the
characters of an acid.
§ 589. Picrotoxin was discovered in 1820 by Boullay. It is usually
prepared by extracting the berries with boiling alcohol, distilling the
alcohol off, boiling the alcoholic residue with a large quantity of water,
purifying the watery extract with sugar of lead, concentrating the
colourless filtrate by evaporation, and crystallising the picrotoxin out of
water. Picrotoxin, so prepared, is probably a mixture of two bodies—
picrotoxinin, C15H16Oc, and picrotin, C15HisOn, although some authors
consider it to be a definite compound of these two bodies.
The mixture crystallises out of water, and also out of alcohol, in
colourless, flexible, four-sided prisms, often arborescent, and possessing a
silky lustre. They are unalterable in the air, soluble in 150 parts of
cold, and 25 parts of boiling water, dissolving easily in acidified water, in
spirit, in ether, in amyl alcohol, and chloroform. They are without smell,
but have an extremely bitter taste. Caustic ammonia is also a solvent.
The crystals are neutral in reaction. They melt at 199°–200° C. to
a yellow mass ; at higher temperatures giving off an acid vapour, with
a caramel-like odour, and lastly carbonising. Picrotoxin in cold concen-
trated sulphuric acid dissolves with the production of a beautiful gold-
yellow to saffron-yellow colour, which becomes, on the addition of a trace
of potassic bichromate, violet passing into brown. An alcoholic solution
turns a ray of polarised light to the left [a]p =–28.1°.
Concentrated aqueous solutions of alkalies and ammonia decompose
picrotoxin fully on warming. It reduces alkaline copper solution, and
colours bichromate of potash a beautiful green. The best test for its
presence is, however, as follows:—The supposed picrotoxin is carefully
dried, and mixed with thrice its bulk of saltpetre, the mixture moistened
with sulphuric acid, and then decomposed with soda-lye in excess, when
there is produced a transitory brick-red colour. For the reaction to
succeed, the picrotoxin should be tolerably pure. * *
is dissolved by acetic acid, filtered, and again precipitated by ammonia. This
precipitate is dried, treated with cold alcohol to separate a yellow resinous sub-
stance, and lastly with ether, which dissolves out the menispermine, but leaves the
paramenispermine. ~.
Menispermine forms white semi-transparent, four-sided, truncated prisms, melt-
ing at 120°, decomposed at a higher temperature, insoluble in water, but dissolving
in warm alcohol and ether. Combined with 8 atoms of water it crystallises in needles
and prisms. The crystals are without any taste ; in combination with acids, salts
may be formed.
Paramienispermine forms four-sided prisms, or radiating crystalline masses,
melting at 250°, and subliming undecomposed. The crystals are soluble in absolute
ether, insoluble in water, and scarcely soluble in ether.
Paramenispermine dissolves in acids, but apparently without forming definite
Salts.
§ 590, 591.] . PICROTOXIN. 467
Solutions of picrotoxin are not precipitated by the chlorides of
platinum, mercury, and gold, iodide of potassium, ferro- and ferri-cyanides
of potassium, nor by picric nor tannic acids.
Picrotoxinin (C18H1606) is best obtained by brominating picrotoxin
in hot solution with a slight excess of bromine water, and removing the
excess of bromine from the crystalline monobromopicrotoxinin, which is
separated by means of zinc dust and acetic acid. It crystallises from
hot water in colourless anhydrous crystals, and from cold water
in rhombic plates. It melts at 200°–201”; with H2SO, it gives an
intense orange-red colour. Bromopicrotoxinin (C15H15BrO3) melts at
259°–260°.
Picrotin (C15His0,) separates out on cooling the filtrate from the
bromopicrotoxinin; it may be purified by washing with small quantities
of hot chloroform and recrystallising from water. It forms small
needles or rhombic prisms melting at 248°–250”; it is soluble in absolute
alcohol or acetic acid, and only slightly in ether, chloroform, and benzene.
It reduces Fehling's solution and has (a)p=-64'70°; it forms a number
of derivatives, such as benzoylpicrotin (C15H170, Bz), crystallising from
absolute alcohol in colourless crystals—m.p. 236°; acetylpicrotin
(Ch. HºO, Ac), m.p. 244"–245°; anhydrodiacetylpicrotin (C15H1,064C2);
and diacetylpicrotin (C15H16O. Ac2), an oil.”
§ 590. Fatal Dose.—Vossler killed a cat in two hours with a dose of
12 grim. (18 grain); and another cat, with the same dose, died in 45
minutes. Falck destroyed a young hound with '06 grm. (92 grain)
in 24 to 26 minutes. Given by subcutaneous or intravenous injection,
it is, as might be expected, still more lethal and rapid in its effects. In
an experiment of Falck's, '03 grim. (.46 grain), injected into a vein,
destroyed a strong hound within 20 minutes; 016 grim. (24 grain),
injected under the skin, killed a guinea-pig in 22 minutes; and 012
grim. (18 grain) a hare in 40 minutes. Hence it may be inferred that
from 2 to 3 grains (12.9 to 19:4 centigrims.) would, in all probability, be
a dangerous dose for an adult person.
§ 591. Effects on Animals.-The toxic action of picrotoxin on fish
and frogs has been proposed as a test. The symptoms observed in fish
are mainly as follows:–The fish, according to the dose, show uncertain
motions of the body, lose their balance, and finally float to the surface,
lying on one side, with frequent opening of the mouth and gill-covers.
These symptoms are, however, in no way distinguishable from those
induced by any poisonous substance in the water, or by many diseases
to which fish are liable. Nevertheless, it may be conceded that in
certain cases the test may be valuable—if, e.g., beer be the matter
of research, none of the methods used for the extraction of picrotoxin
* R. J. Meyer and P. Benger, Ber., xxxi., 1898.
468 POISONs: THEIR EFFECTS AND DETECTION. [$ 592–594.
will be likely to extract any other substance having the poisonous action
described on fish, so that, as a confirmatory test, this may be of use.
Frogs, under the influence of picrotoxin, become first uneasy and
restless, and then somewhat somnolent ; but after a short time tetanic
convulsions set in, which might lead the inexperienced to imagine that
the animal was poisoned by strychnine. There is, however, one marked
distinction between the two — viz., that in picrotoxin poisoning an
extraordinary swelling of the abdomen has been observed, a symptom
which, so far as known, is due to picrotoxin alone. The frog is, therefore,
in this instance, the most suitable object for physiological tests.
Beer extract containing picrotoxin is fatal to flies; but no definite
conclusion can be drawn from this, since many bitter principles (notably
quassia) are in a similar manner fatal to insect life. -
§ 592. Effects on Man,—Only two fatal cases of poisoning by picro-
toxin are on record. In 1829 several men suffered from drinking rum
which had been impregnated with Cocculus indicus; one died, the rest
recovered. In the second case, a boy, aged 12, swallowed some of a
composition which was used for poisoning fish, the active principle of
which was Cocculus indicus; in a few minutes the boy experienced a
burning taste, he had pains in the gullet and stomach, with frequent
vomiting, and diarrhoea. A violent attack of gastro-enteritis supervened,
with fever and delirium; he died on the nineteenth day. The post-mortem
signs were those usual in peritonitis : the stomach was discoloured
and its coats thinner and softer than was natural ; there were also other
changes, but it is obvious that, as the death took place so long after the
event, any pathological signs found are scarcely a guide for future cases.
§ 593. Physiological Action.—The convulsions are considered to arise
from an excitation of the medulla oblongata ; the vagus centre is stimu-
lated, and causes spasm of the glottis and slowing of the heart's action
during the attack. Rohrig also saw strong contraction of the uterus
produced by picrotoxin. According to the researches of Crichton Browne,
chloral hydrate acts in antagonism to picrotoxin, and prevents the con-
vulsions in animals if the dose of picrotoxin is not too large.
§ 594. Separation from Organic Matters.-Picrotoxin is extracted
from aqueous acid solutions by either chloroform, amyl alcohol, or ether;
the first is the most convenient. Benzene does not extract it, if employed
in the same manner. On evaporation of the solvent the crude picrotoxin
can be crystallised out of water, and its properties examined.
R. Palm” has taken advantage of the fact that picrotoxin forms a
stable compound with freshly precipitated lead hydroxide, by applying
this property as follows:—The solution supposed to contain picrotoxin is
evaporated to dryness, and the extract then taken up in a very little
* J. Pharm. (5), xvii. 19–20.
$ 394A) TUTIN–CORIAMYRTIN. - 469
water, acidified and shaken out with ether. The ether is evaporated,
the ethereal extract dissolved in a little water, the aqueous solution
filtered through animal charcoal, and precipitated by means of lead
acetate, avoiding excess. The solution is filtered, and shaken with freshly
prepared lead hydroxide. The lead hydroxide is dried and tested direct
for picrotoxin; if it does contain picrotoxin, then, on adding to it con-
centrated H2SO4, a beautiful saffron-yellow is produced as bright as if the
substance was pure picrotoxin.
III.--Tutin—Coriamyrtin.
§ 594A. There are three species of Coriaria in New Zealand–C. Sar-
mentosa, C. arborea, and C. Tutu ; the latter is commonly known as the
tree toot. From the New Zealand plants Easterfield and Aston” have
separated a crystalline non-nitrogenous glucoside, tutin, very nearly
allied to a glucoside previously separated from the European species by
Ribau, and named by him coriamyrtin.
The chemical differences between these two principles are as
follows:—
Tutin Coriamyrtin
C.-Ho,0 C #.
Solubility in 100 parts of 17.11-20\-77 15H18O3
water . e tº & 1-8 at 10° 1°44 at 22°
Solubility in 100 parts of
alcohol . g e { } 8'2 at 16° 2°00 at 22°
Reaction with HI followed
with potash . e & Nil Magenta colour
Concentrated HGSO; . * { Blood-red colour Dirty yellow
Subliming point te * About 120° About 150°
The Tutu plants are highly toxic to animals who have not become
immune by eating small quantities; for the native cattle in the Tutu
districts apparently consume moderate amounts of the shrubs with
impunity, whereas other cattle become seriously ill. Both coriamyrtin
and tutin belong pharmacologically to the picrotoxin group of substances.
Tutin is somewhat less toxic than coriamyrtin. There is first depression,
followed by Salivation ; the pulse is slowed, the respirations increased in
frequency, and, finally, clonic convulsions occur: 129 mgrms. killed a
kitten weighing 1 kilogramme in 40 minutes; 1 mgrm, induced in a cat,
2 kilogrns. in weight, a convulsive seizure, and the animal did not
recover for 24 hours.
The method of extracting tutin is, briefly, as follows:—The plant,
finely divided, is boiled with water, this aqueous extract precipitated by
alcohol, the filtrate freed from aleohol, and the tutin extracted by ether.
* Easterfield and Aston, Journ. Chem. Soc., Trans., 1901.
47O POISONs: THEIR EFFECTS AND DETECTION. [$ 595-597.
IV.-The poison of Illicium Religiosum—A Japanese Plant.
§ 595. A new poison belonging to the picrotoxin class has been described by Dr.
A. Langaard. In 1880, 5 children in Japan were poisoned by the seeds of the
Illicium religiosum : 3 of the children died. Dr. Langaard then made various ex-
periments on animals with an active extract prepared by exhaustion with spirit, and
ultimate solution of the extract in water. Eykmann has also imperfectly examined
the chemistry of the plant, and has succeeded in isolating a crystalline body which
is not a glucoside ; it is soluble in hot water, in chloroform, ether, alcohol, and
acetic acid, but it is insoluble in petroleum ether ; it melts at 175°, and above that
temperature gives an oily sublimate. Langaard’s conclusions are that all parts of
the plant are poisonous. The poison produces excitation of the central apparatus of
the medulla oblongata and clonic convulsions analogous to those produced by picro-
toxin, toxiresin, and cicutoxin. Before the occurrence of convulsions, the reflex ex-
citability of frogs is diminished, the respiratory centre is stimulated, hence frequency
of the respiration. Small doses cause slowing of the pulse through stimulation of the
vagus and of the peripheral terminations of the vagus; in the heart the functional
activity is later diminished. Small doses kill by paralysing the respiratory centre ;
large, by heart paralysis. The proper treatment seems to be by chloral hydrate, for
when animals are poisoned by small lethal doses it appears to save life, although
when the dose is large it has no effect.–Ueber die Giftwirkung von Japanischem
Sternanis (Illicium religiosum, Sieb.), Virch. Archiv, Bd. lxxxvi., 1881, S. 222.
W. Pieric Acid and Pierates.
OH
§ 596. Picric Acid, C.HaNaOr, or C6H < is trinitrophenol; it
- ^(No.), -
forms a number of salts, all of which are more or less poisonous. Picric
acid is much used in the arts, especially as a dye. The pure substance
is in the form of pale yellow crystals, not very soluble in cold water,
but readily soluble in hot water, and readily soluble in benzene, ether,
and petroleum ether. The solution is yellow, tastes bitter, and dyes
animal fibres, such as wool ; but it can be washed out of plant fibres
such as cotton.
§ 597. Effects of Picric Acid.—Picric acid and its salts have a ten-
dency to decompose the elements of the blood, and to produce methae-
moglobin ; picric acid is also an exciter of the nervous system, producing
convulsions. To these two effects must be added a third; in acid solu-
tion it has a strong affinity for albumin, so that if it meets with an acid
tissue it combines with the tissue, and in this way local necroses are set
up. The action on albumin is somewhat weakened by the reduction in
the body of part of the picric acid to picraminic acid, C.H2(NO2), NH3OH,
a substance that does not so readily form compounds with albuminous
matters. Doses of 0:5 to 0-9 grm. (about 8 to 14 grains) may be taken
§ 598, 599.] PICRIC ACID—GICUToxin. 47 I
several days in succession without marked symptoms. Ultimately, how-
ever, what is known as “picric jaundice’ appears, the conjunctiva and
the whole skin being stained more or less yellow. The urine, at first of a
dark yellow, is later of a red-brown colour. Dyspepsia, with flatulence and
an inclination to diarrhoea, have been noticed. A single dose of a gramme
(15:4 grains) caused in a case described by Adler * pain in the stomach,
headache, weakness, diarrhoea, vomiting of yellow matters, quickening
and afterwards slowing of the pulse ; the skin was of a brown-yellow
colour, and there were nervous symptoms. The urine was ruby-red. In
both faeces and urine picric acid could be recognised. The excretion of
picric acid continued for six days. A microscopical examination of the
blood showed a diminution of the red blood corpuscles, an increase in
the white. Chéron f has described a case in which the application of
0.45 grm. (6.9 grains) to the vagina produced yellowness of the skin in
an hour, and the urine was also coloured red. Erythema, somnolence,
burning and smarting in the stomach and in the kidneys were also
noticed.
§ 598. Tests.-Picric acid is easily separated from either tissues or
other organic matters. These are acidified with sulphuric acid and then
treated with 95 per cent. alcohol; the alcohol is filtered off, distilled,
and the residue treated with ether ; this last ethereal extract will con-
tain any picric acid that may be present.
If the ether extract contains much impurity, it may be necessary to
drive off the ether, and to take up the residue with a little warm water,
then to cool, filter through a moistened filter-paper, and test the aqueous
solution. Picric acid, warmed with KCN and KHO, gives a blood-red
colour, from the production of iso-purpurate of potash. Ammoniacal
copper sulphate forms with picric acid yellow-green crystals which
strongly refract the light. If a solution of picric acid be reduced by the
addition of a hydrochloric acid solution of stanmous chloride, the sub-
sequent addition of ferric chloride produces a blue colour, due to the
formation of amidoimidophenol hydrochloride, C.H.OH(NH2)(NH), HCl,
WI.-Cicutoxin.
§ 599. The Cicuta virosa, a not very common umbelliferous plant
growing in moist places, is extremely poisonous. It is from 3 to 4 feet
in height, with white flowers; the umbels are large, the leaves are tri-
partite, the leaflets linear lanceolate acute, serrate decurrent ; the calyx
has five leaf-like teeth, the petals are obcordate with an inflex point;
the carpels have five equal broad flattened ridges with solitary stripes.
* Wiener med. Woch., 1880, 819. i J. Chéron, Jowrm. de Thér., 1880, 121.
472 POISONs: THEIR EFFECTS AND DETECTION. [$ 600, 601.
Böhm” succeeded, in 1876, in separating an active principle from this
plant. The root was dried, powdered, and exhausted with ether; on
evaporation of the ether the extract was taken up with alcohol, and after
several days' standing the filtrate was treated with petroleum ether; after
removing the petroleum, the solution was evaporated to dryness in a
vacuum ; it was found to be a resinous mass, to which was given the
name cicutoxin. It was fully soluble in alcohol, ether, or chloroform,
and was very poisonous, but what its exact chemical nature may be is
still unknown.
§ 600. Effects on Animals.-Subcutaneously injected into frogs,
cicutoxin acts something like picrotoxin, and something like the barium
compounds. Ten to fifteen minutes after the injection the animal
assumes a peculiar posture, holding the legs so that the thigh is stretched
out far from the trunk, and the leg at right angles with the thigh ; volum-
tary motion is only induced by the strongest stimuli, and when the
frog springs, he falls down plump with stiffly stretched-out limbs. The
frequency of breathing is increased, the muscles of the abdomen are
thrown into contraction, and, the lungs being full of air, on mechanical
irritation there is a peculiar loud cry, depending upon the air being
forced under the conditions detailed through the narrow glottis.
Tetanic convulsions follow, gradually paresis of the extremities appears,
and, lastly, full paralysis and death; these symptoms are seen after
doses of from 1 to 2 mgrms. The lethal dose for cats is about 1
centigrim. per kilo. Diarrhoea, salivation, and frequent breathing are
first seen, and are followed by tonic and clonic convulsions; then there
is an interval, during which there is heightened excitability of reflex
action, so that noises will excite convulsions. Small doses by exciting
the vagus slow the pulse; larger doses quicken the pulse, and raise the
arterial pressure. Cicutoxin is supposed to act specially on the medulla
oblongata, while the spinal cord and the brain are only secondarily
affected.
§ 601. Effects on Man.-F. A. Falck was able to collect thirty-one
cases of poisoning by cicuta; of these 14 or 45.2 per cent. died. The
symptoms are not dissimilar to those described in animals. There are
pain and burning in the stomach, nausea, vomiting, headache, and then
tetanic convulsions. These, in some cases, are very severe, and resemble
those induced by strychnine; but in a few cases there is early coma
without convulsions. There is also difficulty or absolute impossibility
of swallowing. In fatal cases the respiration becomes stertorous, the
pulse small, the pupils dilated, and the face cyanotic, and death occurs
within some four hours, and in a few cases later. The fatal dose is
unknown.
* Arch. f. cap. Path., Bd. v., 1876.
§ 602–6O4.] CENANTHE CROCATA, 473
§ 602. Separation of Cicutoxin from the Body.—An attempt might
be made to extract cicutoxin from the tissues on the same principles as
those by which it has been separated from the plant, and identified by
physiological experiments. In all recorded cases, identification has been
neither by chemical nor physiological aids, but by the recognition of
portions of the plant.
VII.-AEthusa Cynapium (Fool's Parsley).
§ 603. This plant has long been considered poisonous, and a number
of cases are on record in which it is alleged that death or illness resulted
from its use. Dr. John Harley,” however, in an elaborate paper, has
asserted the innocence of this plant, and has analysed the cases on
record. He has experimented on himself, on animals, and on men,
with the expressed juice and with the tincture. The results were
entirely negative; some of the published cases he refers to conium, and
others to aconite. The discussion does not seem entirely closed, for
Dr. Davison f relates a case of serious illness he attended in which he
identified the plant taken by the patient as that of fool's parsley.
VIII.-OEnanthe Crocata.
§ 604. The Water Hemlock. ;-This, a poisomous umbelliferous
plant, indigenous to England, and growing in moist places such as
ditches, etc., is in flower in the month of August. It resembles some-
what celery, and the root is something like the parsnip, for which it
has been eaten. All parts of the plant are said to be poisonous, but
the leaves and stalks only slightly so, while the root is very deadly.
We unfortunately know nothing whatever about the active principles
of the plant; its chemistry has yet to be worked out. M. Toulmouche
(Gaz Med., 1846) has recorded, as the expert employed in the case,
an attempt to murder by using the wºmanthe as a poison; a woman
scraped the root into her husband's soup with evil intent, but the taste
was unpleasant, and led to the detection of the crime. The root has
* St. Thomas’ Hospital Reports, N.S., 1875.
† Brit. Med Jourm., 1904, vol. ii. 124.
# The earliest treatise on poisoning by the water-hemlock is by Wepfer—Cicuta,
Aquat. Historia et Noza, 1679. For cases, see Trojanowsky, Dorp. med. Złg., 1875;
Meyer, Med. Zeitg. f. Preussen, 1842; Schlesier in Casper's Wochenschrift, 1843;
Maly, (Ester. med. Wochenschr., 1844; Badgeley, Montreal Med. Gaz., 1844; Lender,
Viertelj. f. ger. Med., 1865; Gampf, Cöln. Pharm. Zeity., 1875; and the treatises of
Taylor and others.
474 POISONS: THEIR EFFECTS AND DETECTION. [$605, 606.
been mistaken several times for parsnip and other edible roots, and has
thus led to poisonings. The case of 36 soldiers poisoned in this way, in
1758, has been recorded by Orfila; there was one death. In 1803 three
soldiers were poisoned at Brest—1 died. In Woolwich, Bossey witnessed
the poisoning of 21 convicts who ate the roots and leaves of the plant—
6 died. In 1858 there were several sailors poisoned in a similar way—
2 died ; while there have been numerous cases in which the plant has
been partaken of by children.
§ 605. The effects of the poison may be gathered from a case of poison-
ing * which occurred in 1882 at Plymouth; a Greek sailor, aged thirty,
found on the coast what he considered “wild celery,” and ate part of the
root and some of the stem. Two hours after this he ate a good meal and
felt perfectly well, but fifteen minutes later he suddenly and violently
vomited; the whole contents of the stomach were completely evacuated.
In five minutes he was completely unconscious, and had muscular twitch-
ings about the limbs and face. There was a copious flow of a thick
tenacious mucus from the mouth which hung about the lips and clothing
in viscid strings. Twenty-four hours after the poisoning he was admitted
into the South Devon Hospital apparently semi-comatose; his legs dragged,
and he had only feeble control of them ; the extremities were cold, but
there was general free sweating. He could be roused only with difficulty.
There were no spasms, the pupils were dilated and sluggish, the respira-
tion only 14 per minute. Twelve hours after admission he became warmer,
and perspired freely; he slept continuously, but could easily be roused.
On the following day he was quite conscious, and made a good recovery.
Two companions who had also eaten a smaller quantity of the hemlock
dropwort, escaped with some numbing sensations, and imperfect control
over the extremities. In the Woolwich cases the symptoms seem to
have been something similar; in about twenty minutes, one man, without
any apparent warning, fell down in strong convulsions, which soon ceased,
although he looked wild; a little while afterwards his face became bloated
and livid, his breathing stertorous and convulsive, and he died in five
minutes after the first symptoms had set in. A second died with similar
symptoms in a quarter of an hour; a third died in about an hour, a fourth
in a little more than an hour; two other cases also proved fatal, one in
nine days, the other in eleven. In the two last cases there were signs of
intestimal irritation. The majority of the others fell down in a state of
insensibility with convulsions, the after-symptoms being more or less
irritation of the intestinal canal.
§ 606. Post-mortem Appearances.—It was noticed in the Woolwich
cases that those who died quickly had congestion of the cerebral vessels,
and, in one instance, there was even extravasation of blood, but the man
* Lancet, Dec. 18, 1882.
§ 607.] OIL OF SAWIN. 475
who died first of all had no congestion of the cerebral vessels. The
lining membrane of the wind-pipe and air-tubes was intensely injected
with blood, and the lungs were gorged with fluid blood; the blood in
the heart was black and fluid. The stomach and intestines were exter-
nally of a pink colour. The mucous membrane of the stomach was much
corrugated, and the follicles particularly enlarged. In the two protracted
cases the stomach was not reddened internally, but the vessels of the
brain were congested.
IX. —Oil of Savin.
§ 607. The leaves of the Sabina communis (Juniperus Sabina), or
common savin, an evergreen shrub to be found in many gardens, contains
a volatile oil, which has highly irritant properties. Savin leaves are
occasionally used in medicine, maximum dose 1 grm. (15°4 grains).
There is also a tincture—maximum dose 3 c.c. (about 45 mins.)—and
an ointment made by mixing eight parts of savin tops with three of
yellow wax and sixteen parts of lard, melting and digesting for twenty
minutes, and then straining through calico. The oil, a tincture, and an
ointment, are officinal pharmaceutical preparations.
The oil of savin is contained to the extent of about 2 per cent. in the
leaves and 10 per cent, in the fruit. It has a peculiar odour, its specific
gravity is '89 to '94, and it boils at 155° to 160°. An infusion of savin
leaves (the leaves being drunk with the liquid) is a popular and very
dangerous abortive.
It is stated by Taylor that oil of savin has no abortive effect, save
that which is to be attributed to its general effect upon the system ; but
this is erroneous. Röhrig found that, when administered to rabbits, it
had a very evident effect upon the pregnant uterus, throwing it into a
tetanic contraction. The action was evident after destruction of the
spinal cord. The plant causes great irritation and inflammation, whether
applied to the skin or taken internally. The symptoms are excruciating
pain, vomiting, and diarrhoea, and the person dies in a kind of collapse.
In a case in which the senior author was engaged some years ago, a
woman, pregnant by a married man, took an unknown quantity of
infusion of savin tops. She was violently sick, suffered great pain,
with diarrhoea, and died in about 26 hours. The pharynx was much
reddened, and the gullet even congested ; the stomach was inflamed, and
contained some greenish matter, in which savin tops were detected,
a few drops of a strong savin-like smelling oil were separated by distilla-
tion. The time which would elapse between the swallowing of the
poison and the commencement of the pain was an important factor in
476 POISONs: THEIR EFFECTS AND DETECTION. [$608–610.
this case, for the man was accused of having supplied her with the
infusion. From the redness of the pharynx, and, generally, the rapid
irritation caused by ethereal oils, a few minutes only must have
passed between the taking of the liquid and the sensation of consider-
able burning pain; although it is laid down in some works, as, for
example, Falck's Toacicologie, that commonly the symptoms do not
commence for several hours. Symptoms which have been noticed
in many cases are—some considerable irritation of the urinary organs,
such as strangury, bloody urine, etc.; in a few cases vomiting of blood,
in others anaesthesia, convulsions, and coma. Death may occur within
twelve hours, or may be postponed for two or three days.
§ 608. Post-mortem Appearances.—More or less inflammation of
the bowels, stomach, and intestinal tract, with considerable congestion
of the kidneys, are the signs usually found. -
§ 609. Separation of the Poison and Identification.—Hitherto
reliance has been placed entirely on the finding of the savin tops, or
on the odour of the oil. There is no reliable chemical test.
X.—Croton Oil.
§ 610. Croton oil is an oil expressed from the seeds of Croton tiglium,
a plant belonging to the natural order Euphorbiaceae, growing in the
West Indies. The seeds are oval in shape, not unlike castor-oil seeds,
and about three-eighths of an inch in length. Both the seeds and the
oil are very poisonous. The chemical composition of croton oil can
scarcely be considered adequately settled. The most recent view, how-
ever, seems to be that it contains a fixed oil (C.H.O.) with certain
glycerides.” On Saponifying and decomposing the soap a series of
volatile fatty acids can be distilled over, the principal of which are
methyl crotonic acid, with small quantities of formic, acetic, iso-butyric,
valeric, and perhaps propionic, and other acids.f The peculiar pro-
perties of croton are due rather to the fixed oil than to the volatile
principles. The only officinal preparation in the British pharmacopoeia
is a “croton oil liniment,” containing one part of croton oil to seven of
equal parts of oil of cajuput and rectified spirit.
* G. Schmidt, Arch. Pharm. [3], xiii. 213–229. Schlippe, Liebig's Annalen,
cv. 1. Geuther and Fröhlich, Zeitschrift f. Chem., 1870, 26 and 549; Journ. Chem.
Society, March 1879, p. 221.
+ Benedikt has found 0'55 per cent. of unsaponifiable matter in croton oil.
Lewkowitsch gives the iodine value 1017 to 1047, and solidifying point as 18.6°–
19.0°. (Cheml. Analysis of the Oils, Fats, and Waales, by R. Benedikt, translated
and enlarged by J. Lewkowitsch, London, 1895.)
§ 611-613.] CROTON OIL. 477
§ 611. Dose.—The oil is given medicinally as a powerful purgative
in doses up to 65 mgrms. (about a grain). It is used externally as an
irritant or vesicant to the skin. A very dangerous dose would be from
fifteen to twenty times the medicinal dose.
Effects.-Numerous cases of poisoning from large doses of croton
oil are recorded in medical literature, but the sufferers have mostly
recovered. The symptoms are pain, and excessive purging and
vomiting. .
In the case of a chemist,” who took half an ounce of impure croton
oil instead of cod-liver oil, the purging was very violent, and he had
more than a hundred stools in a few hours; there was a burning pain in
the gullet and stomach, the skin was cyanosed, the pupils dilated, and
great faintness and weakness were felt, yet the man recovered. A child,
aged four, recovered from a teaspoonful of the oil given by mistake
directly after a full meal of bread and milk. In five minutes there
were vomiting and violent purging, but the child was well in two days.
A death occurred in Paris, in 1839, in four hours after taking two and
a half drachms of the oil. The symptoms of the sufferer, a man, were
those just detailed, namely, burning pain in the stomach, vomiting, and
purging. Singularly enough, no marked change was noticed in the
mucous membrane of the stomach when examined after death. An
aged woman died in three days from a teaspoonful of croton-oil embro-
cation ; in this case there were convulsions.
In the case of Reg. v. Massey and Ferraud, f the prisoners were
charged with causing the death of a man, by poisoning his food with
jalap and six drops of croton oil. The victim, with others who had
partaken of the food, suffered from vomiting and purging; he became
better, but was subsequently affected with inflammation and ulceration
of the bowels, of which he died. In this case it was not clear whether
the inflammation had anything to do with the jalap and croton oil or
not, and the prisoners were acquitted. In a criminal case in the United
States, a man, addicted to drink, was given, when intoxicated, 2 drachms
of croton oil in a glass of whisky. He vomited, but was not purged,
and in about twelve hours was found dead. The mucous membrane of
the stomach and small intestines proved to be much inflamed, and in
some parts eroded, and croton oil was separated from the stomach.
§ 612. Post-mortem. Appearances.—Inflammation of the stomach
and intestines are the signs usually found in man and animals.
§ 613. Chemical Analysis.-The oil may be separated from the con-
tents of the stomach by ether. After evaporation of the ether, the
blistering or irritant properties of the oil should be essayed by placing a
droplet on the inside of the arm.
* Révue de Thérapeut., May 1881. i Orfila, t. i. p. 108.
478 POISONs: THEIR EFFECTS AND DETECTION. [$ 614, 615.
XI.-The Toxalbumins of Castor-Oil Seeds and of Abrus.
§ 614. The Toxalbumin of Castor-Oil Seeds.-In castor-oil seeds,
besides the well-known purgative oil, there exists an albuminous body
intensely poisonous, which has been carefully investigated by Stillmark,”
under the direction of Kobert.f Injected into the circulation it is more
poisonous than strychnine, prussic acid, or arsenic ; and since the pressed
seeds are without taste or smell, this poison has peculiar dangers of its
OWI). -
It is essentially a blood poison, coagulating the blood.
The blood, if carefully freed from all fibrin, is yet again brought to
coagulation by a small amount of this body.
If castor-oil seeds are eaten, a portion of the poison is destroyed by
the digestive processes; a part is not thus destroyed, but is absorbed,
and produces in the blood-vessels its coagulating property. Where this
takes place, ulcers naturally form, because isolated small areas are
deprived of their blood supply. These areas thus becoming dead, may
be digested by the gastric or intestinal fluids, and thus, weeks after,
death may be produced. The symptoms noted are mausea, vomiting,
colic, diarrhoea, tenesmus, thirst, hot skin, frequent pulse, sweats,
headache, jaundice, and death in convulsions or from exhaustion.
Animals may be made immune by feeding them carefully with small
doses, gradually increased.
The post-mortem appearances are ulceration in the stomach and
intestines. In animals the appearances of haemorrhagic gastro-enteritis
with diffuse nephritis, haemorrhages in the mesentery, and so forth have
been found.
§ 615. Toxalbumin of Abrus.-A toxalbumin is found in the Abrus
precatorius (Jequirity) which causes quite similar effects and symptoms.
That it is not identical is proved by the fact that, though animals may
become immune by repeated doses of jequirity against “Abrin,” the
similar substance from castor-oil seeds only confers immunity against
the toxalbumin of those seeds, and not against abrin; and similarly
abrin confers no immunity against the castor albumin. Either of these
substances applied to the conjunctiva produces coagulation in the
vessels and a secondary inflammation, to which in the case of jequirity
has been given the name of “jequirity-ophthalmia.”
The general effect of these substances, and, above all, the curious fact
that a person may acquire by use a certain immunity from otherwise fatal
* H. Stillmark, Dorp. Arb., Bd. iii., 1889. + Kobert's Lehrbuch, 453-456.
£ Heinr. Hellin, Der giftige Eiweisskorper-Abrin w. Seine Wirkwng auf das.
Blut. Inaug-Diss., Dorpat, 1891.
§ 616, 617.] ICTROGEN. 479
doses, is so similar to poisonous products evolved in the system of persons
suffering from infectious fevers that they have excited of late years much
interest, and a study of their methods of action will throw light upon
many diseased processes.
At present there are no chemical means of detecting the presence of
the toxalbumins mentioned. Should they be ever used for criminal
purposes, other evidence will have to be obtained.
XII.-Ictrogen.
§ 616. Ictrogen.—Warious lupins, e.g. Lupinus luteus, L. angusti-
folius, L. thermis, L. linifolius, L. hirsutus, contain a substance of which
nothing chemically is known, save that it may be extracted by weakly
alkaline water, and which has been named “ictrogen "; this must not
be confused with the alkaloid of lupins named “lupinine,” a bitter-tast-
ing substance. In large doses a nerve poison, ictrogen has the unusual
property of acting much like phosphorus. It causes yellow atrophy of
the liver, and produces the following symptoms :-Intense jaundice: at
first enlargement of the liver, afterwards contraction ; somnolence, fever,
paralysis. The urine contains albumen and the constituents of the bile.
After death there is found to be parenchymatous degeneration of the
heart, kidneys, muscles, and liver. If the animal has suffered for some
time, the liver may be cirrhotic.
Hitherto the cases of poisoning have been confined to animals.
Many thousands of sheep and a few horses and deer have, according to
Kobert, died in Germany from eating lupin seeds. Further information
upon the active principles of lupins may be obtained by referring to the
following treatises: — G. Schneidemuhl, Die lupinen Krankheit der
Schafe; Vorträge f. Thierarzte. Ser. 6, Heft. 4, Leipzig, 1883. C.
Arnold and G. Schneidemuhl, Vierter Beitrag zur Klarstellung der
Ursache u. des Wesens der Lupinose, Luneburg, 1883; Julius Lowenthal,
Ueber die physiol. u. toacicol. Wirkungen der Lupinemalkaloide, Inaug-
Diss., Konigsberg, 1888.
XIII.-Cotton Seeds.
§ 617. Cotton seeds, used as an adulterant to linseed cake, etc.,
have caused the death of sheep and calves. Cotton seeds contain
a poison of which nothing is chemically known, save that it is
poisonous. It produces anaemia and cachexia in animals when given in
small repeated doses.
48O POISONS : THEIR EFFECTS AND DETECTION, [$ 618.
After death the changes are, under these circumstances, confined to
the kidney; these organs showing all the signs of nephritis. If, how-
ever, the animal has eaten a large quantity of cotton seeds, then there
is gastro-enteritis, as well as inflammation of the kidneys.
XIV.-Lathyrus Sativus.
§ 618. Various species of vetchlings, such as L. sativus, L. cicera,
L. clymenum, are poisonous, and have caused an epidemic malady in
parts of Spain, Africa, France, and Italy, among people who have eaten
the seeds. The symptoms are mainly referable to the nervous system,
causing a transverse myelitis and paraplegia. In this country it is
chiefly known as a poisonous food for horses; the last instance of horse-.
poisoning by lathyrus was that of horses belonging to the Bristol
Tramways and Carriage Company.* The company bought some Indian
peas; these peas were found afterwards to consist mainly of the seeds
of Lathyrus sativus, for out of 335 peas no fewer than 325 were the
seeds of Lathyrus. The new peas were substituted for the beans the
horses had been having previously on the 2nd November, and the
horses ate them up to the 2nd December. Soon after the new food had
been given, the horses began to stumble and fall about, not only when
at work, but also in their stalls; to these symptoms succeeded a paralysis
of the larynx; this paralysis was in some cases accompanied by a curious
weird screaming, which once having been heard could never be forgotten ;
there was also gasping for breath and symptoms of impending suffoca-
tion. A few of the horses were saved by tracheotomy. Some died of
suffocation ; one horse beat its brains out in its struggles for breath ;
127 horses were affected—12 died.
The above train of symptoms has also been recorded in similar cases;
added to which paralysis of the lower extremities is frequent. After
death atrophy of the laryngeal muscles, wasting of the nervus recurrens,
and atrophy of the ganglion cells of the vagus nucleus as also of the
multipolar ganglion cells in the anterior horns of the spinal cord, have
been found.
The active principle of the seeds has not been satisfactorily isolated.
The symptoms suggest the action of a toxalbumin. Teilleux found a
resin acid ; Louis Astier a volatile alkaloid, and he explains the fact that
the seeds, after being heated, are no longer poisonous owing to the
dissipation of this alkaloid.
* Bristol Tramways and Carriage Company v. Weston & Co., Times, July 17,
1894.
$ 619–622.] ARUM-MALE FERN. 48 I
XV.-Arum—Bryony—Locust Tree—Male Fern.
$ 619. Arum maculatum, the common cuckoo-pint, flowering in
April and May, and frequent in the hedges of this country, is
extremely poisonous. Bright red succulent attractive berries are
seen on a single stalk, the rest of the plant having rotted away,
and these berries are frequently gathered by children and eaten.
The poison belongs to the class of acrid irritants, but its real nature
remains for investigation.
Some of the species of the same natural order growing in the Tropics
are far more intensely poisonous.
§ 620. The Black Bryony.—Tamus communis, the black bryony, a
common plant by the wayside, flowering in May and June, possesses
poisonous berries, which have been known to produce death, with
symptoms of gastro-enteritis. In smaller doses the berries are stated to
produce paralysis of the lower extremities.*
$621. The Locust Tree.—The Robinia pseudo-acacia, a papilionaceous
tree, contains a poison in the leaves and in the bark. R. Coltmann f
has recorded a case in China of a woman, twenty-four years of age,
who, at a time of famine, driven by hunger, ate the leaves of this tree.
She became ill within forty-eight hours, with high fever; the tongue
swelled and there was much erysipelatous-like infiltration of the
tissues of the mouth ; later, the whole body became swollen. There
was constipation, and so much oedema of the eyelids that the eyeballs
were no longer visible. Recovery took place without special treat-
ment. Power and Cambier f have separated from the bark an
albumose, which is intensely poisonous, and is probably the cause
of the symptoms detailed. -
§ 622. Male Fern.--An ethereal extract of Aspidium Filiac mas is
used as a remedy against tape-worm.
Poullson Š has collected up to the year 1891 sixteen cases of
poisoning by male fern; from which it would appear that 7 to
10 grims. (103 to 154 grains) of the extract may be fatal to a child,
and 45 grns. (rather more than 1% oz.) to an adult. The active
principle seems to be filicic acid and the ethereal oil. Filicic acid,
under the influence of Saponifying agencies, breaks up into butyric
acid and phloroglucin.
The symptoms produced are pain, heaviness of the limbs, faintness,
somnolence, dilatation of the pupil, albuminuria, convulsions, lockjaw,
* Contagne, Lyon med., xlvi., 1884, 239.
f Medical and Swrgical Reporter, lxi., 1889.
: Pharm. Journ., 1890, 711, § Arch. eam. P., Bd. xxix.
3 I
482 POISONS : THEIR EFFECTS AND DETECTION. [$ 622.
and collapse. In animals there have also been noticed salivation, amau-
rosis, unsteady gait, dragging of the hind legs, dyspnoea, and paralysis
of the breathing centres. The post-mortem appearances which have
been found are as follows:—Redness and swelling with haemorrhagic
spots of the mucous membranes of the stomach and intestines;
acute oadema of the brain and spinal cord with petechia in the
meninges; the kidneys inflamed, the liver and spleen congested, and
the lungs oadematous.
There is no characteristic reaction for male fern; the research
most likely to be successful is to attempt to separate from an
ethereal extract filicic acid, and to decompose it into butyric acid
and phloroglucin; the latter tinges red a pine splinter moistened with
hydrochloric acid.
PART VII.-Poisons DERIVED FROM LIVING OF
DEAD ANIMAL SUBSTANCES.
DIVISION I.-POISONS SECRETED BY LIVING
ANIMALS.
I.—Poisonous Amphibia. "
§ 623. The Salamander.—The glands of the skin of certain amphibia
possess a secretion that is poisonous; the animal is unable to empty the
poison glands by any voluntary act, but the secretion can readily be
obtained by pressure.
In 1899, Faust * made a research on the salamander, using no less
than a thousand of these small amphibia, and separated two active bases
in the form of crystalline sulphates.
The animals, killed by chloroform, were finely minced, and the product
extracted with water acidified by acetic acid, at a boiling temperature.
The extract was precipitated by lead acetate, the excess of lead got rid
of by sulphuric acid ; the bases precipitated by phospho-tungstic acid, and
set free by baryta ; the solution thus obtained had to be purified from a
substance giving a biuret reaction. After more than one precipitation
with phospho-tungstic acid, the final solution is exactly neutralised with
sulphuric acid and evaporated to dryness; the yellow residue is dissolved
in alcohol, and ether added until a turbidity results. After a few days,
if the liquid be kept at a low temperature, crystals appear; the sub-
stance is separated, purified, and finally dissolved in hot water, and the
solution allowed to cool slowly. In this, fine needle-like crystals were
obtained, to which Faust ascribes the formula (CºHso N2O), + H2SO, and
gives the name of Samandarin sulphate. The sulphate is optically
active (ap= – 53:69"). A few of the crystals treated in a test-tube with
concentrated hydrochloric acid and boiled for a few minutes gives a
solution at first violet, and finally deep blue. The free base
* Die Thierischen Gifte, Braunschweig, 1906.
483
484 POISONS: THEIR EFFECTS AND DETECTION. [$ 624–626.
“Samandarin’ is an oil of a pale yellow colour. A second alkaloid
(CooHa NO), + H2S0, was obtained by Faust, the sulphate of which is
less soluble than that of Samandarin ; to this he gives the name of
Samandaridin sulphate. It is optically inactive. The crystals are in
the form of rhombic plates or tables. There is more samandaridin to
be obtained from the salamander than Samandarin, the proportion being
about 2 to 1. On dry distillation with zinc dust an alkaline distillate
is obtained, from which Faust isolated isochinolin ; the same author
states that the more volatile constituents of the decomposition give the
reactions of pyrrol. With regard to the chemical relationship between
the two alkaloids, Faust suggests that samandarin possesses one more
methyl-pyridin group, C.H. (CHS)N, than Samandaridin.
$ 624. Poisoning by the Samandarins produce symptoms strikingly
similar to those of rabies, in all its three stages—viz., the excitable stage,
with exaltation of the reflexes, restlessness, acceleration of the respira-
tion, dilatation of the pupil, and increased secretion of the nasal and
buccal secretion ; next, the convulsive stage, with catching respiration,
dyspnoea, and convulsions; and, lastly, the paralytic stage ending in
death, the cause of death usually being paralysis of the respiratory
centre.
Like rabies also, when once the characteristic symptoms develop, no
case of recovery (in animals) is known—death sooner or later supervenes.
The fatal dose is surprisingly small—subcutaneous injections of 0-7
mgrm. to 0.9 mgrm. Samandarin per kilo. of body weight is fatal,
according to Faust, to dogs; but with regard to Samandaridin, this
substance is eight times weaker, and therefore the fatal dose is about
6 to 7 mgrms. per kilo.
§ 625. The Water Salamander (Triton cristatus).-Vulpino (1856)
and Capparelli (1883) have, to a certain extent, investigated a thick
creamy-looking secretion in the skin glands of the water salamander.
Capparelli obtained 40 grms, of the secretion from three hundred Tritons.
The secretion was acid ; the active constituent could be extracted from
the acid solution by ether, was nitrogen-free and volatile at the ordinary
temperature. The Triton poison has a haemolytic action on the red blood
corpuscles—increases the blood pressure and paralyses ultimately the
heart; its action on the circulation agrees generally with that of
Bufotalin, to which it may be chemically allied.
§ 626. Poisons of the Toad (Bufo vulgaris).-The toad secretes a
poison from its skin which has received considerable attention, and has
been investigated by Fornara (1817), Calmels (1884), Heuser (1902),
E. S. Faust, and others. -
Faust * was successful in obtaining two very definite substances—the
* Die Thierischen Gifte, Braunschweig, 1906.
§ 627.] POISONOUS AMPHIBIA. ** 485
one crystalline, Bufonin (Cai H, O,); the other amorphous, Bufotalin
(CºPIA601).
Bufonin crystallises out of an alcoholic extract of the toad's skin in
fine needles or in thicker prisms; after repeated crystallisation the m.p.
is 152°. Bufonin is soluble in chloroform, benzene, and hot alcohol; not
very soluble in ether, nor in water, nor in cold alcohol. A little
bufonin dissolved in chloroform, and then strong sulphuric acid added,
so as to form two strata of the liquids, gives at the point of contact a
deep red zone. On mixing the chloroform solution this becomes dark
red and, finally, purple red. The acid shows a green fluorescence.
Bufonin dissolved in acetic anhydride and, mixed with strong sulphuric
acid, gives the same play of colours as cholesterin—the final colour
is dark green. Phisalix and G. Bertrand, * however, consider bufonin
as simply cholesterin mixed with a little bufotalin.
Bufotalin is obtained from the same alcoholic extract. After sepa-
rating the bufonin, by treating the residue with water, adding lead
acetate to purify, getting rid of the excess of lead by the addition of
just sufficient sulphuric acid, and precipitating the bufotalin by
mercuric potassium iodide, the precipitate is treated with silver oxide
and shaken with chloroform ; from the chloroform solution the bufotalin
may be obtained by precipitating with petroleum ether.
Bufotalin is easily soluble in alcohol, chloroform, acetic acid, and
acetone; it is not very soluble in water, about 2% per million ; it is
insoluble in petroleum ether. The reaction in water is acid, and it
forms soluble compounds with the alkalies. It is precipitated by tannin,
but from such precipitate cannot be recovered, forming apparently fast
compounds with the zinc or lead oxide, the reagents usually used to
decompose tannates. -
Bufonin and bufotalin possess similar poisonous properties; but the
action of bufonin is much weaker than that of bufotalin.
These substances are heart poisons, and have a similar, if not an
identical, action to the digitalins; in this connection it is interesting to
observe that the digitalis group has but little action on the toad, and
that the blood of the toad contains probably the same poisons, i.e.
bufonin and bufotalin. The lethal dose of bufotalin, according to
Faust, for mammals is 3 mgrim. per kilo. of body weight (1 per two
million) if injected subcutaneously; but very much larger doses may
be taken by the mouth. When swallowed, bufotalin excites considerable
irritation of the mucous membrane of the alimentary tract, causing
sickness and diarrhoea; if applied to the conjunctiva, the eye becomes
red and inflamed.
§ 627. The Heloderma.-The Mexican lizard Heloderma horridum, as
* Compt. Rend., 1902.
486 POISONS : THEIR EFFECTS AND DETECTION. [$ 628.
well as H. suspectum, have furrowed teeth and an enormously developed
submaxillary gland, so that on anatomical grounds one would surmise
that their bite was poisomous. Experiments have shown that the secretion
is highly toxic, killing small animals, such as rabbits, in a very few
minutes, in subcutaneous doses equal to 10 mgrms, of the dried poison.
It is apparently a heart poison, but nothing is known of its composition.
Sautesson,” from a partial chemical examination, believes that the poison
is partly a nuclein-holding substance and partly an albumose.
II.-The Poison of the Scorpion.
§ 628. There are several species of scorpions. The small European
variety (Scorpio europaeus) is found in Italy, the south of France, and
the Tyrol; the African scorpion (Bothus afer, L.), which attains the
length of 16 cm., is found in Africa and the East Indies; Androctonus
funestus is found in north and mid Africa, and attains a length of 9 cm.;
and the Androctonus occitanus, 8-5 cm. long, in Spain, Italy, Greece,
and North Africa.
In the last joint of the tail the scorpion is provided with a poisonous
apparatus, consisting of two oval glands, the canal of which leads into a
round bladder, and this last is connected with a sting. When the
sting is inserted, the bladder contracts, and expels the poison through
the hollow sting into the wound. The smaller kinds of scorpion sting
with as little general effect as a hornet, but the large scorpion of Africa
is capable of producing death. There is first irritation about the
wound, and an erysipelatous inflammation, which may lead to gangrene.
Vomiting and diarrhoea then set in, with general weakness and a fever,
which may last from one to one and a half days; in the more serious
cases there are fainting, delirium, coma, convulsions, and death.
According to G. Sanarelli f the blood corpuscles of birds, fishes, frogs,
and Salamanders are dissolved by the poison; only the nucleus remain-
ing intact ; the blood corpuscles of warm-blooded animals are not
affected. W. H. Wilson; found that in guinea-pigs the poison caused
hyper-secretion and death from asphyxia. The coagulability of the
blood was not altered.
Valentin made some experiments on frogs with the Androclonus
Occitanus. He found that soon after the sting the animal remains quiet,
but on irritation it moves, and is thrown into a transitory convulsion;
* Faust, Die Thierischen Gifte, Braunschweig, 1906.
t G. Sanarelli, Bollet, della Soc. della Sez dei cult. delle Scienze med., v., 1888,
† Proc. Physiol. Soc., 1904.
202.
§ 629.] POISONOUS FISH. 487
to this follow twitchings of single muscular bundles. The frog is pro-
gressively paralysed, and the reflex irritability is gradually extinguished
from behind forwards; at first the muscles may be excited by electrical
stimuli to the nerves, but later they are only capable of contraction by
direct stimuli. Scorpion poison has but little, if any, effect taken by
the mouth ; experiments have been made on dogs by Blanchard show-
ing that they can eat scorpions without injury. -
III.-Poisonous Fish.
§ 629. A large number of fish possess poisonous properties; in some
cases the poison is local, in others the poison is in all parts of the body.
The Muraena helena has a sort of pouch connected with four strong
conical erectile teeth or fangs, not dissimilar to the poison apparatus
of a snake; its bite is said to cause toxic symptoms in man.
Many fish are provided with poison glands in connection with the
fins or special weapons, and such are used for purposes of defence. For
example, Synance: a brachio is provided with a back fin consisting of 13
spines, each of which has two poison reservoirs; the reservoirs are
connected with 10 to 12 tubular glands which secrete the poison, a
clear feebly acid bluish fluid, exciting in a concentrated condition local
gangrene; the constitutional effects, according to Pohl (Prager med.
Wochenschrift, 1893), in frogs experimentally injected with the poison
are mainly referable to the action of the poison on the heart, which
it directly paralyses. Bottard has recorded five fatal cases in man.
The Fugu-Poison of Japan.—The Japanese chemists have given the
name of Fugu-poison to that which is found in the ovaries of various
species of Tetrodon, a common fish in Japanese waters. Although con-
centrated in the ovaries, small quantities of the poison have been found
in the liver and the blood. The various species known of Tetrodon are,
with the exception of Tetrodon cutaneus, all poisonous, but in unequal
degrees. The most poisonous are :—Tetrodon chrysops, pardalis,
vermicularis, and poecilonotus ; while less poisonous are Tetrodom rubripes,
porphyréus, stictonotus, and rivulatus; it is believed that the same
poison exists in all the fishes named. D. Takahashi and G. Inoko,” in
1890, began a chemical research upon the poison of the Tetrodon genus;
and G. Tahara, in 1894, separated two principles, the one crystalline, the
other amorphous—Tetrodonin and Tetrodonic acid. The fresh roe of
the fish, after being mashed, is submitted to dialysis; the dialysate
is purified by lead acetate, and then precipitated- by alcohol; a
crystalline mass results, being a mixture of tetrodonin and tetrodonic
* Zeitschrift d. med. Ges. in Tokio, viii.
488 POISONS : THEIR EFFECTS AND DETECTION. [$630.
acid. The latter is separated by dissolving in water and converting it
by means of silver acetate into a silver salt; the tetrodonin is then
precipitated by alcohol.
Tetrodonin is crystalline, neutral in reaction, soluble in water; the
aqueous solution not precipitable by the usual group alkaloidal reagents.
It is insoluble in ether, benzene, and carbon disulphide; it is with
difficulty soluble in alcohol; 50 mgrms, of this substance injected into
a dog weighing 19 kilogm. killed it in half an hour.
Tetrodonic acid is amorphous and hygroscopic ; 10 mgrms. per kilo.
apparently kills dogs in about thirty minutes.
The action of the poison on animals consists in a rapid paralysing
effect on certain regions of the central nervous system, first the respira-
tory centre and then the vaso-motor centre being attacked ; at the same
time a curarin-like paralysis of the peripheral ends of the motor nerves
is observed, which in frogs may be very complete. The heart is not
affected directly, and continues to beat after the cessation of the
respiration. The blood-pressure sinks on account of the paralysis
of the vaso-motor centre. The symptoms in man are similar to those
in animals, and may be gathered from the following account of a
typical case recorded by Takahashi and Inoko.
A man in Kinshin (Japan), at 2 P.M., ate five pieces of a Tetrodon
(species not known). Four hours afterwards he complained of an uneasy
feeling in the epigastrium; the pulse at that time was normal. Womit-
ing was excited by tickling the back of the throat. Quite suddenly the
patient was incapable of walking, and he was soon completely paralysed.
Motion of the tongue was difficult, and his speech was indistinct. Later,
cyanosis, diminished frequency of breathing, and dilatation of the pupil
were observed. The corneal reflex disappeared, and the body tempera-
ture Sank. Artificial respiration and injection of camphor and strychnine
gave no relief, and death quietly followed five hours after the meal.
Neither in animals nor in man are the post-mortem appearances
distinctive.
§ 630. Other Poisonous Fish.—Some fishes are poisonous on account
of the food they live upon; the Meletta venenosa is only poisonous when
it feeds upon a certain green monad; Clupea thrissa, C. venenosa, and
certain species of Scarus neither possess poison glands nor poisonous
ovaries, but also derive their poisonous properties from their food.
In the West Indies it is well known that fish caught off certain coral
banks are unwholesome, while the same species caught elsewhere may be
eaten with safety. *g.
A good many shell-fish, especially mussels, occasionally cause intense
poisonous symptoms; those usually noticed are high fever, nettle-rash,
dilated pupils, and diarrhoea. It may be that in these cases a toxine,
§ 63OA.] POISONOUS SPIDERS AND INSECTS. 489
the product of bacterial action, has been ingested. To the agency of
bacteria has been ascribed illness produced in Russia by a good many
fish of the sturgeon species. The symptoms are those of cerebro-spinal
paralysis. The “Icthyismus gastricus” of Germany may belong to the
same type. Prochorow * has described illness from ingestion of Petro-
myzon fluviatilis in Russia. Whether the fish was eaten raw or cooked,
the effect was the same, producing a violent diarrhoea, dysenteric in
character. Even the broth in which the fish had been boiled produced
symptoms. Fresh blood of the eel is stated to be intensely poisonous;
this property is apparently due to a toxalbumin ; Pennavaria f relates
the case of a man who took, in 200 c.c. of wine, 0.64 kilo. of fresh eel
blood, and suffered from diarrhoea with symptoms of collapse.
In the Linnean Transactions for November, 1860, is recorded a fatal
accident, which took place on board the Dutch ship Postillion at
Simon's Bay, Cape of Good Hope. The boatswain and purser's steward
partook of the liver of the toad fish (Tetrodon Honkengo, Bloch); within
twenty minutes the steward died. In ten minutes the boatswain was
violently ill; the face flushed, the eyes glistening and the pupils con-
tracted ; there was cyanosis of the face, the pulse was weak and inter-
mittent, and swallowing was difficult ; the breathing became embarrassed,
and the body generally paralysed. Death took place in seventeen
minutes. The liver of one fish only is said to have been eaten. This
might weigh 4 drachms. If the account given is literally correct, the
intensity of the poison equals that of any known substance.
The poisonous nature of the goby has also led to several accidents,
and we possess a few experiments made by Dr. Collas, f who fed chickens
with different parts of the fish, and proved that all parts were alike
poisonous. The effects were slow in developing; they commenced in
about an hour or an hour and a half, and were well developed in
five hours, mainly consisting of progressive muscular weakness and
prostration. Death occurred without convulsions.
IV.-Poisonous Spiders and Insects.
§ 630A. The most important species of spiders known to be
poisonous are:– -
Nemasia caementaria, the Minier spider of Costa Rica, is believed
to belong to this class, and is said to cause great injury to horses, oxen,
and other domestic animals; Theraphosa avicularia, the bird spider of
* Pharmac, Ztg., 1885. f Il Farmacista Italiano, xii., 1888.
# Soc. Sci. Rev., July 19, 1862; Brit. and For. Med. Chir. Rev., October 1862,
p. 536.
490 POISONS : THEIR EFFECTS AND DETECTION [$ 63OA.
the Brazils; Theraphosa Blondii, the bush spider of South America and
the West Indies; and Theraphosa Javanensis, a big red-brown spider found
in Java–are all giant tropical hairy spiders, possessing large poison
glands, and whose bite is capable of causing serious symptoms.
The Malmignette (Lathrodectes tredecim-guttatus) is only 8–12 mm.
long ; it has a blackish body; on the underpart of the abdomen are to
be found thirteen triangular or half-moon shaped spots (hence the name);
it is found in Tuscany, Corsica, Sardinia, and the lower Wolga. The
nomadic tribes in South Russia are said to have lost 70,000 cattle, in
1838 and 1839, through the bite of this small insect.
A variety—the Kara-Kurt of the Tartars = “black wolf”—is Lathro-
decies lugubris, common in South Russia, and attaining a length of 2 cm.
The Kara-Kurt poison is not only to be found in special glands, but
is also diffused through the body. According to Kobert, who has
investigated this poison, it is a generic type of the poison of spiders;
the active principle is neither a glucoside, an acid, nor an alkaloid. It
does not dialyse, and drying destroys its activity; it has the characters
of a toxalbumin, and has much similarity to the action of Ricin and
Abrin. The Kara-Kurt poison dissolves the colouring matter of the red
blood corpuscles, even with a dilution of 1 : 127,000; it has a paralysing
effect on the heart, either due to action on the motor ganglia, or, possibly,
a direct action on the muscle itself. The blood-pressure sinks, the walls
of the smallest arteries and capillaries become so changed, as to allow
the transudation of blood and serum, producing punctiform hamorrhages
and Oedema. This is best seen in the lungs. The poison also has a
paralysing action on the central nervous system, but it is not clear as to
whether this action is primary, or whether it depends on the circulation
troubles.
The fatal dose of the poison injected subcutaneously, or intravenously,
is extremely small. Cats are killed by quantities equal to 0-2 to 0-35
mgrim. per kilo. body weight. Repeated injections of non-fatal doses
confer immunity. - -
The Epeira diadema, the ordinary cross-spider, so called from cross-
shaped whitish spots on the abdomen, is common in Europe generally.
Kobert has investigated the poison it possesses and finds it of the same
class as that of the Kara-Kurt, but slightly weaker; he states, however,
that in a single female cross-spider there is enough poison to kill a
thousand cats.
Lycosa tarantula, a spider from 3 to 3-5 cm. long, occurs in Italy,
Spain, and Portugal. Zangrilli has observed several cases of tarantula
bite; soon after the occurrence the part bitten is anaesthetic, after a few
hours there are convulsive shiverings of the legs, cramps of the muscles,
inability to stand, spasm of the pharyngeal muscles, quickening of the
§ 631–634.] CANTHARIDES. 49 I
pulse, and a three days' fever, with vomiting of yellow bilious matter;
recovery follows after copious perspiration. In one case there was tetanus,
and death on the fourth day. The extraordinary effects attributed to
the bite of the tarantula, called tarantism in the Middle Ages, are well
detailed by Hecker; * this excitement was partly hysterical and partly
delirious, and has not been observed in modern times.
Dax has described the effects of the bite of the L. malmignatus; it
occasioned headache, muscular weakness, pain in the back, cramps, and
dyspnoea; the symptoms disappeared after several days.
§ 631. The katipo is a small poisonous spider confined to New
Zealand. Mr. W. H. Wright has recorded the case of a person who, in
1865, was bitten by this spider on the shoulder. The part rapidly
became swollen, and looked like a large nettle-rash wheal; in an hour
the patient could hardly walk, the respiration and circulation were both
affected, and there was great muscular prostration ; but he recovered in
a few hours. In other cases, if the accounts given are to be relied upon,
the bite of the spider has produced a chronic illness, accompanied by
wasting of the body, followed by death after periods varying from six
weeks to three months.f
§ 632. Ants.-The various species of ants possess at the tail special
glands which secrete formic acid. Certain exotic species of ants are
provided with a sting, but the common ant of this country has no special
piercing apparatus. The insect bites, and then squirts the irritating
secretion into the wound, causing local symptoms of swelling and
inflammation.
§ 633. Wasps, etc.—Wasps, bees, and hornets all possess a poison-bag
and sting. Josef Lauyer (Archiv f. exp. Pathol., 1897) collected the
stings and poison-bags of 25,000 bees. These were treated by a modified
Stas-Otto process, and ultimately a substance obtained which gave pro-
nounced alkaloidal reactions. Intravenous injection of 6 c.c.m. of 1:5
per cent. Solution of the natural poison killed a dog weighing 4.5 kilos. ;
there were general convulsions, with trismus, and nystagmus rising to
emprosthotonos, and the animal died from the cessation of respiration.
The poison dissolves the blood corpuscles, and the post-mortem appear-
ances show strong hyperamia and haemorrhages.
§ 634. Cantharides.—Commercial cantharides is either the dried
entire, or the dried and powdered blister-beetle, or Spanish fly
(Cantharis vesicatoria). The most common appearance is that of a
greyish-brown powder, containing shining green particles, from which
* “The Epidemics of the Middle Ages,” by J. F. C. Hecker, translated by
B. G. Babington, M.D., F.R.S. (The Dancing Mania, chap. ii., etc.)
t Transac. of the New Zealand Inst., vol. ii., 1869; Brit. and For. Mcd. Chir.
Review, July 1871, p. 230.
492 POISONS: THEIR EFFECTS AND DETECTION. [$ 635.
cantharidin is readily extracted by exhausting with chloroform, driving
off the chloroform by distillation or evaporation, and subsequently
treating the extract with bisulphide of carbon, which dissolves the fatty
matters only. Finally, the cantharidin may be recrystallised from
chloroform, the yield being .380 to 570 per cent. Ferrer found in the
wings and their cases, 082 per cent. ; in the head and antennae, '088;
in the legs, '091; in the thorax and abdomen, 240 per cent. Wolff
found in Lytta aspera, ’815 per cent. ; Ferrer in Mylabris cichorei,
‘l per cent. ; in M. punctum, 193; and in M. pustulata, 33 per cent.
of cantharidin.
§ 635. Cantharidin (CoHa20,) has two crystalline forms--(1)
Right-angled four-sided columns with four surfaces, each surface
being beset with needles; and (2) flat tables. It was at one time
considered an acid anhydride, but H. Meyers' researches have
shown that it is a 3-lactone of a ketonic acid, the structural formula
of which is :—
CH2—COOH
* *
CH, C—
* N /
CO
CH2
CH
CH2 Nº.
CH2
It is soluble in alkaline liquids, and can be recovered from them by
acidifying and shaking up with ether, chloroform, or benzene ; it is
almost completely insoluble in water. 100 parts of alcohol (99 per
cent.) dissolve at 18° 0-125 part; 100 of bisulphide of carbon, at the
same temperature, 0.06 part; ether, 'll part ; chloroform, 12 part ;
and benzene, 2 part. Cantharidin can be completely sublimed,
if placed in the subliming cell (described at p. 259), floating on
mercury; a scanty sublimate of crystals may be obtained at so low
a temperature as 82°5°; at 85°, and above, the sublimation is
rapid. If the cantharidin is suddenly heated, it melts; but this is
not the case if the temperature is raised gradually. The tube
melting-point is as high as 218". Potassic chromate with sulphuric
acid decomposes cantharidin with the production of the green
oxide of chromium. An alkaline solution of permanganate, iodic
acid, and sodium amalgam, are all without influence on an alcoholic
solution of cantharidin. With bases, cantharidin forms crystallisable
salts, and, speaking generally, if the base is soluble in water, the
“cantharidate” is also soluble ; the lime and magnesic salts dissolve
readily. From the soda or potash salt, mineral acid will precipitate
crystals of cantharidin; on heating with pentasulphide of phosphorus,
o-xylol is produced.
§ 636—638.] CANTHARIDES. 493
§ 636. Pharmaceutical Preparations of Cantharides.—The P.B.
preparations of cantharides are—Acetum cantharides, or vinegar of
cantharides, containing about 04 per cent. of cantharidin.
Tincture of cantharides, containing about 005 per cent. of
cantharidin.
A solution of cantharides for blistering purposes, Liquor epispasticus,
a strong solution of the active principle in ether and acetic acid,
containing about 16 per cent. of cantharidin.
There are also—An ointment; a blistering paper, Charta epispastica;
a blistering plaster, Emplastrum cantharides; and a warm plaster,
Emplastrum calefaciens.
§ 637. Fatal Dose.—It is difficult to state the fatal dose of can-
tharidin, the unassayed powder or tincture having mostly been taken.
A young woman died from 1-62 grim. (25 grains) of the powder, which
is perhaps equivalent to 6.4 mgrms. (I grain) of cantharidin, whilst the
smallest dose of the tincture known to have been fatal is (according to
Taylor) an ounce. This would be generally equivalent to 15 mgrms.
(24 grain). Hence the fatal dose of cantharidin may be approximately
stated as from 6 mgrms. upwards. But, on the other hand, recovery
has taken place from very large doses. .
§ 638. Effects on Animals.-Animals are unequally susceptible to
the action of cantharidin. For example, hedgehogs and swallows are
able to take large relative doses with impunity. Ellinger has shown
that the whole of the poison is excreted unchanged by means of the
kidneys of the hedgehog, therefore the kidney cells must be highly
resistant to cantharidin ; other “kidney poisons,” such as potassic
chromate, cause as much change in the hedgehog's kidneys as in other
animals, so that the immunity is one for cantharidin alone. The
resistance is not absolute ; 0°l grm. causes nephritis, and, in a few days,
death. Radecki’ found that cantharidin might even be injected, in
quantities equal to 15–30 mgrms, into the blood of fowls without
any injury, and frogs also seem to enjoy the same immunity; while
dogs, cats, and other animals are sensitive to the poison. Galippe
ascertained that after the injection of 5 mgrms. into the veins of
a dog, there was exaltation of the sexual desire; the pupils quickly
dilated, the dog sought a dark place, and became sleepy. Animals
when poisoned die in asphyxia from paralysis of the respiratory centre.
Schachowa i made some observations on the effect of cantharides on the
renal excretion of a dog fed daily with 1 grm. in powder. On the third
day, pus corpuscles were noticed; on the fifth, bacteria; on the
thirteenth, the urine contained a large quantity of fatty matters, and
* Die Cantharidin Vergift., Diss., Dorpat, 1806.
+ Unters. iiber die Nieren, Diss., Bern, 1877; Cornil, Gaz. Méd., 1880.
494 POISONS : THEIR EFFECTS AND I) ETECTION, [$ 639.
several casts; and on the seventeenth, red shrivelled blood corpuscles
were observed. Ye
Effects on Man.—Heinrich * made the following experiments upon
himself:-Thirty living blister-beetles were killed, and digested, without
drying, in 35 grms, of alcohol for fourteen days; of this tincture ten
drops were taken. There ensued immediately a feeling of warmth in
the mouth and stomach, salivation, the pulse was more frequent than in
health, there was a pleasant feeling of warmth about the body, and
some sexual excitement lasting three hours. In half an hour there was
abdominal pain, diarrhoea, and tenesmus, and frequent painful micturi-
tion. These symptoms subsided in a few hours, but there was a want of
appetite, and pain about the kidneys lasting until the following day.
In the second experiment, on taking 1 cgrrm. of cantharidin, there were
very serious symptoms of poisoning. Blisters formed on the tongue, and
there was salivation, with great difficulty in Swallowing, and a general
feeling of illness. Seven hours after taking the poison, there were
frequent micturitions of bloody urine, diarrhoea, and vomiting. Twenty
hours after the ingestion the face was red, the skin hot, the pulse twenty
beats beyond the normal pulsation, the tongue was denuded to two-thirds
of its extent of its epithelium, and the lips and mucous membrane were
red and swollen; there was great pain in the stomach, intestines, and
in the neighbourhood of the kidneys, continuous desire to micturate,
burning of the urethra, and swelling of the glands. There was no
sexual excitement whatever; the urine was ammoniacal, and contained
blood and pus; the symptoms gradually subsided, but recovery was not
complete for fourteen days. -
§ 639. The foregoing is a fair picture of what may be expected in
cantharides poisoning. It is remarkable that the popular idea as to the
influence of cantharidin in exciting the sexual passion, holds good only
as to the entire cantharides, and not with cantharidin. It is very
possible that cantharidin is not the only poisonous principle in the insect.
The symptoms in other cases, fatal or not, have been as follows:–Imme-
diate burning in the mouth and throat, extending to the stomach and
alimentary canal, and increasing in intensity until there is considerable
pain. Then follow salivation, difficulty in swallowing, and vomiting, and
generally diarrhoea, pain in the kidneys, irritation of the bladder,
priapism, and strangury, are all present. The pulse is accelerated, the
breathing disturbed, there are pains in the head, and often mydriasis,
giddiness, insensibility, delirium, and convulsions; trismus has been
noticed. The desire to micturate frequently is urgent, the urine is
generally bloody, and contains pus. Pregnant women have been known
to abort. In a few of the cases in which a different course has been
* Schroff, Zeitschrift d. Ges, d. Aerzte in Wien, 13, 56.
§ 640, 641.] CANTHARIDES. 495
run, the nervous symptoms have predominated over those of gastro-
intestinal irritation, and the patient has sunk in a kind of collapse.
In a case of chronic poisoning by cantharides, extending over three
months, and recorded by Tarchioni Bonfanti,” after the first dose
appeared tetanic convulsions, which subsided in twenty-four hours,
there was later cystitis, and from time to time the tetanic convulsions
returned; gastro-enteritis followed with frequent vomiting, when, can-
tharides being found in the matters ejected, the otherwise obscure
nature of the illness was shown.
In a case recorded by Sedgwick, f following the gastro-enteric
symptoms, there were epileptic convulsions; in this instance also was
noticed an unpleasant smell, recalling the notion formerly held that
cantharides imparted a peculiar odour to the breath and urine. In
a case of chronic poisoning related by Tardieu, six students, during
several months, used what they thought was pepper with their food,
but the substance proved to be really powdered cantharides. The
quantity taken each day was probably small, but they suffered from
pain about the loins, and also irritation of the bladder. There was no
sexual excitement.
§ 640. Post-mortem. Appearances. –In a French criminal case, in
which a man poisoned his step-brother by giving cantharides in soup, the
pathological signs of inflammation of the gastro-intestinal tract were
specially evident, the mouth was swollen, the tonsils ulcerated, the
gullet, stomach, and intestines were inflamed, and the mucous membrane
of the intestines covered with purulent matter. In another case there
was an actual perforation 3 inches from the pylorus. The inflammatory
appearances, however, are not always so severe, being confined to
swelling and inflammation without ulceration. In all cases there has
been noted inflammation of the kidneys and urinary passages, and this
is seen even when cantharidin is administered to animals by subcuta-
neous injection. In the urine will be found blood and fatty epithelial
casts, as well as pus. The contents of the stomach or the intestines will
probably contain some remnants of powdered cantharides, if the powder
itself has been taken.
§ 641. Tests for Cantharidin, and its Detection in the Tissues,
etc.—The tests for cantharidin are—(1) Its form, (2) its action in
the subliming cell, and (3) its power of raising a blister.
The most convenient method of testing its vesicating properties, is to
allow a chloroformic solution of the substance supposed to be cantharidin
to evaporate to dryness, to add to this a drop of olive oil (or almond oil),
and to take a drop up on the smallest possible quantity of cotton wool,
and apply the wool to the inside of the arm, covering it with good oilskin,
* Gaz. Med. Ital. Lomb., 1863. f Med. Times, 1864.
496 POISONS: THEIR EFFECTS AND DETECTION. [$ 64.I.
and strapping the whole on by the aid of sticking-plaster. In about an
hour or more the effect is examined. The thin skin of the lips is far
more easily blistered than that of the arm, but the application there is
inconvenient.
Dragendorff has ascertained that cantharidin is not present in the
contents of a blister raised by a cantharides plaster, although it has been
found in the urine of a person treated by one ; and Pettenkofer has also
discovered cantharidin in the blood of a boy to whose spine a blister had
been applied.
The great insolubility of cantharidin in water has led to various
hypotheses as to its absorption into the system. It is tolerably easily
dissolved by potash, soda, and ammonia solutions, and is also taken up in
small proportion by sulphuric, phosphoric, and lactic acids. The result-
ing compounds quickly diffuse themselves through animal membranes.
Even the salts with lime, magnesia, alumina, and the heavy metals, are
not quite insoluble. A solution of salt with cantharidin, put in a
dialysing apparatus, separates in twenty-four hours enough cantharidin
to raise a blister.
Cantharidin has actually been discovered in the heart, brain, muscles,
contents of the stomach, intestines, and faeces (as well as in the blood
and urine) of animals poisoned by the substance. A urine containing
cantharidin is alkaline and albuminous. Cantharidin, although readily
decomposed by chemical agents, is so permanent in the body that it has
been detected in the corpse of a cat eighty-four days after death.
In any forensic case, the defence will not improbably be set up that
some animal (e.g. a fowl poisoned by cantharides) has been eaten and
caused the toxic symptoms, for cantharides is an interesting example of
a substance which, as before stated, for certain animals (such as rabbits,
dogs, cats, and ducks) is a strong poison, whilst in others (e.g. hedge-
hogs, fowls, turkeys, and frogs), although absorbed and excreted, it
appears, save in large doses, to be inert. Experiment has shown that a
cat may be readily poisoned by a fowl Saturated with cantharides; and
in Algeria the military surgeons meet with cystitis among the soldiers,
caused by eating frogs in the months of May and June, the frogs living
in these months almost exclusively on a species of Cantharis.
Dragendorff recommends the following process:–The finely-pulped
substance is boiled in a porcelain dish with potash-lye (1 part of potash
and 12 to 18 of water) until the fluid is of a uniform consistence. The
fluid, after cooling, is (if necessary) diluted with an equal bulk of water,
for it must not be too thick; then shaken with chloroform in order to
remove impurities; and after separation of the chloroform, strongly
acidified with sulphuric acid, and mixed with about four times its volume
of alcohol of 90 to 95 per cent. The mixture is kept for some time at a
§ 641.] CANTHARIDES. 497
boiling temperature, filtered hot, and the alcohol distilled from the fil-
trate. The watery fluid is now again treated with chloroform, as above
described. The chloroform extract is washed with water, the residue
taken up on some hot almond oil, and its blistering properties investi-
gated. The mass, heated with potash in the above way, can also be
submitted to dialysis, the diffusate supersaturated with sulphuric acid,
and shaken up with chloroform.
In order to test further for cantharidin, it can be dissolved in the
least possible potash or soda-lye. The solution, on evaporation in the
water-bath, leaves crystals of a salt not easily soluble in alcohol, and
the watery solution of which gives with chloride of calcium and baryta.
a white precipitate; with sulphate of copper and sulphate of protoxide
of nickel, a green; with cobaltous sulphate, a red; with sugar of lead,
mercury chloride and argentic nitrate, a white crystalline precipitate.
With palladium chloride there occurs a yellow, hair-like, crystalline
precipitate ; later crystals, which are isomorphous with the nickel and
copper salts.
If the tincture of cantharides has been used in considerable quantity,
the urine may be examined ; in such a case there will collect on the
surface drops of a green oil, which may be extracted by petroleum
ether; this oil is not blister-raising. Cantharides in powder may, of
course, be detected by its appearance.
To the question whether the method proposed would extract any
other blister-producing substance, the answer is negative, since ethereal
oil of mustard would be decomposed, and the active constituents of the
Euphorbias do not withstand the treatment with KHO. Oils of
anemone and anemonin are dissolved by KHO, and again separated
out of their solutions; but their blistering property is destroyed. They
are volatile, and found in anemone and some of the Ranunculaceae. In
the Aqua pulsatilla there is an oil of anemone, which may be obtained
by shaking with ether; but this oil is not permanent, and if the Aqua
pulsatilla stand for a little time, it splits up into anemonic acid and
anemonin, and then cannot be reobtained. A blistering substance,
obtained from the Anacardia orientalia and the fruit of the Anacardium
occidentale and Semecarpus anacardium, is not quite destroyed by a
short action with potash, but is by one of long duration; this substance,
however, cannot be confused with cantharidin, for it is oily, yellow,
easily soluble in alcohol and ether, and differs in other respects.
32
498 POISONs: THEIR EFFECTS AND DETECTION. [$642,643.
W.—Poisonous Snakes.
§ 642. The poisonous snakes are classified as follows:—
A. CoI,UBRIDAE, WENENOSA.
I. Opistoglypha (suspected snakes, “serpentes suspecti”).—Furrowless
teeth in the fore-part of the upper jaw, behind one or several poison
fangs. They are almost all poisonous, but seldom dangerous to man
or the larger animals. They are represented by Homalopsina, the
water snakes; Dipsadomorphinae, whip snakes; and Elachistodontinae.
II. Proteroglypha. —Furrowed teeth. The teeth in the fore-part of
the upper jaw are provided with a deep groove or furrow, in combination
with very often highly developed poison glands. This division includes
the sea-snakes Hydrophinae and the Elapinae. .
B. WIPERIDAE.
I. Crotalinae (pit vipers).-Head very broad. On both sides of the
head, between the eyes and nostrils, a deep depression or pit ; hence the
Ila, Iſle. -
II. Viperinae (vipers).—Head very broad, but possessing no pit like
the Crotalinae.
The Opistoglyphae are poisonous to small animals, and species belong-
ing to this order have occasionally caused illness in man.*
The Proteroglyphae include most of the poisonous snakes other than
vipers; to this order belong —
The sea-snakes (Hydrophinae), common in the Indian Ocean and in
the Pacific. The poison of the Enhydrina bengalensis has been investi-
gated by Leonard Rogers; he found it less resistant to heat than the
cobra poison; its physiological action strongly resembled that of the
cobra, but since the lethal dose for birds was so small as '05 mgrm, per
kilo., it appeared to be ten times stronger or more concentrated.
Fraser and Elliott have also made some observations on the poison
of Enhydrina valakadien, and found that the dried poison killed cats in
the proportion of '02 mgrm, rabbits '06 mgrm., and rats -09 mgrm.
per kilo. of body weight. c
§ 643. The Poison of the Cobra.-The poison excreted from the
salivary glands of the cobra di capello is one of the most deadly animal
fluids known. When first ejected, it is an amber-coloured, rather
syrupy, frothy liquid, of specific gravity 1-046, and of feeble acid
reaction; it dries rapidly on exposure to air to a yellow film, which
readily breaks up into brilliant yellow granules, closely imitating
* J. J. Quelch, Proceedings of the Zoological Society, 1898.
§ 643.] COBRA POISON. 499
crystals. The yellow powder is very acrid and pungent to the nostrils,
and excites a painful (though transitory) inflammation, if applied to
the mucous membrane of the eye; the taste is bitter, and it raises
little blisters on the tongue. It is perfectly stable, can be heated
to 100° C. without decomposition for a short time, and preserves its
activity for an indefinite time. The dried poison as described is
perfectly soluble in water, and if the water is added in proper
proportions, the original fluid is without doubt reproduced, the solution
usually depositing a sediment of epithelial débris, and often containing
little white threads.
The poison has been examined by several chemists, with various
results. The senior author isolated, in 1876, a crystalline principle as
follows:—The yellow granules were dissolved in water, the albumen which
the venom so copiously contains coagulated by alcohol, and separated by
filtration; the alcohol was then driven off at a gentle heat, the liquid
concentrated to a small bulk, and precipitated with basic acetate of
lead. The precipitate was separated, washed, and decomposed in the
usual way by SH2, and on removing the lead sulphide, crystals having
toxic properties were obtained. The authors have been unable, through
want of material, to deal with the suggestion of F. Norris Wolfenden that
the crystals were those of gypsum, their toxic properties being due to
adhering impurities.
Pedler, * precipitating the albumen by alcohol, and then to the
alcoholic solution adding platinic chloride, obtained a semi-crystalline
precipitate, which from an imperfect combustion he thinks may have
something like the composition PtCl2(C17H2:NAO, HCl)g.
The latest observer of the cobra poison, Edwin Stanton Faust,f claims
to have shown that the essential constituent of the cobra poison is a
nitrogen-free substance, belonging pharmacologically to the group of
the picrotoxins, sapotoxins, and sphacelo-toxins. To this substance he
gives the name of “ophiotoxin.”; he has obtained it in aqueous solution,
but directly the aqueous solution is concentrated in a vacuum, the
white residue obtained is in most cases inactive. The solution froths
on shaking; if injected subcutaneously it has but little action ; on the
other hand, if injected intravenously the ordinary effects of cobra
poison are produced. Hence Faust appears to believe that the poison of
the cobra is some compound of his ophiotoxin and an albuminoid body:
the combination being easily dissolved. He thinks that there is some
analogy between the cobra poison and the jalapin-elaterin group, in
which the free acids and their salts are inactive ; while, on the other
hand, the anhydrides are active.
* Proc. Roy. Soc., vol. xxvii. p. 17.
+ Die thierischen Gifte, Braunschweig, 1906.
5OO POISONS: THEIR EFFECTS AND DETECTION. [$ 644,645.
The blood of the cobra is also poisonous. A Calmette * has
found that 2 c.c. of fresh cobra blood injected into the peritoneum
of a rabbit weighing 1.5 kilo., causes death in six hours; the same
dose of the defibrinated blood injected into the veins is fatal in three
minutes.
§ 644. Fatal Dose.—From one of the senior author's experiments on
cats, rabbits, and birds, it seems probable that the least fatal dose for cats
and rabbits lies between 7 and 9 mgrm, per kilo., and for birds some-
where about 7 mgrm. per kilo. of the dried poison; the venom contains
about 60 per cent. of albuminous matter, and about 10 per cent, of
poisonous substance; therefore, the lethal power is represented by
something like '07 to 0.9 mgrm. per kilo., if the pure toxic principle
free from albumen and diluting impurities be considered. Calmette
calculated the fatal dose for a man at 10 mgrms, Fraser 31°7 mgrms,
and Elliott about 30 mgrms.
§ 645. Effects on Animals.-There has been much exact physio-
logical work done on the cobra poison since the last edition of this
work. One of the most complete researches is that by H. R. Elliott; f
he has confirmed the fact that cobra venom raises the blood-pressure ;
this action can be traced in the vessels of the frog, down to dilutions of
1 in ten million. If the solution is concentrated, it acts directly on
the isolated frog's ventricle, killing it in systole; but if the solution is
weak, the action of the heart is stimulated; this brings cobra venom
into line, pharmacologically, with the glucosides of the Strophantin
group. Elliott found that atropine sulphate and cobra venom in the
same solution intensify each other.
Cobra venom acts powerfully on the mammalian heart ; the action
is dual.
(1) A direct action on the muscular fibres or on the nerve endings.
(2) An action on the intra-cardial vagal mechanism.
Concentrated solutions cause irregular and extreme cardiac excita-
tion, with early death in systole; with less concentrated solutions, the
early stage of excitement yields to a prolonged phase in which the
tonic action of the poison in the heart is most pronounced, the beat is
regular, steady, and strong.
When given subcutaneously in low lethal doses, death occurs from
paralysis of the respiratory centre; there is a gradually increasing
venosity of the blood, and if life is prolonged beyond the usual term
(five hours) the phrenic and other motor nerves may become paralysed.
If a large dose be given intravenously, the respiration may cease
almost at once. By applying cobra venom direct to the exposed
medulla oblongata of the rabbit, Elliott has shown that the respiratory
* Compt. rend. Soc. de Biol., 1894. f Phil. Trans., 1905.
§ 646.] COBRA POISON. 5OI
centre can be paralysed without the phrenic nerve ends or the heart
being appreciably affected.
If very large doses be given, the direct action of the poison on the
heart may produce death by cardiac failure. Such large doses cause (a)
a sudden fall of blood-pressure; (b) a subsequent rise, if the dose has
not been too large; (c) a final fall to zero.
Cobra poison, in common with that of most of the Colubridae, prevents
the coagulation of the blood, in contradistinction to the viper poisons,
which strongly coagulate blood; both classes of poison appear to dis-
solve out the red colouring matter of the blood.
The post-mortem appearances are not very distinctive; at the
point of injection, there is often a slight haemorrhagic oedema.
The liver and the spleen show on their surfaces circumscribed
haemorrhagic spots; the peritoneum, the meninges, endocardium,
pleura, and mucous membranes show frequently ecchymoses, and
the blood is fluid and dark.
§ 646. Effects on Man.—By far the best account hitherto published
of the effects of the cobra poison is a paper by Dr. Wall,” in which
he points out the very close similarity between the symptoms produced
and those of glosso-pharyngeal paralysis. This is well shown in the
following typical case:—A coolie was bitten on the shoulder about
twelve at midnight by a cobra ; he immediately felt burning pain at
the spot bitten, which increased. In fifteen minutes afterwards he
began, he said, to feel intoxicated, but he seemed rational, and
answered questions intelligently. The pupils were natural, and the
pulse normal; the respirations were also not accelerated. He next
began to lose power over his legs, and staggered. In thirty minutes
after the bite his lower jaw began to fall, and frothy viscid mucous
saliva ran from his mouth ; he spoke indistinctly, like a man under
the influence of liquor, and the paralysis of the legs increased.
Forty minutes after the bite, he began to moan and shake his head
from side to side, and the pulse and respirations were somewhat
accelerated ; but he was still able to answer questions, and seemed
conscious. There was no paralysis of the arms. The breathing
became slower and slower, and at length ceased one hour and ten
minutes after the bite, the heart beating for about one minute after
the respiration had stopped. .
There is often very little sign of external injury, merely a scratch or
puncture being apparent, but the areolar tissue lying beneath is of a
purple colour, and infiltrated with a large quantity of coagulable, purple,
* “On the Difference of the Physiological Effects Produced by the Poison of
Indian Venomous Snakes,” by A. T. Wall, M.D., Proc. Roy. Soc., 1881, vol. xxxii.
p. 333.
5O2 POISONS : THEIR EFFECTS AND DETECTION. [$ 647.
blood-like fluid. In addition, the whole of the neighbouring vessels are
intensely injected, the injection gradually diminishing as the site of the
poisoned part is receded from, so that a bright scarlet ring surrounds a
purple area, and this in its turn fades into the normal colour of the
neighbouring tissues. At the margin is also a purple blood-like fluid,
replaced by a pinkish serum, which may often be traced up in the
tissues surrounding the vessels that convey the poison to the system,
and may extend a considerable distance. These appearances are to be
accounted for in great part by the irritant properties of the cobra
venom. The local hyperaemia and the local pain are the first symptoms.
In man there follows an interval (which may be so short as a few
minutes, or so long as four hours) before any fresh symptoms appear;
the average duration of the interval is, according to Dr. Wall, about an
hour. When once the symptoms are developed, then the course is
rapid, and, as in the case quoted, a feeling like that of intoxication is
first produced, and then loss of power over the legs. This is followed
by a loss of power over the speech, over swallowing, and the movement
of the lips; the tongue becomes motionless, and hangs out of the
mouth ; the saliva is secreted in large quantities, and runs down the
face, the patient being equally unable to swallow it or to eject it, and
the glosso-pharyngeal paralysis is complete.
§ 647. Cobra Anti-toxin.—All the so-called antidotes, such as gold
chloride, potassic permanganate, and others, have proved to be useless;
for, although chemical agencies may make the poison clinging to the
wound inert, such reagents fail to neutralise the absorbed poison. It
had long been known that animals dosed subcutaneously by quantities
of cobra or other snake venom, insufficient to kill, acquired a certain
degree of immunity against the same poison ; this induced Calmette to
endeavour to obtain an anti-venom serum on the same principle, as to
preparation, as the well-known commercial anti-toxin for diphtheria. In
this Calmette, working in the Lille Institute, has been to a great
extent successful. Horses and donkeys are the animals selected to
produce the immunising and curative serum ; these animals are injected
with ever-increasing doses of cobra poison, until they bear without
reacting two hundred times the otherwise deadly dose—e.g. the fatal
dose for a horse is about 10 mgrms. of the dried cobra venom, and a
horse after successful treatment will bear the injection of a quantity
equal to no less than 2 grms. Many animals during the process die of
endocarditis or nephritis, which affections must therefore be considered
as true sequelae to chronic cobra poisoning. The serum obtained from
the blood of an animal which is considered highly resistant is tested
by mixing a definite quantity of it with an equally definite quantity of
cobra venom, and injecting it into some small animal. The serum is
§ 647A] FOISONOUS SNAKES. 503
considered sufficiently active if 2 c.c. of serum mixed with 1 mgrm. of
cobra venom produces no poisonous symptoms when injected into a
rabbit, and if 2 c.c. of the serum injected into a rabbit 2 kilogrammes
in weight protects it from the effects of 1 mgrm. of cobra venom in-
jected subcutaneously an hour later.
The serum is preserved with strict antiseptic precautions in 10-c.c.
tubes; it is said not to lose its activity for two years or even longer.
Another method of preserving the serum is drying it at a low tempera-
ture; it then appears in commerce as light dry yellow scales, which for
subcutaneous use are dissolved in water at the time. For ten years
now the Pasteur Institute at Lille has prepared this form of anti-toxin;
at first it was hoped that in such a substance was to be found a general
remedy for, or protection against, snake bite, but this is not so ; its action
is confined to either the particular species of snake venom, or species
nearly allied, against which the horse was immunised. Experiments are,
however, being made in order to obtain if possible a general sort of
serum, by operating with mixtures of venoms; whether success will be
attained time alone can show.
$647A. Other Colubrine Snakes.—Bungarus fasciatus, or the Banded
Krait, acts similarly to the cobra poison ; but since its activity is
destroyed by heating from 73°–75°, it is less stable.
Bungarus caeruleus, or the Krait, one of the most dreaded of the
Indian snakes, is said to be even more virulent than the cobra.*
Naja Bungarus, or the Hamadryad, possibly the largest poisonous
snake in the world, growing to over 13 feet in length ; the Naja haje
(Cleopatra's asp); Elaps corallinus, the brilliant red coral snake of
America; the Elapinſe of Australia—all possess a venom having a
physiological action similar to that of the cobra.
The Viperidae.—The chief poisonous snakes belonging to the
Viperidae, besides the true vipers, are the American rattlesnakes,
belonging to the genus Crotalus—viz., the Lachesis muta (Crotalus
nutus), commonly called the surucucu, or bushmaster of the Dutch
colonists of Surinam, one of the largest venomous snakes; the Copper-
head, also known under the name of Chunk-head; Deaf Adder and
Pilot snake (Trigonocephalus contortus); various species of Bothrops in
the Brazils. There is also a species of Trimeresurus in one of the
Japanese islands, which appears to be specially aggressive, and kills
some 48–70 hours after the bite.
The poisons of these snakes appear to be different from that of the
cobra and more analogous to the poison of the true vipers.
* Leonard Rogers, M.D., Phil. Transac., 1904. Major R. H. Elliott and
W. C. Sillar, M.B., ibid. Some Observations on the Poison of the Banded Krait
(Bungarws fasciatus), by Capt. George Lamb, M.D. Glas., Calcutta, 1904.
504 POISONS: THEIR EFFECTS AND DETECTION. [$647B,647C.
§ 647B. Duboia Russellii.—The Duboia russellii or Russell's viper is
one of the best known and most deadly of the Indian vipers. The
poison of the viper differs from that of the cobra in causing greater
local effect; it also coagulates the blood instead of making it more fluid.
Viper poison apparently digests fibrin; it is not very stable, as a heat
of about 80°–85° destroys it. The effects of the poison of this viper
are also different from those of the cobra. The action commences by
violent general convulsions, which are often at once fatal, or may be
followed by rapid paralysis and death ; or these symptoms, again, may
be recovered from, and death follow at a later period. The convulsions
do not depend on asphyxia, and with a small dose may be absent. The
paralysis is general, and may precede for some time the extinction of
the respiration ; the pupils are widely dilated, there are bloody dis-
charges, and the urine is albuminous. Should the victim survive the
first effects, then blood-poisoning may follow, and a dangerous illness
result, often attended with copious hæmorrhages. A striking example
of this course is recorded in the Indian Med. Gaz., June 1, 1872.
A Mahommedan, aged 40, was bitten on the finger by Russell's viper;
the bitten part was soon after excised, and stimulants given. The hand
and arm became much swollen, and on the same day he passed blood by
the rectum, and also bloody urine. The next day he was sick, and still
passing blood from all the channels; in this state he remained eight days,
losing blood constantly, and died on the ninth day. Nothing definite is
known of the chemical composition of the poison; it is probably qualita-
tively identical with “viperin.”
§ 647C. The Poison of the Common Viper.—The common viper still
abounds in certain parts of Great Britain, as, for example, on Dartmoor.
The venom was analysed in a partial manner by Valentin. In 1843
Prince Lucien Bonaparte separated a gummy varnish, inodorous,
glittering, and transparent, which he called echºdnin or viperim ; it was
a neutral nitrogenous body without taste, it arrested the coagulation of
the blood, and, injected into animals, produced all the effects of the
bite of the viper. Phisalix and G. Bertrand have studied the symptoms
produced in small animals after injection. A guinea-pig, weighing
500 grms., was killed by 0°3 grn. of the dried venom dissolved in
5000 parts of saline water; the symptoms were nausea, quickly passing
into stupor. The temperature of the body fell. The autopsy showed
the left auricle full of blood, the intestine, lungs, liver, and kidneys
injected. The blood of the viper is also poisonous, and produces the same
symptoms as the venom.* The puff adder (Vipera arietans) is found in
south and equatorial Africa; the Hottentots use either the crushed head
or the poison glands as an arrow poison. -
* Compt, rend. Soc. de Biol., t. v. 997.
§ 647D.] MAMMALIAN POISON. 505
WI. Mammalian Poison.
§ 647D. Epinephrin (adrenalin-suprarenin), C, HisOAN.—This sub-
stance was first isolated in an impure condition from the suprarenal gland
by Abel and Crawford in 1897, and has received much attention since
that date on account of its extraordinary physiological activity. The
researches of a number of chemists—e.g. Von Furth, Pauly, Jowettº—
have now settled the constitutional formula of epinephrin, showing it to
be a methylamino-derivative of catechol:
OH
ſNoh
NZ
CH(OH)
CH.NHCH,
On oxidation with permanganate, formic and oxalic acids are obtained
and methylamine; on fusion with KOH, the resulting product con-
tains proto-catechuic acid; on complete methylation and subsequent
oxidation with permanganate, it yields trimethylamine and veratric acid.
All these reactions are consistent with the above formula.
Jowett and Barger have further confirmed the constitution of
epinephrin by the synthesis of a methylene ether:
which, on treatment with HCl at 150°, yields a substance having the
chemical and physiological properties of epinephrin (Journ. Chem. Soc.,
Trans., 1905). H. D. Dakin has shown that, starting with catechol,
a body may be prepared having the same formula as epinephrin and
having the same reaction, and of great physiological activity, but it is
optically inactive. A number of allied substances have also been
prepared which cause a rise in the blood-pressure (Proc. Physiol. Soc.,
1905. J. Physiol. xxxii.). -
Epinephrin is obtained from the suprarenal glands by precipitating
the aqueous extract by lead acetate or alcohol to get rid of impurities,
and finally adding ammonia. From the ammoniacal liquid, small crystals
ultimately separate; these are dissolved repeatedly in acid and
precipitated by ammonia: it has also been obtained pure by first
* “The Constitution of Epinephrine,” by Hooper Albert Dickinson Jowett,
Journ. Chem. Soc., Trans., 1904.
506 POISONs: THEIR EFFECTS AND DETECTION. [$ 647E,648.
converting epinephrin into a salt, dissolving in alcohol, and fractionally
precipitating with ether.
Epinephrin is soluble with difficulty in cold water, but better in hot ;
it is insoluble in chloroform, amyl-alcohol, carbon disulphide, ether,
acetone, and petroleum ether; in alcohol it is slightly soluble. The
caustic alkalies dissolve it, but neither the carbonates of the alkalies nor
ammonia.
It is not precipitated by the group alkaloidal reagents; it reduces
Fehling's solution, and also ammoniacal silver solution. It forms soluble
salts with acids, reacts feebly alkaline to litmus paper, and its aqueous
solution becomes red on exposure to the air, turning later to brown.
The addition of ferric chloride to such solution produces a characteristic
green colour. Epinephrin polarises; its specific rotation, according to
Jowett, is [a]p = – 32-0°. +
§ 647E. Physiological Action of Epinephrin.—The primary action is
on the blood-vessels and the heart. Applied to the skin or to a mucous
membrane, it produces an extraordinary contraction of capillaries and
arteries, so as to diminish greatly the blood supply; hence its great
use in surgery. If injected intravenously, fractions of a mgrm. cause
in dogs or rabbits a large sudden increase of the blood-pressure; but in
consequence of destruction or change of the poison, this increased blood-
pressure is of very short duration. After subcutaneous doses of
epinephrin, glycosuria has been observed. W. Erb, junior,” has found
that if from 0-1 to 1 mgrm. of epinephrin is injected into rabbits for a
length of time—e.g. 10–60 days—disease of the aorta and other large
arteries is induced.
Death occurs from heart paralysis or arrest of the respiration.
There is great danger in treating human patients with subcutaneous
injections of epinephrin, if the heart is already weakened by disease;
in such a case death may occur, probably from the sudden stress put
on the circulation from the increased blood-pressure.
DIVISION II.—PTOMAINES-ANIMAL TOXINEs.
§ 648. In the last edition of this work a ptomaine was defined as
a basic chemical substance derived from the action of bacteria on
nitrogenous substances. This definition can no longer be accepted, for
ptomaines may be produced by the action of enzymes, without the
intervention of bacterial life. The word “ptomaine” itself is open to
objection, and although still used in newspapers and popular diction,
* Archiv f. eacp. Path, w. Pharmakologie, 1905.
§ 649, 650.] ANIMAL TOXINES. 507
is getting rare in the stricter language of recent pharmacology and
physiology. It will be best at present to classify the so-called ptomaines
as “animal toxines,” a large number of which appear to be the pro-
duction of special bacteria —in some, and indeed in most cases, they
appear to be the excretory products of the bacteria ; on the other hand,
it has been shown that the typhoid bacillus, the Bacillus coli communis,
the Bacillus enteritidis, Gaertner, and the Bacillus dysenteriae, all contain
endo-toxines, which have a similar physiological action, causing in the
rabbit great lowering of the body temperature, diarrhoea, prostration,
with sudden collapse and death. The foul-smelling bodies occurring in
putrefactive processes, contrary to general belief, have but slight
physiological action.
Isolation of Animal Toxines.
§ 649. Gautier's “Process.-The liquid is acidified with oxalic acid,
warmed, filtered, and distilled in a vacuum.
In this way pyrrol, skatol, phenol, indol, and volatile fatty acids are
separated and will be found in the distillate. The residue in the retort
is treated with lime, filtered from the precipitate that forms, and distilled
in a vacuum, the distillate being received in weak sulphuric acid. The
bases accompanied with ammonia distil over. The distillate is now
neutralised by sulphuric acid f and evaporated nearly to dryness,
separating the mother liquid from sulphate of ammonia, which crystallises
out. The mother liquids are treated with absolute alcohol, which dis-
solves the sulphates of the ptomaines. The alcohol is got rid of by
evaporation, the residue treated with caustic soda, and the bases
shaken out by successive treatment with ether, petroleum ether, and
chloroform. The residue remaining in the retort with the excess of
lime is dried, powdered, and exhausted with ether; the ethereal extract
is separated, evaporated to dryness, the dry residue taken up in a
little water, slightly acidulated, and the bases precipitated by an
alkali.
§ 650. Brieger's Process.-Brieger f thus describes his process:–
The matters are finely divided and boiled with water feebly acidulated
with hydrochloric acid.
Care must be taken that, on boiling, the weak acid reaction is
retained, and that this manipulation only lasts a few minutes.
* Ptomaines et Leucomaines, E. J. A. Gautier, Paris, 1886.
1. The first acid apparently is so dilute that the distillate more than neutralises
it, hence more sulphuric acid is added to complete neutralisation.
# Unterswchwrºgen über Ptomaine, Theil iii., Berlin, 1886.
508 POISONS : THEIR EFFECTS AND DETECTION. [$650.
The insoluble portion is filtered off, and the filtrate evaporated, either
in the gas-oven or on the water-bath, to syrupy consistency. If the
substances are offensive, as alcoholic and watery extracts of flesh usually
are, the use of Bocklisch's simple apparatus (see diagram) is to be
recommended. The filtrate to be evaporated is
placed in a flask provided with a doubly per-
forated caoutchouc cork carrying two bent tubes;
the tube b terminates near the bottom of the
flask, while the tube a terminates a little above
the level of the fluid to be evaporated. The
tube a is connected with a water pump which
sucks away the escaping steam. In order to
avoid the running back of the condensed water
forming in the cooler part of the tube, the end
of the tube a is twisted into a circular form.
Through the tube b, which has a fine capillary
bore, a stream of air is allowed to enter, which
keeps the fluid in constant agitation, continually
destroying the scum on the surface, and avoiding
sediments collecting at the bottom, which may
cause fracture of the flask. According to the
regulation of the air current, a greater or smaller vacuum can be pro-
duced. The fluid, evaporated to the consistency of a syrup, is treated
with 96 per cent. alcohol, filtered, and the filtrate precipitated with
lead acetate. -
The lead precipitate is filtered off, the filtrate evaporated to a syrup,
and the syrup again treated with 96 per cent. alcohol. This is again
filtered, the alcohol got rid of by evaporation, water added, the lead
thrown down by SH2, and the fluid, after the addition of a little
hydrochloric acid, evaporated to the consistence of a syrup; this syrup
is exhausted with 96 per cent. alcohol, and precipitated with an alcoholic
solution of mercury chloride. The mercury precipitate is boiled with
water, aud by the different solubility of the mercury salts of certain
ptomaines some separation takes place. If it is suspected that some of
the basic toxines may have been separated with the lead precipitate,
this lead precipitate can be decomposed by SH2 and investigated. “I
have only (says Brieger) in the case of mussels been able to extract from
the lead precipitate small quantities of ptomaines.”
The mercury filtrate is freed from mercury and evaporated, the
excess of hydrochloric acid being carefully neutralised by means of soda
(for it must only be slightly acid); then it is again treated with alcohol,
so as to separate as much as possible the inorganic constituents. The
alcoholic extract is evaporated, dissolved in a little water, neutralised
b (?,

§ 651.] ANIMAL TOXINES. 509
with soda, acidulated with nitric acid, and precipitated with phospho-
molybdic acid. The phospho-molybdic acid precipitate is decomposed
with neutral lead acetate, which process may be facilitated by heating on
the water-bath. After getting rid of the lead by treatment with SH2,
the fluid is evaporated to a syrup and alcohol added, by which process
many basic toxines may be eliminated as hydrochlorates; or they can
be converted into double salts (of platinum or gold) for the purpose of
separation. In the filtrate from phospho-molybdate, bases may also be
found by treating with lead acetate to get rid of the phospho-molybdic acid,
and then adding certain reactives. Since it is but seldom that the hydro-
chlorates are obtained in a state of purity, it is preferable to convert the
substance separated into a gold or platinum salt or a picrate, since the
greater or less solubility of these compounds facilitates the purification of
individual members; but which reagent is best to add, must be learned
from experience. The melting-point of these salts must always be
taken, so that an idea of their purity may be obtained. It is also to be
noted that many gold salts decompose on warming the aqueous solution;
this may be avoided by the addition of hydrochloric acid. The hydro-
chlorates of these bases are obtained by decomposing the mercury, gold,
or platinum combinations by the aid of SH2, while the picrates can be
treated with hydrochloric acid and shaken up with ether, which latter
solvent dissolves the picric acid.
Considerable difficulty in the purification of the bases is caused by
a nitrogenous, amorphous, non-poisonous, albumin-like substance, which
passes into all solutions, and can only be got rid of by careful pre-
cipitation with an alcoholic solution of lead acetate, in which it is
soluble in excess. This albuminoid forms an amorphous compound with
platinum, and acts as a strongly reducing agent (the platinum compound
contains 29 per cent, platinum). When this albuminoid is eliminated,
then the hydrochlorates or the double salts of the bases crystallise.
§ 651. The Benzoyl Chloride Method.—The fatty diamines in dilute
aqueous solutions, shaken with benzoyl chloride and soda, are converted
into insoluble dibenzoyl derivatives; these may be separated from
benzamide and other nitrogenous products by dissolving the precipitate
in alcohol, and pouring the solution into a large quantity of water.”
Compounds which contain two amido groups combined with one
and the same carbon atom, do not yield benzoyl derivatives when
shaken with benzoyl chloride and soda. Hence this reaction can be
utilised for certain substances only. The solution must be dilute,
because concentrated solutions of creatine, creatinine, and similar bodies
also give precipitates with benzoyl chloride; no separation, however,
occurs unless these bodies are in the proportion of five per thousand,
* L. V. Udrànsky and Baumann, Ber., xxi. 2744.
5 IO POISONS : THEIR EFFECTS AND DETECTION. [$ 652.
The process is specially applicable for the separation of ethylene-
diamine, pentamethylenediamine (cadaverine), and tetramethylenedia-
mine (putrescine) from urine. In a case of cystimuria Udränsky and
E. Baumann * have found 0.24 grm. of benzoyltetramethylenediamine,
0.42 grm. of benzoylpentamethylenediamine in a day. Diamines are
absent in normal faeces and urine. Stadthagen and Brieger f have also
found, in a case of cystinuria diamines, chiefly pentamethylenediamine.
The operation is performed by making the liquid alkaline with soda
so that the alkalinity is equal to about 10 per cent., adding benzoyl
chloride, shaking until the odour of benzoyl chloride disappears, and
then filtering; to the filtrate more benzoyl chloride is added, the liquid
shaken, and, if a precipitate appears, this is also filtered off, and the
process repeated until all diamines are separated.
The precipitate thus obtained is dissolved in alcohol, and the
alcoholic solution poured into a considerable volume of water and
allowed to stand over night ; the dibenzoyl compound is then usually
found to be in a crystalline condition. The compound is crystallised
once or twice from alcohol or ether, and its melting-point and properties
studied. Mixtures of diamines may be separated by their different
solubilities in ether and alcohol.
A solution of 0:00788 grn. of pentamethylenediamine in 100 c.c.
of water gave 0-0218 grm. of the dibenzoyl-derivative when shaken with
benzoyl chloride (5 c.c.) and 40 c.c. of soda (10 per cent.) and kept for
twenty-four hours. In a second experiment with a similar solution only
0-0142 grm. of dibenzoyl-derivative was obtained ; ; hence the process is
not a good quantitative process, and, although convenient for isolation,
gives, so far as the total amount recovered is concerned, varying results.S
§ 652. The Amines. – The amines are bases originating from
ammonia and built on the same type. Those that are interesting as
poisons are monamines, diamines, and the quaternary ammonium bases.
Considered as compound ammonias, the amines are divided into
primary or amide bases, secondary or imid bases, and tertiary or nitrile
bases, according as to whether one, two, or three atoms of hydrogen
have been displaced from the ammonia molecule by an alkyl ; for
instance, methylamine NH2CHs is a primary or amide base, because
* L. W. Udransky and Baumann, Zeit. f. physiol. Chem..., xiii. 562.
f Arch. pathol. Anatom., Czv. p. 3. £ Ber., xxi. 2744.
§ J. Otori has shown that most of the amines as well as betaine, choline, neurine,
and lysine form difficultly soluble compounds with picro-lonic acid : hence this acid
may be used as a group reagent like benzoyl chloride. A. Loewy and C. Neuberg
have shown that an ether solution of phenylisocyanate is useful for the separation
of certain diamines, compounds with the diamines being readily formed. The
phenyl-diamine compounds are dried, dissolved in pyridine so as to form a saturated
solution ; out of this acetone precipitates (if present) immediately the tetramethylene
derivative, whereas the others require hours to separate (Zeit. f. physiol. Chemie, xliii.).
§ 652.] THE AMINES. . 5 II
only one of the three atoms of H in NH3 has been replaced by methyl ;
similarly, dimethylamine is a secondary or imid base, and trimethyl-
amine is a tertiary or nitrile base.
The quaternary bases are derived from the hypothetical ammonium
hydroxide NH4OH, as, for example, tetraethyl ammonium hydroxide
(C2H5)4N,OH.
The diamines are derived from two molecules of NH, and therefore
contain, instead of one molecule of nitrogen, two molecules of nitrogen ;
in two molecules of ammonia there are six atoms of hydrogen, two,
four, or six of which may be replaced by alkyls; as, for example,
C.H., C.H., C2H4
Né HH – N Néº, N Néj. N
HH HH C2H4
Ethylenedianine. Diethylenediamine. Triethylenediamine.
The monamines are similar to ammonia in their reactions; some of
them are stronger bases; for instance, ethylamine expels ammonia from
its salts. The first members of the series are combustible gases of
pungent odour, and easily soluble in water; the higher homologues are
fluids; and the still higher members solids.
The hydrochlorides are soluble in absolute alcohol, while chloride of
ammonium is insoluble; this property is taken advantage of for separat-
ing amines from ammonia. The amines form double salts with platinic
chloride; this is also utilised for recognition, for the purpose of separa-
tion, and for purification ; for instance, ammonium-platinum-chloride on
ignition yields 43.99 per cent. of platinum, and methylamine-platinum-
chloride yields 47.4 of platinum. It is comparatively easy to ascertain
whether an amine is primary, secondary, or tertiary.
The primary and secondary amines react with nitrous acid, but not
the tertiary; the primary amines, for instance, are converted into
alcohols, and there is an evolution of nitrogen gas; thus methylamine is
decomposed into methyl alcohol, nitrogen, and water.
CH, NH, 4-(OH)N0=CH2(OH) + N,+H,0.
The secondary amines, treated in the same way, evolve no nitrogen,
but are converted into nitrosamines; thus dimethylamine, when treated
with nitrous acid, yields nitrosodimethylamine, *
(CHS),NH+(OH)NO = (CH,),(NO)N +H,0;
and the nitrosamines respond to the test known as Lieberman's nitroso-
reaction, which is thus performed :—The substance is dissolved in
phenol and a few drops of concentrated sulphuric acid added. The
yellow colour at first produced changes into blue by adding to the
acid liquid a solution of potash.
The primary amines, and the primary amines alone, treated with
5 I2 POISONS: THEIR EFFECTS AND DETECTION.
[$ 652.
chloroform and alcoholic potash, yield the peculiarly offensive smelling
carbylamine or isonitrile (Hofmann's test),
NH,(CHA) + CHCl, +3KOH =C=N.-CH, +3KC1+3H,0.
Again, the primary bases, when treated with corrosive sublimate and
carbon disulphide, evolve sulphuretted hydrogen, and mustard oil is
produced, e.g., -
NH3(C.H.) + CS, = CSTN—C, H, 4-H, S.
Ethylamine. Ethylmustard oil.
Where a sufficient quantity of an amine is obtained, the primary,
secondary, or tertiary character of the amine may be deduced with
certainty by treating it with methyl or ethyl iodide.
A molecule of the base is digested with a molecule of methyl iodide
and distilled with potash; the distillate is in the same manner again
treated with methyl iodide and again distilled ; and the process is
repeated until an ammonium base is obtained, which will take up no
more iodide. If three methyl groups were in this way introduced, the
original substance was primary ; if two, secondary; if one, tertiary.
The quaternary bases, such as tetraethyl ammonium oxhydrate, de-
compose, on heating, into triethylamine and ethylene; the corresponding
methyl compound in like manner yields trimethylamine and methyl-
alcohol.
On the other hand, the primary, secondary, and tertiary bases do not
decompose on heating, but volatilise without decomposition.
The chief distinctions between these various amines are conveniently
put into a tabular form as follows:–
Primary, Secondary, Tertiary, Quaternary,
NH2R. NHR2. NR3. NR4(OH).
On treating with methyl
iodide it takes up the
following number of
methyl groups, . . . . 3 2 1
Reaction with nitrous
acid, . Decomposes | Formation of
with evolu- | n it ros-
tion of ni amine.
trogen gas.
Mustard oil, &c., on treat-
ment with CS2 and sub-
limate, . . . . . Mustard oil
formed.
Chloroform and alcoholic
potash, . Formation of
c a r by 1-
amine.
Effect of strong heat, . Sublimes. Sublimes. Sublimes. Decomposes.
On addition of acids, . Combines to | Combines to Combines to e - e.
form salts. form salts. form salts.
§ 653–659.] THE AMINES. 5 I 3
§ 653. Methylamine, CH3NH2. —This is a gas at ordinary temperatures ; it is
inflammable, and possesses a strong ammoniacal odour. It has been found in herring
brine, and is present in cultures of the comma bacillus; it has also been found in
poisonous sausages, but it is not in itself toxic.
It forms crystalline salts, such as, for example, the hydrochloride, the platino-
chloride (Pt=41.4 per cent.), and the aurochloride (Au = 53.3 per cent, when anhy-
drous). The best salt for estimation is the platinochloride, insoluble in absolute
alcohol and ether.
§ 654. Dimethylamine, (CH3)3NH.—Dimethylamine also is a gas; it has been
found in various putrefying substances. It forms crystalline salts, such as the
hydrochloride, the platinochloride (Pt=391 per cent.), and an aurochloride (Au =
51 ‘35 per cent.). It is not poisonous.
In Brieger's process it may occur in both the mercuric chloride precipitate and
filtrate. From cadaverine it may be separated by platinum chloride ; cadaverine
platinochloride is with difficulty soluble in cold water and crystallises from hot water,
while dimethylamine remains in the mother liquor. From choline it may be
separated by recrystallising the mercuric precipitate from hot water. From methyl-
amine it may be separated by converting into chloride and extracting with
chloroform ; dimethylamine chloride is soluble, methylamine chloride insoluble in
chloroform.
§ 655. Trimethylamine, (CH3)3N. — Trimethylamine in the free state is an
alkaline liquid with a fishy odour, boiling at 9:3°; it is not toxic save in large
doses.
It occurs in a great variety of plants, and is also found in putrefying substances.
It is a product of the decomposition of choline, betaine, and neuridine, when these
substances are distilled with potash.
In Brieger's process, if an aqueous solution of mercuric chloride is used as the
precipitant, trimethylamine (if present) will be almost entirely in the filtrate, from
which it can be obtained by getting rid of the mercury by SH2, filtering, evaporating
to dryness, extracting with alcohol, and precipitating the alcoholic solution with
platinic chloride. It forms crystalline salts with hydrochloric acid, platinum
chloride, and gold chloride ; the platinum double salt yields 37 per cent. of
platinum, the gold salt 49.4 per cent. gold. The gold salt is easily soluble, and
this property permits its separation from choline, which forms a compound with
gold chloride soluble with difficulty.
§ 656. Ethylamine, C2H5NH2. —Ethylamine is in the free state an ammoniacal
liquid boiling at 187°. It is a strong base, miscible with water in every proportion.
It has been found in putrefying yeast, in wheat flour, and in the distillation of beet
sugar residues. It is not poisonous; the hydrochloride forms deliquescent plates
melting at 76°–80°; the platinochloride contains 39°1 per cent. of platinum, and
the gold salt 51°35 per cent. of gold. In other words, the same percentages as the
corresponding salts of dimethylamine, with which, however, it cannot be confused.
§ 657. Diethylamine, (C2H5), NH, is an inflammable liquid boiling at 57-5°; it
forms salts with hydrochloric acid, platinum and gold, etc.; the gold salt contains
47.71 per cent. of gold, and its melting-point is about 165°. •.
§ 658, Triethylamine, (C2H5)3M, is an oily base but slightly soluble in water, and
boiling at 89°–89.5°. It gives no precipitate with mercuric chloride in aqueous
solution ; it forms a platinochloride containing 31°8 per cent. of platinum. It has
been found in putrid fish.
§ 659. Propylamine. —There are two propylamines; one, normal propylamine,
CH3CH3. CH3.NH3, boiling at 47°–48°, and iso-propylamine, (CH3)2CH. NH2,
boiling at 31°5°; both are ammoniacal fish-like smelling liquids. The hydro-
chloride of normal propylamine melts at 155°–158°, and iso-propylamine chloride
melts at 139'5°.
33
5 I4 POISONS: THEIR EFFECTS AND DETECTION. [$ 660–662.
It has been found in cultures of human faeces on gelatin. None of the above
amines are sufficiently active in properties to be poisonous in the small quantities
likely to be produced in decomposing foods.
§ 660. Iso-amylamine, (CH3)2CH.CH, CH2, NH2, is a colourless alkaline liquid
possessing a peculiar odour. It boils at 97°–98°. It forms a deliquescent hydro-
chloride. The platinochloride crystallises in golden yellow plates.
Iso-amylamine occurs in the putrefaction of yeast, and is a normal constituent of
cod-liver oil. It is intensely poisonous, producing convulsions.
DIAMINES.
§ 661. Rate of Formation of Diamines.—Diamines are formed in
putrefactive processes generally where there is abundance of nitrogen.
Garcia” has attempted to trace the rates at which they are formed by
allowing meat extracts to decompose, precipitating by benzoyl chloride
(see p. 509) the dibenzoyl compound, and weighing; the following were
the results obtained : —
Time. Weight of benzoyl compound.
24 hours, . e * & * 0-56 grm.
2 days, & * te & wº 0-75 ,,
3 days, e g º © * 0-82 ,
4 days, ſº * tº g * 0-73 , ,
5 days, ge º tº e g 0.57 ,,
6 days, tº e * e & 0.58 ,,
s 662. Ethylidenediamine. —Brieger found in putrid haddock, in the filtrate from
the mercury chloride precipitate:—gadinine, neuridine, a base isomeric with
ethylenediamine C, HaN, (but which Brieger subsequently more or less satis-
factorily identified with ethylidenediamine), muscarine, and triethylamine; these
bases were separated as follows:–
The filtrate from the mercury chloride solution was freed from mercury by SH2,
evaporated to a syrup, and then extracted with alcohol. From the alcoholic solu-
tion platinum chloride precipitated neuridine ; this was filtered off, the filtrate freed
from alcohol and platinum, and the aqueous solution concentrated to a small volume
and precipitated with an aqueous solution of platinum chloride; this precipitated
ethylidene platinum chloride. The mother liquor from this precipitate was concen-
trated on the water-bath, and, on cooling, the platinochloride of muscarine crystal-
lised out. From the mother liquor (freed from the crystals), on standing in a
desiccator, the gadinine double salt crystallised out, and from the mother liquor
(freed from gadinine after removal of the platinum by SH3) distillation with KHO
recovered trimethylamine.
From the platinochloride of ethylenediamine, the chloride can be obtained by
treating with SH2, filtering, and evaporating; by distilling the chloride with a
caustic alkali, the free base can be obtained by distillation.
Ethylidenediamine is isomeric with ethylenediamine, but differs from it in the
following properties:—ethylidenediamine is poisonous, ethylenediamine is non-
poisonous.
Ethylenediamine forms a platinochloride almost insoluble in hot water, while the
ethylidene salt is more easily soluble. The properties of the gold salts are similar,
ethylenediamine forming a difficultly soluble gold salt, ethylidene a rather soluble
gold salt.
* Zeit. f. physiol. Chemie, xvii. 6. 571.
§ 663.] DIAMINES. 5 I 5
Ethylidenediamine forms a hydrochloride, C2H8N22HCl, crystallising in long
glistening needles, insoluble in absolute alcohol, rather soluble in water. The
hydrochloride gives precipitates in aqueous solution with phospho-molybdic acid,
phospho-antimonic acid, and potassium bismuth iodide; the latter is in the form of
red plates.
The platinochloride, C2H8N22HCl, PtCl (Pt=53.6 per cent.), is in the form of
yellow plates, not very soluble in cold water,
Ethylidenediamine, when subcutaneously injected into guinea-pigs,
produces an abundant secretion from the mucous membranes of the
nose, mouth and eyes. The pupils dilate, and the eyeballs project.
There is acute dyspnoea; death takes place after some twenty-four
hours, and the heart is stopped in diastole.
Trimethylenediamine is believed to have been isolated by Brieger
from cultivations in beef broth of the comma bacillus.
It occurs in small quantity in the mercuric chloride precipitate, and
is isolated by decomposing the precipitate with SH2, evaporating the
filtrate from the mercury sulphide to dryness, taking up the residue
with absolute alcohol, and precipitating by an alcoholic solution of
sodium picrate. The precipitate contains the picrate of trimethylene-
diamine, mixed with the picrates of cadaverine and creatinine. Cada-
verine picrate is insoluble in boiling absolute alcohol, the other picrates
soluble; so the mixed picrates are boiled with absolute alcohol, and the
insoluble cadaverine filtered off. Next, the picrates of creatinine and
trimethylenediamine are freed from alcohol, the solution in water
acidified with hydrochloric acid, the picric acid shaken out by treatment
with ether, and then the solution precipitated with platinum chloride ;
the platinochloride of trimethylenediamine is not very soluble, while
creatinine easily dissolves; so that separation is by this means fairly
easy.
It also gives a difficultly soluble salt with gold chloride.
The picrate consists of felted needles, melting-point 198”. Phospho-
molybdic acid gives a precipitate crystallising in plates; potassium
bismuth iodide gives dark-coloured needles. *
It produces in animals violent convulsions and muscular tremors;
but the substance has hitherto been obtained in too small a quantity
to be certain as to its identification and properties.
$663. Neuridine, C.H.I.N.—Neuridine is a diamine, and is apparently
the most common basic product of putrefaction ; it has been obtained
from the putrefaction of gelatin, of horseflesh, of fish, and from the yelk
of eggs. It is usually accompanied by choline, from which it can be
separated by converting the bases into hydrochlorides, choline hydro-
chloride being soluble in absolute alcohol, neuridine scarcely so. Brieger
isolated neuridine from putrid flesh by precipitating the watery extract
with mercuric chloride. He decomposed the mercury precipitate with
5 16 POISONS: THEIR EFFECTS AND DETECTION. [$ 664.
SH2, and, after having got rid of the sulphide of mercury by filtration,
he concentrated the liquid to a small bulk, when a substance separated
in crystals similar in form to urea; this was purified by recrystallisation
from absolute alcohol, and converted into the platinum salt.
Another method which may be used for the separation and purification
of neuridine is to dissolve it in alcohol and precipitate with an alcoholic
solution of picric acid ; the picrate may be decomposed by treatment with
dilute mineral acid, and the picric acid removed by shaking with ether.
The free base has a strong seminal odour. It is gelatinous, and has
not been crystallised. It is insoluble in ether and in absolute alcohol,
and not readily soluble in amyl alcohol. It gives white precipitates with
mercuric chloride, neutral and basic lead acetates. It does not give
Hofmann's isomitrile reaction. When distilled with a fixed alkali, it
yields di- and trimethylamine.
The hydrochloride, C.H11N32.HCl, crystallises in long needles, which
are insoluble in absolute alcohol, ether, benzol, chloroform, petroleum ;
ether, and amyl alcohol; but the hydrochloride is very soluble in water
and in dilute alcohol.
The hydrochloride gives no precipitate with mercuric chloride, potass-
mercuric iodide, potass cadmium iodide, iodine and iodide of potassium,
tannic acid, ferricyanide of potassium, ferric chloride, and it does not
give any colour with Frohde's reagent.
On the other hand, phosphotungstic acid, phospho-molybdic acid,
picric acid, potass-bismuth iodide, platinum chloride, and gold chloride
all give precipitates.
Neuridine hydrochloride is capable of sublimation, and at the same
time it is decomposed, for the sublimed needles show red or blue colours.
Neuridine platinochloride, C.H.I.N.,2HCl, PtClt, yields 38.1 per cent.
of platinum ; it crystallises in flat needles, soluble in water, from which
it is precipitated on the addition of alcohol.
The aurochloride has the formula C.H.I.N.,2HCl2AuCls; it is rather
insoluble in cold water, and crystallises in bunches of yellow needles.
On ignition, it should yield 50.3 per cent. of gold.
The picrate, C.H.I.N2,2C6H2(NO2)3OH, is almost insoluble in cold
water, and crystallises in needles. It is not fusible, but decomposes
at about 230°. -
Neuridine is not poisonous.
§ 664. Cadaverine (Pentamethylenediamine, C.H.I.N., -NH2CH2—
CH2-CH2—CH2CH3NH2) is formed in putrid animal matters, and in
cultures of the genus Spirillum. It has been found in the urine and
faeces in cases of cystimuria, and Roos” has separated it by the benzoyl-
chloride method from the faces of a patient suffering from tertian ague.
* Zeit. f. physiol. Chemie, xvi., 1892.
§ 664.] DIAMINES. 5 17
It may be formed synthetically by dissolving trimethylcyanide in
absolute alcohol, and then reducing by sodium (Mendius' reaction).
Cadaverine is a thick, clear, syrupy liquid, with a peculiar coniine- as
well as a semen-like odour. It absorbs eagerly CO2 from the air, and
ultimately is converted into a solid crystalline mass. It volatilises with
the steam when boiled with water, and may be distilled in the presence
even of the caustic alkalies and the alkaline earth without decomposition.
It does not give oil of mustard when treated with CS, and mercuric
chloride, nor does it give with chloroform and alcoholic potash, carbyl-
amine (isonitrile). If dehydrated by KHO, it boils at from 115°–120°
(Brieger).”
When cadaverine is treated with methyl iodide, two atoms of hydrogen
may be replaced with methyl, forming the base C, H13(CH3)3N, ; the
platinochloride of this last base crystallises in long red needles.
Cadaverine forms well-defined crystalline salts as well as compounds
with metals.
Cadaverine hydrochloride, C.H11N32HCl, crystallises in needles which
are deliquescent, or it may be obtained from an alcoholic solution in
plates. The crystals are insoluble in absolute alcohol, but readily
soluble in 96 per cent, alcohol. Putrescine hydrochloride, on the other
hand, is with difficulty soluble in alcohol of that strength; hence the
two hydrochlorides can be separated by taking advantage of their differ-
ence in solubility in 96 per cent. alcohol; but the better method for
separation is the benzoyl-chloride process (p. 509). On dry distillation-
cadaverine hydrochloride decomposes into NHa, HCl and piperidine
C.H.I.N. The compound with mercury chloride–C.H.I.N.,2HCl,4HgCl,
(Hg = 63-54 per cent.); melting-point, 214"–216?—is insoluble in alcohol
and in cold water; this property is also useful to separate it from putres-
cine, the mercury compound of which is soluble in cold water. The platino-
chloride, C.H.I.N.,2HCl, PtCl, (Pt =38:08 per cent.), crystallises in dirty
red needles; but, by repeated crystallisation, it may be obtained in clear
chrome yellow, short, octahedral prisms; it is soluble with difficulty in
hot water, insoluble in cold water. The salt decomposes at 235°–236°.
The aurochloride–C5H11N32.HCl2AuCl (Au = 61.5 per cent.), melt-
ing-point 188”—crystallises partly in cubes and partly in needles, and
is easily soluble in water. *
Other salts are the picrate, C.H.I.N.,2C6H2(NO2)3OH, melting-point
221° with decomposition; with difficulty soluble in cold, but dissolving
in hot water, and insoluble in absolute alcohol. There are also a neutral
oxalate, C.H11N3, H2C2O4 + 2 H2O, melting-point 160°; and an acid oxalate,
C.H11N32H2C2O4 + H2O, melting-point 143° with decomposition; both
these oxalates are insoluble in absolute alcohol.
* Brieger has also given to the pure base a boiling-point of 175°.
518 POISONS: THEIR EFFECTS AND DETECTION. [$ 665.
Cadaverine dibenzoyl—C, H,0(NHCOC.H.), melting-point 129°–130°
—crystallises in needles and plates, soluble in alcohol and slightly
Soluble in ether, insoluble in water.
It is not acted on by hot dilute acids or alkalies, and when dissolved
in concentrated hydrochloric acid and alcohol it is, only after prolonged
boiling, decomposed into benzoic acid and the free base. The benzoic
acid after getting rid of the alcohol by evaporation, can be removed by
shaking up with ether; then the hydrochloride can be decomposed by an
alkali and the free base obtained, or the platinum salt of cadaverine may
be formed by precipitation with platinum chloride. Should cadaverine
and putrescine be in the same liquid, the dibenzoyl compounds may be
separated as follows:—the crystalline precipitate is collected on a
filter, washed with water until the filtrate runs clear, and then dissolved
in warm alcohol; this solution is poured into twenty times its volume of
ether and allowed to stand; after a short time crystals form of the
putrescine compound, which are far less soluble in alcohol than those of
cadaverine dibenzoyl ; these crystals are filtered off and repeatedly
crystallised from alcohol until the melting-point is about 175°–176”.
The filtrate contains the cadaverine compound; this latter is recovered
by evaporating off the ether-alcohol.
§ 665. Putrescine–Tetramethylenediamine,
C.H.N.-NH.CH,CH.C.H.C.H.NH,
The free base is a clear liquid, with a semen-like odour, boiling-point
135°. It is a common base in putrefying animal substances, and also
occurs in the urine in cases of cystimuria. It can be obtained syntheti-
cally by reducing ethylene cyanide by the action of sodium in absolute
alcohol.
The best method of separating putrescine is the benzoyl chloride
method already given.
Putrescine forms crystalline salts, of which the following are the
most important :—
Putrescine hydrochloride, C4H19N32.HCl, forms long colourless
needles, insoluble in absolute alcohol, easily soluble in water.
The platinochloride, C.His N,2HCl, PtCl, (Pt = 39.2 per cent.), is
with difficulty soluble in cold water. When pure, the salt is in the
form of six-sided plates. -
The aurochloride, C, H, N,2HCl2AuCls 4-2H2O (Au = 513 per cent.),
is insoluble in cold water, in contradistinction to cadaverine aurochloride,
which easily dissolves.
The picrate, C, H, N,2C6H2(NO2)3OH, is a salt of difficult solubility.
It crystallises in yellow plates. It browns at 230°, and melts with
evolution of gas at 250°.
§ 666–669.] DIAMINES. 5 I 9
Dibenzoylputrescine, C.Hs(NHCOCs Hg), forms silky plates or long
needles, melting-point 175°–176”. By boiling it for twelve hours with
alcohol and strong hydrochloric acid the compound may be broken up into
hydrochloride of putrescine and free benzoic acid. As stated before, it
is less soluble in alcohol than the corresponding compound of cadaverine.
Putrescine is not poisonous. On the other hand, by repeated treat-
ment with methyl iodide, it takes up four methyl radicals, and the
tetramethyl compound, C.Hs(CH3), N2, produces symptoms similar to
those of muscarine poisoning.
NH,
§ 666. Metaphenylenediamine, C.H., , is a crystalline sub-
NH.3
stance, melting-point 63", boiling-point 27 6.3% The crystals are easily
soluble in alcohol or ether, with difficulty in water. The least trace of
nitrous acid strikes a yellow colour from the formation of triamidobenzol.
NH,1
§ 667. Paraphenylenediamine, C.H.3 2 , is in the form of
-- NH,4
tabular crystals, melting-point 140°, boiling-point 267°. If this substance
is oxidised with ferric chloride or manganese binoxide and sulphuric acid,
chinone is produced; if treated with SH, and ferric chloride, a violet
sulphur-holding colouring matter, allied to methylene blue, is formed ;
these reactions are tests for the presence of the para-compound.
Both these diamines are poisonous. Metaphenylenediamine pro-
duces, in the dog, the symptoms of an aggravated influenza with con-
tinual sneezing and hoarse cough, which, if the dose is large enough, ends
in coma and death. Paraphenylenediamine produces exophthalmia,
the tissues of the eye undergoing complete alteration.*
Both compounds, in doses of 100 mgrms. per kilo., cause more or
less salivation, with diarrhoea. The para-compound is more poisonous
than the meta-compound. So far, neither of these diamines have
been separated with certainty from the urine of sick persons, nor from
products of decomposition. w
§ 668. Hexamethylenediamine, C.Higns.—Hexamethylenediamine
has been found by A. Garcia i in a putrefying mixture of horse-flesh
and pancreas. * *
§ 669. Diethylenediamine, C, Hio N2, is a crystalline substance,
melting-point 104", boiling-point 145°–146°. After melting, it solidifies
on cooling, forming a hard crystalline mass. It is extremely soluble in
water, and is deposited from alcohol in large transparent crystals. A
technical product called “spermin piperazidin’ or “piperazine” has
been found by A. W. v. Hoffmann i to be identical with diethylene-
* Comptes Rend., cvii. 533–535. + Zeit. f. physiol. Chemie, xvii. 543–555.
† Ber., xxiii. 3297-3303.
52O POISONS: THEIR EFFECTS AND DETECTION. [$ 670, 671.
diamine. The hydrochloride crystallises in colourless needles, insoluble
in alcohol, readily soluble in water. The platinochloride, C, H16N2H2
PtCls, is in small yellow needles, and is fairly easily soluble in hot
water, but dissolves but slightly in hot alcohol. The mercuro-chloride,
C, Hio N2H2HgCl, crystallises in concentrically grouped needles, and is
readily soluble in hot water, but is reprecipitated on adding alcohol.
The picrate, C.H16N2, C, H2(NO2)3OH, crystallises from water in yellow
needles, almost insoluble in alcohol.”
§ 670. Mydaleine is a poisonous base discovered by Brieger in putrid
animal matters. It is probably a diamine, but has not been obtained in
sufficient quantity for accurate chemical study. The platinochloride is
extremely soluble in water, and only comes down from an absolute alcohol
solution. It has been obtained in a crystalline form, giving on analysis
3874 per cent. of platinum, C. 10-83 per cent., H. 3:23 per cent.
Mydaleine is very poisonous. Small quantities injected into guinea-
pigs cause dilatation of the pupil, an abundant secretion from the nose
and eyes, and a rise of temperature. Fifty mgrms, cause death. The
post-mortem appearances are not distinctive ; the heart is arrested in
diastole; the intestines and bladder are contracted. In cats it causes
profuse diarrhoea and vomiting. *
§ 671. Guanidine.—Guanidine may be considered to have a relation
to urea; for, if the oxygen of urea is replaced by the imide group NH,
guanidine originates thus:–
NH, NH,
Urea = o-co Guanidine = NHC(
NH, NH,
Hence guanidine from its structural formula is a carbodiamidimide.
Guanidine may be formed by the action of oxidising agents, such as
potassic chlorate and hydrochloric acid, on guanine ; or by heating
amide cyanide with ammonium chloride, and so forming guanidine
chloride. It is also produced from the oxidation of albumin. When
boiled with baryta-water it decomposes into urea and ammonia. It com-
bines with acids to form salts; the gold salt, CH5NaHCl, AuCl4, is in the
form of long yellow needles, with difficulty soluble in water. Guanidine
nitrate, CH,NaHNO3, is also almost insoluble in cold water and similar
to urea nitrate. By dissolving equivalent parts of phenol and guanidine
in hot alcohol, triphenylguanidine is formed; on adding picric acid to a
solution of triphenylguanidine, phenylguanidine picrate, CH, PhansC.B.,
(NO),OH, is formed, and falls as a precipitate of slender needles, melting-
point 208°; this picrate is very slightly soluble, 1 part dissolving in
12,220 parts of water at 15°. Guanidine is poisonous.f
* Sieber, J., Ber., xxiii. 326–327.
+ O. Prelinger, Momatsb., xiii. 97–100.
§ 672.] METHYLGUANIDINE. 52 I
A method of separating guanidine from urine has been worked out by
Gergers and Baumann.” The principle of the method is based upon
the fact that guanidine is precipitated by mercurous oxide. The
urine is precipitated by hydrate of baryta, the precipitate filtered
off, the alkaline filtrate neutralised by hydrochloric acid, and the
neutral filtrate evaporated to a syrup on the water-bath; the syrup
is exhausted by absolute alcohol, and the alcoholic solution filtered ;
this filtrate is freed from alcohol by distillation, the alcohol-free
residue dissolved in a little water, shaken up with freshly precipi-
tated mercury oxide, and allowed to stand for two days in a warm
place; the precipitate formed is collected, acidulated with HCl and
treated with SH, ; the mercury sulphide thus obtained is separated by
filtration, the filtrate evaporated, and the residue dissolved in absolute
alcohol. This solution is precipitated by platinum chloride, filtered,
separated from any platinum ammonium salt, and evaporated to a small
volume. After long standing the guanidine salt crystallises out. The
best method to identify it appears to be, to ascertain the absence of
ammonia and of urea, and then to gently warm the supposed guanidine
with an alkali, which breaks guanidine up into ammonia and urea,
according to the following equation :
NH-C(NH2), + H2O = NH, + CO(NH,),
The physiological effects of guanidine are as follows:—
A centigrum. of guanidine salt injected into the lymph sac in the back
of frogs produces, after a few minutes, muscular convulsions: first, there
are fibrillar twitchings of the muscles of the back; next, these spread
generally so that the whole surface of the frog seems to be in a wave-like
motion. Irritation of the limbs produces tetanus. There is, at the same
time, increased secretion from the skin. The breathing is irregular. In
large doses there is paralysis and death. The heart is found arrested in
diastole. The fatal dose for a frog is 50 mgrms. ; but 1 mgrm. will pro-
duce symptoms of illness. In dogs there is paralysis, convulsions,
vomiting, and difficult breathing.
NH.CH,
§ 672. Methylguanidine, N=hcº .—Methylguanidine has
NH,
been isolated by Brieger from putrefying horse-flesh; it has also been found
in impure cultures in beef broth of Finkler and Prior's Spirillum Finkleri.
Bocklisch isolated it, working with Brieger's process, from the mercuric
chloride precipitate, after removal of the mercury and concentration of
the filtrate, by adding a solution of sodium picrate. The precipitate
contained the picrate of cadaverine, creatinine, and methylguanidine :
cadaverine picrate, insoluble in boiling absolute alcohol, was separated
* Pfluger's Archiv, xii. 205.
522 POISONs: THEIR EFFECTS AND DETECTION. [$ 673, 674.
by filtering from a solution of the picrates of the bases in boiling absolute
alcohol; the alcohol was evaporated from the filtrate and the residue
taken up with water. From this aqueous solution the picric acid was
removed and then the solution precipitated with gold chloride; methyl-
guanidine was precipitated, while creatinine remained in solution.
Methylguanidine aurochloride, C.H. NaHCl, AuCls (Au = 47.7 per
cent.), forms rhombic crystals easily soluble in alcohol and ether;
melting-point 198°. The hydrochloride, C.H. NaHCl, crystallises in
needles insoluble in alcohol. The picrate, C3H7N,C,EI2(NO2)2OH,
comes down at first as a resinous mass, but, after boiling in water, is
found to be in the form of needles soluble in hot absolute alcohol;
melting-point 192°. The symptoms produced by methylguanidine are
rapid respiration, dilatation of the pupils, paralysis, and death, preceded
by convulsions. The heart is found arrested in diastole.
§ 673. Saprine, C, HiiN.—Saprime is isomeric with cadaverine and
neuridine ; it was found by Brieger in human livers and spleens after
three weeks' putrefaction. Saprine occurs, in Brieger's process, in the
mercury precipitate. Its reactions are very similar to those of cadaverine;
the main difference being that cadaverine hydrochloride gives a crystal-
line aurochloride, saprime does not ; the platinum salt is also more
soluble in water than the cadaverine salt. It is not poisonous.
§ 674. The Choline Group.–The choline group consists of choline,
neurine, betaine, and muscarine.
All these bodies can be prepared from choline ; their relationship to
choline can be readily gathered from the following structural formulae:—
CH,OH CH, CO, H CH,OH
| | | |
CH, CH CH, CHOH
Schºon schºol N(CH2), OH schºol
Choline. Neurine. Betaine. Muscarine.
Choline is a syrup with an alkaline reaction. On boiling with water, it
decomposes into glycol and trimethylamine. It gives, when oxidised,
muscarine. It forms salts. The hydrochloride is soluble in water and
absolute alcohol; neurine hydrochloride and betaine hydrochloride are
but little soluble in absolute alcohol, therefore this property can be
utilised for their separation from choline. The platinochloride is in-
soluble in absolute alcohol; it melts at 225 with effervescence, and
contains 31.6 per cent, of platinum. The mercurochloride is soluble
with difficulty even in hot water. The aurochloride (Au = 44.5 per cent.)
is crystalline, and with difficulty soluble in cold water; but is soluble
in hot water and in alcohol ; melting-point 264 with decomposition.
Choline is only poisonous in large doses.
§ 675, 676] THE CHOLINE GROUP. 523
§ 675. Neurine (Trimethyl-vinyl-ammonium hydrate), C, HaN(CH3),
OH.-Neurine is one of the products of decomposition of choline. It is
poisonous, and has been separated by Brieger and others from decom
posing animal matters. In Brieger's process, neurine, if present, will
be for the most part in the mercuric chloride precipitate, and some
portion will also be in the filtrate. The mercury precipitate is decom-
posed by SH, the mercury sulphide filtered off, and the filtrate, con-
centrated, treated with absolute alcohol and then precipitated by
platinum chloride. It is usually accompanied by choline; the platino-
chloride of choline is readily soluble in water, neurine platinochloride
is soluble with difficulty; this property is taken advantage of, and the
platinochloride crystallised from water until pure. Neurine has a
strong alkaline reaction.
Neurine chloride, C.H.I.N.Cl, crystallises in fine needles. The pla-
tinochloride, (C.His NCI), PtCl, (Pt = 33.6 per cent.), crystallises in
octahedra. The salt is soluble with difficulty in hot water.
The aurochloride, C.His NCIAuCls (Au = 46:37 per cent.), forms flat
prisms, which, according to Brieger, are soluble with difficulty in hot
Water.
Neurine is intensely poisonous, the symptoms being similar to those
produced by muscarine.
Atropine is an antidote to neurine, relieving in suitable doses the
effects, and even rendering animals temporarily immune against the
toxic action of neurine.
When a fatal dose of neurine is injected into a frog there is in a
short time paralysis of the extremities. The respiration stops first, and
afterwards the heart, the latter in diastole.
The symptoms in rabbits are profuse nasal secretion and salivation
with paralysis, as in frogs. Applied to the eye, neurine causes con-
traction of the pupil; to a less degree the same effect is produced by
the ingestion of neurine.
Trimethyloxyammonium hydrochloride causes similar symptoms to
neurine, but the action is less powerful.-W. Cervello, Arch. Ital. Biol.,
vii. 232–233.
§ 676. Betaine.—Betaine may be separated from a solution in alcohol
as large deliquescent crystals; the reaction of the crystals is neutral.
Distilled with potash, trimethylamine and other bases are formed.
Betaine chloride, C5H12NO3Cl, forms plates permanent in the air
and insoluble in absolute alcohol. A solution of the chloride in water
gives, with potassium mercuric iodide, a light yellow or whitish yellow
precipitate, soluble in excess; but on rubbing the sides of the tube
with a glass rod, the oily precipitate crystallises as yellow needles ;
probably this is characteristic.
524 Poisons: THEIR EFFECTS AND DETECTION. [$ 677, 678.
The aurochloride (Au = 43.1 per cent.) forms fine cholesterine plates,
soluble in water; melting-point 209". Betaine is not poisonous.
§ 677. Peptotoxine.—Brieger submitted to the action of fresh gastric
juice moist fibrin for twenty-four hours at blood heat. The liquid was
evaporated to a syrup and boiled with ethylic alcohol, the ethylic
alcohol was evaporated, the residue digested with amylic alcohol, and
the amyl alcohol in its turn evaporated to dryness; the residue was a
brown amorphous mass that was poisonous. It was further purified by
treating the extract with neutral lead acetate and then filtered; the
filtrate was freed from lead by SH, and treated with ether, the ethereal
extract being then separated and evaporated to dryness; this last residue
was taken up with amyl alcohol, the alcohol evaporated to dryness, and
the residue finally taken up with water and filtered. The filtrate is
poisonous. The poisonous substance, to which Brieger gave the pro-
visional name of peptotoxine, is a very stable substance, resisting
the action of a boiling temperature, and • ‘he action of strong alka-
lies. It gives precipitates with alkaloidal group reagents, and strikes a
blue colour with ferric chloride and ferricyanide of potassium. The
most characteristic test seems to be its action with Millon's reagent
(a solution of mercury nitrate in nitric acid containing nitrous acid);
this gives a white precipitate which, on boiling, becomes intensely red.
It is poisonous, killing rabbits in doses of 0.5 grn, per kilogrm., with
symptoms of paralysis and coma. The nature of this substance requires
further elucidation.
§ 678. Pyridine Alkaloid from the Cuttle Fish.—O. de Coninck”
has obtained, by Gautier's process, an alkaloid from the cuttle fish, of
the formula CsPI, N, in the form of a yellow, mobile, strongly odorous
liquid, very soluble in alcohol, ether, and acetone, boiling-point 202°.
It quickly absorbs moisture from the air. It forms two mercuric
chlorides, one of which has the formula (CsIII, N, HCl), HgCl, ; this
compound crystallises in small white needles, slightly soluble in water
and dilute alcohol, but insoluble in absolute alcohol, and decomposing
when exposed to moist air. The other salt is a sesqui-salt, forming
long yellowish needles, insoluble in ordinary solvents, and decomposing
when exposed to moist air. The alkaloid also forms deliquescent very
soluble salts with hydrochloric and hydrobromic acids. A platinum salt
is also formed, (CsIII, N), H2PtCls; it is of a deep yellow colour, almost
insoluble in cold, but soluble in hot water ; it is decomposed by boiling
water, with the formation of a very insoluble compound in the shape
of a brown powder, (CsIIn N), PtCl4. Cominck's alkaloid, on oxidation
with potassic permanganate, yields a gummy acid ; this acid, on purify-
ing it by conversion into a potassium salt and then into a cupric salt, was
* Comptes Rend., cvi. 858, 861, 1604–1605; cviii. 58–59, 809–810.
§ 679, 680.] TETANINE–TETANOTOXINE. 525
found to be nicotinic acid ; so that the alkaloid is undoubtedly a pyri-
dine compound ; indeed, the acid, distilled with lime, yields pyridine.
§ 679. Poisons connected with Tetanus.-Brieger, in 1887, isolated
a base of unknown composition, to which he gave the name of “spasmo-
toxine.” It was produced in cultures of the tetanus bacillus in beef broth.
Two more definite substances have also been discovered, viz., tetanine
and tetanotoxine.
Tetanine, Claha,N,0, is best isolated by the method of Kitasato and
Weyl.” Their method of treating broth cultures of the tetanus bacillus
is as follows:—
The broth is digested with 0:25 per cent. HCl for some hours at
460°, then rendered feebly alkaline, and distilled in a vacuum. The
residue in the retort is then worked up for tetanine by Brieger's
method; the distillate contains tetanotoxine, ammonia, indol, hydrogen
sulphide, phenol, and butyric acid. On treating the contents of the
retort by Brieger's mercury ride method, the filtrate contains most
of the poison. The mercury is removed by SH2, the filtered solution
evaporated and exhausted by absolute alcohol, in which the tetanine
dissolves. Any ammonium chloride is thus separated, ammonium
chloride being insoluble in absolute alcohol. The alcoholic solution,
filtered from any insoluble substance, is next treated with an alcoholic
solution of platinum chloride, which precipitates creatinine (and any
ammonium salts), but does not precipitate tetanine. The platinum
salt of tetanine may, however, be precipitated by the addition of ether
to the alcoholic solution. The platinum salt, as obtained by precipita-
tion from ether, is very deliquescent ; it has, therefore, to be rapidly
filtered off and dried in a vacuum. It can then be recrystallised from
hot 96 per cent. alcohol, forming clear yellow plates; these plates, if
dried in a vacuum, become with difficulty soluble in water.
Tetanine may be obtained as a free base by treating the hydrochloride
with freshly precipitated moist silver oxide. It forms a strongly alkaline
yellow syrup, and is easily decomposed in acid solution, but is permanent
in alkaline solutions.
The platinochloride, as before observed, is precipitable by ether from
alcoholic solution; it contains 28.3 per cent. of platinum, and decom-
poses at 197°.
The base produces tetanus.
§ 680. Tetanotoxine may be distilled, and be found in the distillate
with other matters. It forms an easily soluble gold salt, melting-
point 130°. The platinochloride is soluble with difficulty, and decom-
poses at 240°. The hydrochloride is soluble in alcohol and in water,
melting-point about 205°.
* Zeit. f. Hygiene, viii. 404.
526 Poisons: THEIR EFFECTS AND DETECTION. [$ 681, 682.
Tetanatoxine produces tremor, then paralysis, and lastly, violent
convulsions. -
§ 681. Mydatoxine, C.His NO3−A base obtained by Brieger from
horse-flesh in a putrefactive condition and other substances. It is found
in the mercury chloride precipitate. The free base is an alkaline syrup,
isomeric with the base separated by Brieger from tetanus cultures. The
hydrochloride is a deliquescent syrup, not forming any compound with
gold chloride, but uniting with phospho-molybdic acid in forming a
compound crystallising in cubes. It forms a double salt with gold
chloride, sparingly soluble in water. The platinochloride (Pt - 29 per
cent.) is very soluble in water, but not soluble in alcohol; melting-point
193° with decomposition. *3
The base in large doses is poisonous, causing lachrymation, diarrhoea,
and convulsions.
§ 682. The Poison of Mussels.-Annually a certain number of
people are seriously affected after eating mussels. One of the most
thoroughly investigated series of cases occurred among the stevedores
in 1885,” at Wilhelmhafen. A number of the men collected mussels
adhering to some of the vessels in the harbour, took them home, boiled
them, and they and their families partook of the same. There were nine-
teen serious cases of illness, of which four died. The symptoms occurred
a few hours after the meal. There was a choking sensation, burning
and tingling of the hands and feet. The speech was difficult, and there
was vomiting and diarrhoea. The post-mortem appearances of the fatal
cases showed intense congestion of the mucous membrane of the intes-
times, and haemorrhagic spots in the liver.
Various views have been advanced as to the cause of mussel poisoning,
but it is still obscure; from the experiments of Schmidtmann f and others
it would appear that the mussel derives its toxic properties from the water,
for poisonous mussels taken from stagnant waters and placed in pure sea
water lose the property, to regain it when returned to the same water.
Salkowski found that the poison could be extracted by alcohol, and
could be heated up to 110° without loss of power, but warm sodic carbon-
ate solution destroyed the poison ; f he found that the alcoholic solution
of the non-poisonous mussels was quite clear and colourless; on the other
hand, the liver of poisonous mussels yields a yellow colouring matter
which is changed by concentrated nitric acid into a grass-green colour.
Brieger isolated a substance to which he ascribed the formula
C.H, NO, and named mytilotozine; his process was as follows:—
The mussels were boiled with water acidified by hydrochloric acid;
the liquid was filtered, and the filtrate evaporated to a syrup, and the
* Deutsche Med. Wochemschr., 1885.
+ Virchow's Archiv, 1888. 3: Ibid., 1885.
§ 683.] THE POISON OF MUSSELS. 527
syrup was repeatedly extracted with alcohol. It was found advisable
to exhaust thoroughly with alcohol, otherwise much poison remained
behind. The alcoholic solution was treated with an alcoholic solution
of lead acetate. The filtrate was evaporated and the residue extracted
with alcohol. The lead was removed by SH2, the alcohol distilled off,
water added to the remaining syrup, and the solution decolorised by
boiling with animal charcoal. The solution was neutralised by sodium
carbonate, acidulated with nitric acid, and precipitated with phospho-
molybdic acid. The precipitate was then decomposed by warming with
a neutral solution of lead acetate, and the filtrate (after the removal of
the lead by the action of SH,) was acidulated with HCl and evaporated
to dryness. The residue was then extracted with absolute alcohol,
filtered from any insoluble chloride, e.g., betaine chloride, and pre-
cipitated by mercury chloride in alcohol.
The free base has a most peculiar odour, which disappears on
exposure to air; at the same time, the poisonous properties also diminish.
The base is destroyed by boiling with sodium carbonate; on the other
hand, the hydrochloride may be evaporated to dryness or be boiled
without decomposing. -
The hydrochloride crystallises in tetrahedra ; the aurochloride
crystallises in cubes (Au = 41-66 per cent.). Its melting-point is 182°.
Thesen, operating on large quantities of poisonous mussels by
Brieger's process, however, failed to isolate mytilotoxine, and it is doubt-
ful whether this substance, presuming it to exist, is the real poison.
$683. Tyrotoxicon (Diazobenzol, C.H.N2(OH)).-It appears, from
the researches of Waughan and others, that diazobenzol is liable to be
formed in milk and milk products, especially in summer time. It is
confidently asserted by many that the summer diarrhoea of infants is
due to this toxine ; however that may be, it is well established that
diazobenzol is a violent poison, causing sickness, diarrhoea, and, in large
doses, an acute malady scarcely distinguishable from cholera, and which
may end fatally. There will always be difficulty in detecting it, because
of its instability. The following is the best process of extraction from
milk. The milk will probably be acid from decomposition; if so, the
whey must be separated by dilution and filtration; without dilution it
may be found impracticable to get a clear filtrate. In order to keep the
bulk down, 25 c.c. of the milk may be diluted up to 100 c.c., and,
having obtained a clear filtrate from this 25 c.c. thus diluted, the filtrate
is used to dilute another 25 c.c. of milk, and so on. The acid filtrate is
neutralised by sodium carbonate, agitated with an equal volume of ether,
allowed to stand in a stoppered vessel for twenty-four hours, and the
ether then separated and allowed to evaporate spontaneously. The
residue is acidified with nitric acid and them treated with a saturated
528 POISONs: THEIR EFFECTS AND DETECTION. [$684, 685.
solution of potash, which forms a stable compound with diazobenzol, and
the whole concentrated on the water-bath. On cooling, the tyrotoxicon
compound forms six-sided plates. Before the whole of this process is
undertaken, it is well to make a preliminary test of the milk as follows:
—A little of the ether is allowed to evaporate spontaneously. Place
on a porcelain slab two or three drops of a mixture of equal parts of
sulphuric and carbolic acids, and add a few drops of the aqueous solu-
tion; if tyrotoxicon be present, a yellow to orange-red colour is pro-
duced. A similar colour is also produced by nitrates or nitrites, which are
not likely to be present under the circumstances, milk having mere traces
only of nitrates or nitrites; it may also be due to butyric acid, which,
in a decomposed milk, may frequently be in solution. Therefore, if a
colour occurs, this is not absolutely conclusive ; if, however, no colour
is produced, then it is certain that no diazobenzol has been separated.
That is all that can be said, for the process itself is faulty, and only
separates a fractional part of the whole.
§ 684. Toxines of Hog Cholera.-Toxines have been isolated by F. G.
Novy " from a cultivation of Salmon's bacillus in pork broth. The
fluid possessed a strong alkaline reaction. For the isolation Brieger's
method was used. The mercury chloride precipitate was amorphous and
was converted into a chlorine-free platinum compound, to which was
assigned the composition of CsPIAN, Pt.0s. After separation of this com-
pound, the mother liquor still contained a platinum salt, crystallising in
needles, and from this was obtained the chlorhydrate of a new base, to
which was given the name of Susotozine; it had the composition of
CiołI, N,2HCl, PtCl4. Susotoxine gives general alkaloidal reactions,
and is very poisonous.
§ 685. Other Animal Toxines.—Besides the animal toxines which
have been already described, there are a number of others; the follow-
ing may be mentioned : isoamylamine,i (CHA),CH.CH2CH2NH, ;
butylamine, CH2CH2CH2CH3NH2; dihydrolutidine, C, HiiN ; hydro-
collidine,S CsPIs N ; Ciołł is N (a base isolated by Guareschi and Mosso ||
from ox-fibrin in a state of putrefaction by Gautier's method ; it forms a
crystalline hydrochloride and an insoluble platinochloride ; its action is
like that of curare, but weaker);" aselline, CºgPIs, Nº, isolated from cod-
liver oil; typhotoxine,” C, H17NO2, isolated from cultures of Eberth's
bacillus. So far as the published researches go, it would appear that
other crystalline substances have been isolated from the urine, from the
* Med. News, September 1890. † Hesse, Chim. Jahresb., 1857, 403.
† Gautier, A., and Morgues, Compt. Rend., 1888.
§ Gautier et Etard, Bull. Soc. Chim..., xxxvii., 1882.
| Guareschi et Mosso, Les ptomaines, 1883.
"I Gautier, A., et Morgues, Compt. Rend., 1888.
** Brieger, 1885, Ptomaines, iii.
§ 686.] FOOD POISONING. 529
tissues, and from the secretions of patients suffering from various dis-
eases; the quantity obtained in each case has, however, been, under the
most favourable circumstances, less than a gramme; often only a few
milligrms. To specifically declare that a few milligroms. of a substance
is a new body, requires immense experience and great skill; and, even
where those qualifications are present, this is too often impossible.
This being so, the long list of named animal toxines, such as erysipeline,
varioline, and others, must have their existence more fully confirmed by
more than one observer before they can be accepted as separate entities.
DIVISION III. —FOOD POISONING.
§ 686. A large number of cases of poisoning by food occur yearly ;
some are detailed in the daily press; the great majority are neither
recorded in any journal, scientific or otherwise; nor, on account of their
slight and passing character, is medical aid sought. The greatest portion
of these cases are probably due to toxines existing in the food before
being consumed; others may be due to the action of unhealthy fermenta-
tion in the intestinal canal itself; in a third class of cases, it is probable
that a true zymotic infection is conveyed and develops in the sufferer;
the latter class of cases, as, for instance, the Middlesbrough epidemic
of pleuro-pneumonia, is outside the scope of this treatise.
The development of poisonous toxines in food is largely dependent
on the conditions under which food is kept. Contamination in the
Smallest degree of certain articles of food in summer time may easily
give rise to severe and even fatal diarrhoea, for it may be proved that
seeding sterile broth with healthy excreta, converts the broth, on incubat-
ing at blood heat, into a liquid which is fatal to rodents, the animals
dying from gastro-enteritis.
Confining the attention to cases of food poisoning in which the
symptoms have been closely analysed and described, the reader is referred
to thirteen cases of food poisoning investigated by the medical officers
of the Local Government Board between the years 1878 and 1891, as
follows:— -
1878. A Case of Poisoning at Whitchurch from eating Roast Pork.
—Only the leg of pork was poisonous; other parts were eaten without
injury. Two persons died after about thirty hours' illness. The pork
itself, on a particular Sunday, was innocuous; it became poisomous
between the Sunday and the Monday; the toxicity appeared to gradually
increase, for those who ate it for dinner on the Monday were not taken
ill for periods of from seven to nineteen hours, while two persons who
ate of it in the evening were attacked four hours after eating.
34
53O POISONS: THEIR EFFECTS AND DETECTION. [$ 686.
1880. The Welbeck Epidemic, due to eating cold boiled ham. Over
fifty persons affected. Symptoms commenced in from twelve to forty-
eight hours.
1881. A Series of Poisoning from eating Baked Pork, Nottingham.
–Probably the gravy was the cause and not the pork itself. Many
persons seriously ill. One died.
1881. Tinned American Sausage.—A man in Chester died from
eating tinned American sausage. Poison found to be unequally distri-
buted in the sausage. -
1882. Poisoning at Oldham by Tinned Pigs' Tongues.—Two families
affected. Symptoms commenced in about four hours. All recovered.
After a few days' keeping it would appear that the poison had been
decomposed.
1882. A Family Poisoned by Roast Beef at Bishop Stortford.--
Only a particular piece of the ribs seemed to be poisonous, the rest of
the carcase being innocuous. Symptoms did not commence until
several hours after ingestion. -
1882. Ten different Families at Whitchurch poisoned by eating
Brawn.—First symptoms after about four hours.
1884. Tinned Salmon at Wolverhampton.—Five persons, two being
children, ate of tinned salmon at Wolverhampton. All suffered more or
less. The mother's symptoms began after twelve hours, and she died in
five days; the son died in three days, the symptoms commencing in ten
hours. The post-mortem signs were similar to those from phosphorus
poisoning, viz., fatty degeneration. Mice fed on the material also
suffered, and their organs showed a similar degeneration.
1886. The Carlisle A Case.—At a wedding breakfast in Carlisle
twenty-four persons were poisoned by food which had been kept in
an ill-ventilated cellar. The articles suspected were an American ham,
an open game pie, and certain jellies. The bride died. Symptoms
commenced in from six to forty-three hours.
1886. Poisoning by Veal Pie at Iron Bridge.—Twelve out of fifteen
ate of the pie ; all were taken ill in from six to twelve hours.
1887. Poisoning at Retford of Eighty Persons from eating Pork
Pie or Brawn.—Symptoms commenced at various intervals, from eight
to thirty-six hours.
1889. The Carlisle B Case.—Poisoning by pork pies or boiled salt
pork. Number of persons attacked, about twenty-five.
1891. Poisoning by a Meat Pie at Portsmouth.—Thirteen persons
suffered from serious illness. Portions of the pies were poisonous to
mice. *
* To these may be added the Chadderton case investigated by Dr. Durham. Thirty-
five persons were attacked in Chadderton, with three deaths; twelve in Oldham, one of
§ 686.] FOOD POISONING. 53 I
The symptoms in all these cases were not precisely alike ; but they
were so far identical as to show as great a similarity as in cases when a
number of persons are poisoned by the same chemical substance. Arsenic,
for instance, produces several types of poisoning; so does phosphorus.
Severe gastro-enteric disturbance, with more or less affection of the
nervous system, were the main characteristics. These symptoms com-
menced, as before stated, at various intervals after ingestion of the food;
but they came on with extreme suddenness. Rigors, prostration, giddi-
ness, offensive diarrhoea, followed by muscular twitchings, dilatation of
the pupil, drowsiness, deepening in bad cases to coma, were commonly
observed. The post-mortem appearances were those of enteritis, with
inflammatory changes in the kidney and liver. Convalescence was slow ;
sometimes there was desquamation of the skin.
In many of these cases Dr. Klein found bacteria which, under certain
conditions, were capable of becoming pathogenic ; but in no case does
there seem to have been at the same time an exhaustive chemical
inquiry; so that, although there was evidence of a poison passing
through the kidney, the nature of the poison still remains obscure.
The deaths in England and Wales from unwholesome food during ten
years were as follows:—
DEATHS IN ENGLAND AND WALES FROM UNWHOLESOME FOOD
DURING THE TEN YEARS 1883–1892.
1883. 1884. issis, 1887.| 1888. 1889. 1890. 1891. 1892. Total.
!
- —— – -*- : - - - -ss- –– -------- - - -
Diseased meat, . . . 1 | ... * * * ... I
Poisonous fish, 2 3 2 | 1 l 4 3 2 | 9 || 6 33
Unwholesome brawn, ... | 1 * tº º tº ... 1
Tinned salmon, 2 • . . . . … 2
| Putrid meat, l 1 1 ... I 4
Diseased food, . I * * * * * * tº º - l
Mussels, º l • . . . . . . 1 2
Tinned foods, . - e. 2 & & © 2
Whelks, is * * r * * * * * * I e s g ... . . . . . . . . . . . . . . |
Winkles, . . . . . . ... . . . . . . . . . . . . . . . ... . ... 1 : ... I
Ptomaines, . * * * ... . . . . . . . . . . . . . . . . 1 I
* | 0 || 3 | * | * 5 || 3 || 0 || 6 49
Since 1892, deaths from foods have not been regularly and systemati-
cally extracted by the Registrar General's Department. A few in some
years appear under the diarrhoeal class of disease; the rest apparently
have been registered in various ways; hence no precise knowledge of
the actual number of deaths ascribed to food is available.
which was fatal. Dr. Durham seems to have fairly well established a connection betwee
the outbreak and veal pies infected by the Bacillus enteritidis. B. Med. Journal, 1898
532 POISONS : THEIR EFFECTS AND DETECTION. [$ 687.
§ 687. German Sausage Poisoning.—A series of cases may be picked
out from the accounts of sausage poisoning in Germany, all of which
evidently depend upon a poison producing the same symptoms, and the
essentially distinctive mark of which is extreme dryness of the skin and
mucous membranes, dilatation of the pupil, and paralysis of the upper
eyelids (ptosis). In an uncertain time after eating sausages or some
form of meat, from one to twenty-four hours, there is a general feeling
of uneasiness, a sense of weight about the stomach, nausea, and soon
afterwards vomiting, and very often diarrhoea. The diarrhoea is not
Severe, never assumes a choleraic form, and is unaccompanied by cramps
in the muscles. After a considerable interval there is marked dryness
of the mucous membrane (a symptom which never fails), the tongue,
pharynx, and the mouth generally seem actually destitute of secretion;
there is also an absence of perspiration, the nasal mucous membrane
participates in this unnatural want of secretion, the very tears are dried
up. In a case related by Kraatzer,” the patient, losing a son, was much
troubled, but wept no tear. This dryness leads to changes in the
mucous membrane; it shrivels, and partly desquamates; aphthous
swellings may occur, and a diffuse redness and diphtheritic-like patches
have been noticed. There is obstinate constipation, probably from a
dryness of the mucous lining of the intestines. The breath has an
unpleasant odour, there is often a croupy cough ; the urinary secretion
alone is not decreased but rather augmented. Swallowing may be so
difficult as to rise to the grade of aphagia, and the tongue cannot be
manipulated properly, so that the speech may be almost unintelligible.
At the same time, the motor nerves of the face are affected, the
patient's sight is disturbed, he sees colours or sparks before his
eyes; in a few cases there has been transitory blindness, in others
diplopia. The pupil in nearly all the cases has been dilated, but in
exceptional instances it has been contracted. The levator palpebrae
Superioris is paralysed, and the resulting ptosis completes the picture.
Consciousness remains intact almost to death ; there is excessive weakness
of the muscles, perhaps from a general paresis. If the patient lives
long enough, he gets wretchedly thin, and dies from marasmus. In
more rapidly fatal cases, death follows from respiratory paralysis, with
or without convulsions.
The post-mortem appearances which have been observed are—the
mucous membrane of the mouth, gullet, and throat is white, hard, and
parchment-like ; that of the stomach is more or less injected with
numerous hæmorrhages: the kidneys are somewhat congested, with
some effusion of blood in the tubuli; the spleen is large and very full of
blood, and the lungs are often oedematous, pneumonic, or bronchitic.
* Quoted by Husemann, Vergiftung durch Wurstgift (Maschka's Handbook).
PART VIII.—THE OXALIC ACID GROUP OF POISONS.
§ 688. Oxalic acid is widely distributed both in the free state and
in combination with bases throughout the vegetable kingdom, and it
also occurs in the animal kingdom. In combination with potash it is
found in the Geranium acetosum (L.), Spinacia oleracea (L.), Phytolacca
decandra (L.), Rheum palmatum (L.), Rumex acetosa, Atropa belladonna,
and several others; in combination with soda in different species of
Salsola and Salicornia; and in combination with lime in most plants,
especially in the roots and bark. Many lichens contain half their
weight of calcic oxalate, and oxalic acid, either free or combined, is
(according to the observations of Hamlet and Plowright *) present in all
mature non-microscopic fungi. Crystals of oxalate of lime may be
frequently seen by the aid of the microscope in the cells of plants.
According to Schmidt,f this crystallisation only takes place in the fully
mature cell, for in actively growing cells the oxalate of lime is entirely
dissolved by the albumen of the plant.
In the animal kingdom oxalic acid is always present in the intestinal
contents of the caterpillar. In combination with lime, it is constantly
found in the allantois liquor of the cow, the urine of man, swine, horses,
and cats. With regard to human urine, the presence or absence of
oxalate of lime greatly depends upon the diet, and also upon the indi-
vidual, some persons almost invariably Secreting oxalates, whatever
their food may be.
§ 689. Oxalic Acid, H,C,0,2H,0(90+36), specific gravity 1.64,
occurs in commerce in prismatic crystals, very similar to, and liable to
be mistaken for, either magnesic or zincic sulphates. The crystals are
intensely acid, easily soluble in water (1 part requiring at 14:5° 10'46
parts of water); they are also soluble in 24 parts of cold, and readily in
boiling, alcohol. Oxalic acid is slightly soluble in cold absolute ether;
but ether, although extracting most organic acids from an aqueous
solution, will not extract oxalic acid.
. * Chem. News, vol. xxxvi, p. 93.
t Ann. Chem. Pharm., vol. lxi. p. 297.
533 .
534 , POISONS: THEIR EFFECTS AND DETECTION. [$ 690.
Oxalic acid sublimes slowly at 100°, but rapidly and completely at
150°; the best means of obtaining the pure anhydride is to put a
sufficient quantity of the acid into a strong flask, clamp it by suitable
connections to a mercury pump, and sublime in a vacuum ; in this way
a sufficient quantity may be sublimed a little above 100°. It is well to
remember, not only its low subliming temperature, but also that an
aqueous solution, if kept at 100°, loses acid; hence all evaporating or
heating operations must not exceed 98°, or there will be some loss. The
effect of heat is first to drive off water, then, if continued up to about
190°, there is decomposition into carbon monoxide, carbon dioxide,
water, and formic acid; the two reactions occurring simultaneously—
C.H.O. = CO2 + CO + H2O.
C.H.O. = CO3 + CH,03.
Heated with sulphuric acid to 110°, the following decomposition
takes place:—
H,C,0, = H,O + CO2 + CO.
Oxalic acid decomposes fluor spar, the phosphates of iron, silver, zinc,
copper, and the arseniates of iron, silver, and copper. It may be used
to separate the sulphides of iron and manganese from the sulphides
of zinc, cadmium, uranium, cobalt, mercury, and copper—dissolving
the former, not the latter. Many minerals and other substances are
also attacked by this acid.
If a solution of Oxalic acid in water is boiled with ammonio or sodio
terchloride of gold (avoiding direct exposure to light) the gold is
precipitated—
2AuCls + 3H2C90, -6CO, +6HCl + Aug.
When black oxide of manganese (free from carbonate) is mixed with
an oxalate, and treated with dilute sulphuric acid, the oxalic acid is
decomposed, and carbon dioxide evolved—
MnO, +H,C,0, + H2SO, - MnSO, + 2H3O+ 2CO3.
A similar reaction occurs with permanganate of potash.
If to a solution of oxalic acid, which may be neutralised with an
alkali, or may contain free acetic acid, a solution of acetate of lime be
added, oxalate of lime is thrown down. This salt, important from an
analytical point of view, it will be well to describe.
§ 690. Oxalate of Lime (CaC20, H2O), 1 part = 863 crystallised
oxalic acid. This is the salt which the analyst obtains for the quantita-
tive estimation of lime or oxalic acid; it is not identical with that occur-
ring in the vegetable kingdom, the latter containing 3H2O. Oxalate
of lime cannot be precipitated for quantitative purposes from solu-
tions containing chromium, aluminium, or ferric salts, since somewhat
soluble compounds are formed. It dissolves in solutions of magnesium
§ 691-695.] OXALIC ACID. 535
and manganese salts,” and citrate of soda, and is also decomposed by boil-
ing with solutions of copper, silver, lead, cadmium, zinc, nickel, cobalt,
strontium, or barium salts. It is insoluble in solutions of chlorides of
the alkalies and alkaline earths, and in water, in alkaline solutions, or
in acetic acid; and is soluble in mineral acid only when the acid is
strong and in considerable excess. It is unalterable in the air, and
at 100°. When carefully and slowly ignited it may be wholly converted
into carbonate of lime ; if the heat is not properly managed (that is, if
excessive), caustic lime may be formed in greater or smaller quantity.
§ 691. Use in the Arts.-Oxalic acid is chiefly used by dyers and
calico-printers, but also by curriers and harness-makers for cleaning
leather, by marble masons for removing iron stains, by workers in
straw for bleaching, and it is applied to various household purposes,f
such as the whitening of boards, the removing of iron-mould from
linen, etc. The hydropotassic oxalate (binoxalate of potash), under
the popular names of “essential salt of lemons” and salts of sorrel, is
used for scouring metals and for removing ink-stains from linen.
§ 692. Hydropotassic Oxalate, Binoxalate of Potash, KHC,0,0H,0),
is a white salt, acid in reaction, soluble in water, and insoluble in
alcohol. Heated on platinum foil it leaves potassic carbonate, which
may be recognised by the usual tests. Its aqueous solution gives,
with a solution of acetate or sulphate of lime, a precipitate of calcic
oxalate insoluble in acetic acid.
§ 693. Statistics.-Poisoning by oxalic acid is more frequent in
England than in any other European country. In the ten years ending
December 1903 there were registered in England and Wales 171
oxalic acid deaths. Of these 55 (27 males and 28 females) were
accidental, 114 (65 males, 49 females) were suicidal, and there were
two cases of murder. Oxalic acid occupies about the tenth place among
poisons arranged in order of frequency.
§ 694. Fatal Dose.—The smallest dose of oxalic acid known to have
destroyed life is, according to Dr. Taylor, 3.88 grins. (60 grains); but
recovery has taken place, on prompt administration of remedies, after
eight times this quantity has been swallowed.
With regard to oxalate of soda, or binoxalate of potash, 14.2 grims.
(half an ounce) have been taken without fatal result, although the
symptoms were very serious; and it may be held that about that
quantity would usually cause death. Oxalic acid is not used in
medicine, save as a salt, e.g., oxalate of cerium.
§ 695. Effects of Oxalic Acid and Oxalates on Animals.—The first
cases of poisoning by Oxalic acid occurred early in the nineteenth
* But it is reprecipitated unaltered by excess of alkaline oxalate.
+ A “Liquid Blue,” used for laundry purposes, contains much free oxalic acid.
536 POISONS : THEIR EFFECTS AND DETECTION. [$ 696.
century, a little more than fifty years after its discovery. Thompson *
was the first who attempted, by experiment on animal life, to elucidate
the action of the poison ; he noted the caustic action on the stomach,
and the effects on the heart and nervous system, which he attributed
simply to the local injury through the sympathetic nerves. Orfila t
was the next who took the matter up, and he made several experiments;
but it was Robert Christison Í who distinctly recognised the important
fact that oxalic acid was toxic, quite apart from any local effects, and
that the soluble oxalates, such as sodic and potassic oxalates, were
violent poisons.
§ 696. Kobert and Küssner § have made some extended researches
on the effects of sodic oxalate on rabbits, cats, dogs, guinea-pigs, hedge-
hogs, frogs, etc.—the chief results of which are as follows:–On
injection of sodic oxalate solution in moderate doses into the circula-
tion, the heart's action, and, therefore, the pulse, become arhythmic ;
and a dicrotic or tricrotic condition of the pulse may last even half a
day, while at the same time the frequency may be uninfluenced. The
blood-pressure also with moderate doses is normal, and with small
atoxic doses there is no slowing of the respiration. On the other hand,
toxic doses paralyse the respiratory apparatus, and the animal dies
asphyxiated. With chronic and subacute poisoning the respiration
becomes slower and slower, and then ceases from paralysis of the
respiratory muscles. The first sign of poisoning, whether acute or
chronic, is a sleepy condition; dogs lie quiet, making now and then
a noise as if dreaming, mechanical irritations are responded to with
dulness. The hind extremities become weak, and then the fore. This
paresis of the hind extremities, deepening into complete paralysis,
was very constant and striking. Take, for example (op. cit.), the
experiment in which a large cat received in six days five subcu-
taneous injections of 5 c.c. of a solution of sodic oxalate (strength
1 : 30), equalling 16 grm. ; the cat died, as it were, gradually from
behind forwards, so that on the sixth day the hinder extremities were
fully motionless and without feeling. The heart beat strongly. The
temperature of the poisoned animal always sinks below the normal
condition. Convulsions in acute poisoning are common, in chronic
quite absent ; when present in acute poisoning, they are tetanic or
strychnic-like. In all the experiments of Kobert and Küssner, lethal
doses of soluble oxalates caused the appearance of sugar in the urine.
J. Uppmain || made forty-nine experiments on dogs, in which he
* Lond. Med. Rep., vol. iii. p. 382. t Traité de Towicologie.
† Edin. Med. and Surg. Journ., 1823.
s “Exper. Wirkungen der Oxalsåure,” Virch. Archiv, Bd. lxxvii. S. 209.
| Allg. Med, central Žtg., 1877.
§ 697, 698.] OXALIC ACID, 537
administered relatively large doses by the stomach; no poisonous effect
followed. Emil Pfeiffer * gave a dog in three successive days 2, 5, and
lastly 1 grm. oxalic acid with meat, but no symptoms resulted. Yet
that Oxalic acid, as sodic oxalate, is poisonous to dogs, if it once gets
into the circulation, cannot be disputed. The accepted explanation is
that the large amount of lime phosphates in the digestive canal of dogs
is decomposed by oxalic acid, and the harmless lime oxalate formed.
Oxalic acid is absorbed into the blood, and leeches have been known
to die after their application to a person who had taken a large dose.
Thus Christison f quotes a case related by Dr. Arrowsmith, in which
this occurred :—“They were healthy, and fastened immediately ; on
looking at them a few minutes after, I remarked that they did not seem
to fill, and on touching one it felt hard, and instantly fell off motionless
and dead ; the others were in the same state. They had all bitten, and
the marks were conspicuous, but they had drawn scarcely any blood.
They were applied about six hours after the acid had been taken.”
§ 697. Effects of Vaporised Oxalic Acid.—Eulenberg has experi-
mented on pigeons on the action of oxalic acid when breathed. In one
of his experiments, 75 grm. of the acid was volatilised into a glass
shade in which a pigeon had been placed; after this had been done five
times in two minutes, there was uneasiness, shaking of the head, and
cough, with increased mucous secretion of the nasal membrane. On
continuing the transmission of the vapour, after eight minutes there
was again restlessness, shaking of the head, and cough ; after eleven
minutes the bird fell and was convulsed. On discontinuing the sub-
limation, it got up and moved freely, but showed respiratory irritation.
On the second day after the experiment, it was observed that the bird's
note was hoarse, on the fourth day there was slowness of the heart's
action and refusal of food, and on the sixth day the bird was found dead.
Examination after death showed slight injection of the cerebral mem-
branes; the cellular tissue in the neighbourhood of the trachea contained
in certain places extravasations of blood, varying from the size of a pea
to that of a penny; the mucous membrane of the larynx and trachea
was swollen and covered with a thick croupous layer; the lungs were
partially hepatised, and the pleura thickened; the crop as well as the
true intestines still contained some food.]
§ 698. The Effects of Oxalic Acid and Hydropotassic Oxalate on
Man.—The cases of oxalic poisoning have been invariably due to either
Oxalic acid or hydropotassic oxalate, the neutral sodic or potassic oxalates
baving hitherto in no instance been taken. The symptoms, and even
the locally destructive action of oxalic acid and the acid oxalate, are so
* Archiv der Pharm. (3 R.), Bd. xiii. S. 544, 1878.
t Treatise on Poisons. † Gewerbe Hygiene, p. 423.
538 POISONS: THEIR EFFECTS AND DETECTION. [$ 698.
similar that neither from clinical nor post-mortem signs could they be
differentiated by anyone not having a previous knowledge of the case.
The external application of oxalic acid does not appear to cause
illness; workmen engaged in trades requiring the constant use of the
acid often have the nails white, opaque, and brittle; but no direct injury
to health is on record.
A large dose of either causes a local and a remote effect ; the local is
very similar to that already described as belonging to the mineral acids;
7.e. more or less destructive of the mucous membranes with which the
acid comes in contact. The remote effects may only be developed after
a little; they consist essentially of a profound influence on the nervous
system. Though more than 120 cases of oxalic acid poisoning have
occurred since Christison wrote his treatise, his graphic description still
holds good. “If,” says he, “a person immediately after swallowing a
solution of a crystalline salt, which tasted purely and strongly acid, is
attacked with burning in the throat, then with a burning in the stomach,
vomiting, particularly of bloody matter, imperceptible pulse, and
excessive languor, and dies in half an hour, or still more, in twenty,
fifteen, or ten minutes, I do not know any fallacy which can interfere
with the conclusion that Oxalic acid was the cause of death. No parallel
disease begins so abruptly, and terminates so soon ; and no other
crystalline poison has the same effect.” The local action is that of a
solvent on the mucous tissues. If from 10 to 30 grns, are swallowed,
dissolved in water, there is an immediate sour taste, pain, burning in
the stomach, and vomiting. The vomit may be colourless, greenish, or
black, and very acid; but there is a considerable variety in the
symptoms. The variations may be partly explained by saying that, in
one class of cases, the remote or true toxic effects of the poison pre-
dominate; in a second, the local and the nervous are equally divided ;
while in a third, the local effects seem alone to give rise to symptoms.
In a case at Guy's Hospital, in 1842, there was no pain, but vomiting
and collapse. In another case which occurred in 1870, a male (aged 48)
took 10-4 grms. (162 grains); he had threatening collapse, cold sweats,
white and red patches on the tongue and pharynx, difficulty in swallow-
ing, and contracted pupils. Blood was effused from the mouth and anus;
on the following day there were convulsions, coma, and death thirty-six
hours after taking the poison. In another case, there was rapid loss of
consciousness and coma, followed by death in five hours. Death may be
very rapid; e.g., in one case (Med. Times and Gaz., 1868) it took place
in ten minutes; there was bleeding from the stomach, which doubtless
accelerated the fatal result. Orfila has recorded a death almost as rapid
from the acid oxalate of potash; a woman took 15 grims. ; there was no
vomiting, but she suffered from fearful cramps, and death ensued in
§ 699.] - OXALIC ACID, 539
fifteen minutes. In another case, also recorded by Orfila, there was
marked slowing of the pulse, and Soporific tendencies. With both oxalic
acid and the acid oxalate of potash, certain nervous and other sequelae
are more or less constant, always provided time is given for their
development. From the experiments already detailed on animals, one
would expect some paresis of the lower extremities, but this has not
been observed in man. There is more or less inflammation of the
stomach, and often peritonitis; in one case (Brit. Med. Journal, 1873)
there were cystitis and acute congestion of the kidneys with albuminuria.
In two cases quoted by Taylor there was a temporary loss or en-
feeblement of voice; in one of the two the aphonia lasted for eight
days. In the other, that of a man who had swallowed about 7 grms.
(# oz.) of oxalic acid, his voice, naturally deep, became in nine hours
low and feeble, and continued so for more than a month, during the
whole of which time he suffered in addition from numbness and ting-
ling of the legs. As a case of extreme rarity may be mentioned that
of a young woman,” who took 12 grns. (185 grains) of the acid oxalate
of potash, and on the third day died; before death exhibiting delirium
so active and intense that it was described as “madness.”
§ 699. Physiological Action.—Putting on one side the local effects
of oxalic acid, and regarding only its true toxic effects, there is some
difference of opinion as to its action. L. Hermann considers it one of
the heart poisons, having seen the frog's heart arrested by subcutaneous
doses of sodic oxalate, an observation which is borne out by the experi-
ments of Cyon,i and not negatived by those of Kobert and Küssner.
The poison is believed to act on the extracardial ganglia. Onsum; held
at one time a peculiar theory of the action of oxalic acid, believing
that it precipitated as oxalate of lime in the lung capillaries, causing
embolic obstruction ; but this view is not now accepted—there are too
many obvious objections to it. Kobert and Küssner do not consider
oxalic acid a heart poison, but believe that its action is directed to the
central nervous system, as attested by sinking of the blood-pressure, the
arhythm and retardation of the pulse, the slow breathing, the paralytic
symptoms, and the fibrillary muscular contraction ; but, with regard to
the latter, Locke $ has observed that a frog's Sartorius, immersed in 0-75
sodium oxalate solution, becomes in a few seconds violently active, much
more so than in Biederman's normal Saline solution. After thirty to
* Journ. de Chim. Méd., 1839, p. 564.
+ Virchow's Archiv, Bd. xx. S. 233.
† Almen afterwards supported Onsum’s view; he made a number of microscopical
observations, and appears to have been the first who identified oxalate of lime in the
kidneys (Upsala, Läkareförenings forhandl., Bd. ii. Hft. iv. S. 265).
§ F. S. Locke, J. Phys., xv. 119 ; Journ. Chem. Soc., 1893, 480.
54O POISONS: THEIR EFFECTS AND DETECTION. [$700, 701.
forty-five minutes it loses its irritability, which, however, it partially
recovers by immersion in 0-6 sodium chloride solution. He thinks this
may explain the symptoms of fibrillary muscular contraction observed
by Kobert and Küssner, which they ascribe to an action on the central
nervous system.
§ 700. Pathological Changes.—Kobert and Küssner observed that
when oxalate of soda was subcutaneously injected into animals, there
was often abscess, and even gangrene, at the seat of the injection. If
the poison were injected into the peritoneal cavity, death was so rapid
as to leave little time for any coarse lesions to manifest themselves.
They were not able to observe a cherry-red colour of the blood, nor did
they find oxalate of lime crystals in the lung capillaries; there were
often embolic processes in the lung, but nothing typical. They came,
therefore, to the conclusion that the state of the kidneys and the urine
was the only typical sign. The kidneys were dark, full of blood, but
did not show any microscopic hamorrhages. Twelve hours after taking
the poison there is observed in the cortical substance a fine striping
corresponding to the camaliculi; in certain cases the whole boundary
layer is coloured white. If the poisoning lasts a longer time, the
kidneys become less blood-rich, and show the described white striping
very beautifully; this change persists several weeks. The cause of this
strange appearance is at once revealed by a microscopical examination;
it is due to a deposition of oxalate of lime ; no crystals are met with in
the glomerules. Both by the microscope and by chemical means it may
be shown that the content of the kidney in oxalates is large.” So far
as the tissues generally are concerned, free oxalic acid is not likely to
be met with ; there is always present sufficient lime to form lime oxalate.
The urine was always albuminous and contained a reducing substance,
which vanished about the second day after the dose. Hyaline casts and
deposits of oxalates in the urine never failed.t
§ 701. Observations of the pathological effects of the oxalates on
man have been confined to cases of death from the corrosive substances
mentioned, and hence the intestinal tract has been profoundly affected.
In the Museum of St. Thomas' Hospital is a good example of the
effects produced. The case was that of a woman who had taken a large,
unknown quantity of oxalic acid, and was brought to the hospital dead.
* The important fact of the oxalate-content of kidneys and urine, and the expul-
sion of casts, was first observed by Mitscherlich in 1854. He noticed in a rabbit, to
which had been given 7:5 grms, of oxalic acid, and which had died in thirteen
minutes, “renes paululum magis Sangwine replete videbantur, in wrima multa corpora
inveniebantur, quae tubulos Bellenianos explese videntwr” (De acidi acetici, owalici,
tartarici, citrici, formici, et boracici, etc., Berlin).
+ Rabuteau has discovered by experiment that even the oxalates of iron and
copper are decomposed and separated by the kidneys. Gaz, Méd. de Paris, 1874.
§ 702, 703.] OXALIC ACID. 54 I
The mucous membrane of the gullet is much corrugated and divided
into numerous parallel grooves, these again by little transverse grooves,
so that the intersection of the two systems makes a sort of raised
pattern. It is noted that in the recent state the mucous membrane
could be removed in flakes; in the upper part it was whitish, in the
lower slate-coloured. The stomach has a large perforation, but placing
the specimen beside another in the same museum which illustrates the
effect of the gastric juice, in causing an after-death solution of a portion
of the stomach, it was difficult to differentiate between the two. The
mucous membrane had the same shreddy flocculent appearance, and is
soft and pale. The pyloric end is said to have been of a blackish colour,
and no lymph was exuded.
§ 702. The pathological changes by the acid oxalate of potash are
identical with those of oxalic acid, in both, the gullet and stomach
being nearly always more or less inflamed or corroded ; the inflammation
in a few cases has extended right through into the intestinal canal ;
there are venous hyperaemia, haemorrhages, and swelling of the mucous
membrane of the stomach. The haemorrhages are often punctiform, but
occasionally larger, arranged in rows on the summits of the rugae; some-
times there is considerable bleeding. In the greater number of cases
there is no actual erosion of the stomach, but the inner layer appears
abnormally transparent. On examining the mucous membrane under
the microscope, Lesser * has described it as covered with a layer which
strongly reflects light, and is to be considered as caused by a fine preci-
pitate of calcic oxalate. Lesser was unable to find in any case oxalic
acid crystals, or those of the acid oxalate of potash. There are many
cases of perforation on record, but it is questionable whether they are
not all to be regarded as post-mortem effects, and not life-changes; at
all events, there is little clinical evidence to support the view that
these perforations occur during life. In the case (mentioned ante) in
which death took place by coma, the brain was hyperaemic. The
kidneys, as in the case of animals, show the white zone, and are con-
gested, and can be proved by microscopical and chemical means to be
rich in oxalates.
§ 703. Separation of Oxalic Acid from Organic Substances, the
Tissues of the Body, etc.—From what has been stated, no investigation
as to the cause of poison, when oxalic acid is suspected, can be con-
sidered complete unless the analyst has an opportunity of examining
both the urine and the kidneys; for although in most cases—when the
acid itself, or the acid potassic salt has been taken—there may be ample
evidence, both chemical and pathological, it is entirely different if a
case of poisoning with the neutral sodic salt should occur. In this event
* Virchow's Archiv, Bd. lxxxiii. S. 218, 1881.
542 POISONS : THEIR EFFECTS AND DETECTION. [$ 703.
there may be no congested appearance of any portion of the intestinal
canal, and the evidence must mainly rest on the urine and kidneys.
Oxalic acid being so widely distributed in the vegetable kingdom, the
expert must expect, in any criminal case, to be cross-examined by
ingenious counsel as to whether or not it was possible that the acid
could have entered the body in a rhubarb-pie, or accidentally through
Sorrel mixed with greens, etc. To meet these and similar questions it
is important to identify, if possible, any green matters found in the
stomach. In any case, it must be remembered that although rhubarb
has been eaten for centuries, and every schoolboy has occasionally
chewed small portions of sorrel, no poisoning has resulted from these
practices. When Oxalic acid has been taken into the stomach, it will
invariably be found partly in combination with lime, soda, ammonia,
etc., and partly free; or if such antidotes as chalk has been administered,
it may be wholly combined. Vomiting is nearly always present, and
valuable evidence of Oxalic acid may be obtained from stains on sheets,
carpets, etc. In a case of probably suicidal poisoning, the senior author
found no oxalic acid in the contents of the stomach, but some was
detected in the copious vomit which had stained the bed-clothes. The
urine also contained a great excess of oxalate of lime—a circumstance
of little value taken by itself, but confirmatory with other evidence.
If a liquid is strongly acid, oxalic acid may be separated by dialysis
from organic matters, and the clear fluid thus obtained precipitated by
sulphate of lime, the oxalate of lime being identified by its microscopic
form and other characters.
The usual general method for the separation of oxalic acid from
organic substances or mixtures is the following:—Extract with boiling
water, filter (which in some cases must be difficult or even impossible),
and then precipitate with acetate of lead. The lead precipitate may
contain, besides oxalate of lead, phosphate, chloride, sulphate, and
various organic substances and acids. This is to be decomposed by
sulphuretted hydrogen, and on filtering off the sulphide of lead, oxalic
acid is to be tested for in the filtrate. This process can only be
adopted with advantage in a few cases, and is by no means to be
recommended as generally applicable. The best general method, and
one which insures the separation of Oxalic acid, whether present as a free
acid, as an alkaline, or a calcic oxalate, is perhaps the following:—The
substance or fluid under examination is digested with hydrochloric acid
until a fluid capable of filtration is obtained ; the free acid is neutralised
by ammonia in very slight excess, and permitted to deposit, and the
fluid is then carefully decanted, and the deposit thrown on a filter. The
filtrate is added to the decanted fluid, and precipitated with a slight
excess of acetate of lime—this precipitate, like the first, being collected
§ 703.] oxalic ACID. t 543
on a filter. The first precipitate contains all the oxalic acid which was
in combination with lime; the second, all that which was in the free
condition. Both precipitates should be washed with acetic acid. The
next step is to identify the precipitate which is supposed to be oxalate
of lime. The precipitate is washed into a beaker, and dissolved with
the aid of heat by adding, drop by drop, pure hydrochloric acid; it is
then reprecipitated by ammonia, and allowed to subside completely,
which may take some time. The supernatant fluid is decanted, and the
precipitate washed by subsidence; it is lastly dried over the water-bath
in a tared porcelain dish, and its weight taken. The substance is then
identified by testing the dried powder as follows:—
(a) It is whitish in colour, and on ignition in a platinum dish leaves
a grey carbonate of lime. All other organic salts of lime—viz., citrate,
tartrate, etc. —on ignition become coal-black.
(b) A portion suspended in water, to which is added some sulphuric
acid, destroys the colour of permanganate of potash—the reaction being
similar to that on p. 534—a reaction by which, as is well known, Oxalic
acid or an oxalate may be conveniently titrated. This reaction is so
peculiar to oxalic acid, that there is no substance with which it can be
confounded. It is true that uric acid in an acid solution equally de-
colorises permanganate, but it does so in a different way; the reaction
between oxalic acid and permanganate being at first slow, and after-
wards rapid, while the reaction with uric acid is just the reverse—at
first quick, and towards the end of the process extremely slow.
(c) A portion placed in a test-tube, and warmed with concentrated
sulphuric acid, develops on warming carbon monoxide and carbon
dioxide; the presence of the latter is easily shown by adapting a cork
and bent tube to the test-tube, and leading the evolved gases through
baryta water. -
Alexander Gunn” has described a new method of both detecting and
estimating Oxalic acid ; it is based on the fact that a small trace of Oxalic
acid, added to an acid solution of ferrous phosphate, strikes a persistent
lemon-yellow colour; the depth of colour being proportionate to the
amount of oxalic acid,
The reagents necessary for both quantitative and qualitative testing
are as follows:—A standard solution of oxalic acid, of which 100 c.c.
equal l grm., and a solution of ferrous phosphate, containing about 12:5
per cent. of Fes2PO4, with excess of phosphoric acid.
Into each of two Nessler graduated glasses 7-5 c.c. of the ferrous
phosphate solution are run and made up to 50 c.c. with distilled water;
both solutions should be colourless; 1, 2, or more c.c. of the solution
to be tested are then run into one of the Nessler glasses; if oxalic acid
* Pharm. Journal, 1893, 408.
544 PoſsONS: THEIR EFFECTS AND DETECTION. [$ 704, 705.
be present, a more or less deep tint is produced; this must be imitated
by running the standard solution of oxalic acid into the second Nessler
cylinder—the calculation is the same as in other colorimetric estima-
tions. It does not apear to be reliable quantitatively, if alum is present;
and it is self evident that the solution to be tested must be fairly free
from colour.
§ 704. Oxalate of Lime in the Urine.—This well-known urinary
sediment occurs chiefly as octahedra, but hour-glass, contracted or
dumb-bell-like bodies, compound octahedra, and small, flattened, bright
discs, not unlike blood discs, are frequently seen. It may be usually
identified under the field of the microscope by its insolubility in acetic
acid, whilst the ammonio mag. phosphate, as well as the carbonate of
lime, are both soluble in that acid. From urates it is distinguished by
its insolubility in warm water. A chemical method of separation is as
follows:—The deposit is freed by subsidence as much as possible from
urine, washed with hot water, and then dissolved in hydrochloric acid
and filtered; to the filtrate ammonia is added in excess. The precipitate
may contain phosphates of iron, magnesia, lime, and oxalate of lime.
On treatment of the precipitate by acetic acid, the phosphates of the
alkaline earths (if present) dissolve ; the insoluble portion will be either
phosphate of iron, or oxalate of lime, or both. On igniting the residue
in a platinum dish, any oxalate will be changed to carbonate, and the
carbonate of lime may be titrated with d. n. HCl acid and cochineal
solution, and from the data thus obtained the oxalate estimated. The
iron can be tested qualitatively in the acid solution by ferrocyanide of
potassium, or it can be determined by the ordinary methods. If the
qualitative detection of oxalate of lime in the deposit is alone required,
it is quite sufficient evidence should the portion insoluble in acetic acid,
on ignition in a platinum dish, give a residue effervescing on the addition
of an acid. -
§ 705. Estimation of Oxalic Acid.—Oxalic acid is estimated in the
free state by direct weighing, or by titration either with alkali or by
potassic permangamate, the latter being standardised by oxalic acid. If
(as is commonly the case) oxalic acid is precipitated as oxalate of lime,
the oxalate may be—
(a) Dried at 100° and weighed directly, having the properties already
described.
(b) Titrated with dilute sulphuric acid and permanganate.
(c) Ignited, and the resulting carbonate of lime weighed; or
dissolved in standard acid and titrated back—one part of calcic carbonate
corresponds to 1-26 part of crystallised oxalic acid, or 0.90 part of
H2C2O4; similarly, 1 c.c. of standard acid equals 05 of calcic carbonate
(or 063 of crystallised oxalic acid).
§ 706.] OXALIC BASES. 545
(d) The oxalate may be dissolved in the smallest possible amount of
hydrochloric acid, and boiled with ammonio chloride of gold, avoiding
exposure to light ; every part of gold precipitated corresponds to '961
part of crystallised oxalic acid.
(e) The oxalate may be placed in Geissler's carbonic acid apparatus,
with peroxide of manganese and diluted sulphuric acid. The weight of
the gas which at the end of the operation has escaped, will have a
definite relation to that of the oxalate, and if multiplied by 1:4318 will
give the amount of crystallised oxalic acid.
CERTAIN OXALIC BASES-OXALMETHYLINE–OXALPROPYLINE.
§ 706. Hugh Schulz” and Mayer have contributed the results of some important
researches bearing upon a more exact knowledge of the effects of the oxalic group of
poisons, and upon the relation between chemical constitution and physiological
effects. They experimented upon oacalmethyline, chloroacalmethyline, and oacalpropy-
line.
Chloroxalmethyline (C6H3Cl]N2) is a liquid, boiling at 205°, with a weakly narcotic
smell. A solution of the hydrochlorate of the base was employed. Subcutaneous
injections of '05 grim. into frogs caused narcosis, and both this and the ethylic com-
pound deranged the heart's action, decreasing the number of beats. Thus 05 grim.
decreased the number of the beats of the heart of a frog in the course of one and
three-quarter hours as follows: 72, 60, 56, 50, 44, 40, 35, 0.
Oxalmethyline produces somewhat similar symptoms, but the nervous system is
more affected than in that which contains chlorine.
Oxalpropyline also causes marcosis, and afterwards paralysis of the hinder ex-
tremities and slowing of the heart.
The difference between the chlorime-free and the chlorine-containing oxalic bases
are summarised as follows:
FROGS.
CHLoRINE-HOLDING BASES. CHLORINE-FREE BASEs.
Notable narcosis; no heightened reflex Narcosis occurs late, and is little pro-
action, muscular cramps, nor spontaneous nounced ; a notable increase of reflex
convulsions. excitability; more and more muscular
paralysis; between times, muscular
Cramps.
CATS.
CHLoRINE-HOLDING BASEs. CHLORINE-FREE BASEs.
Notable narcosis and salivation ; no Great excitement; general shivering,
mydriasis; convulsions and paralysis; no rising to pure clonic convulsions; para-
change in the respirations. lysis of the hind legs; notable mydriasis,
jerking, and superficial respiration; weak
Ila,TCOS1S,
DOGS.
Notable narcosis; occasional vomiting ; Narcosis evident ; the rest as in cats.
the rest as in cats.
* “Beitrag zur Kenntniss der Wirkung der Oxalbasen auf den Thierkörper,”
Arch, f, exper. Path, w, Pharm., 1882,
35
PART IX. —INORGANIC POISONS.
I.—PRECIPITATED FROM A HYDROCHLORIC ACID SOLU-
TION BY HYDRIC SULPHIDE—PRECIPITATE YELLOW
OR ORANGE.”
Arsenic—Antimony—Cadmium.
1. ARSENIC,
§ 707. Metallic Arsenic, atomic weight, 75; specific gravity of amor-
phous arsenic, 4:7; of crystalline, 5:7; sublimes without fusion in small
quantities at 110° (230° F.) Guy. It occurs in commerce in whitish-
grey, somewhat brittle, crystalline masses, and is obtained by subjecting
arsenical pyrites to sublimation in earthen retorts, the arsenic being
deposited in suitable receivers on sheet iron. There is an allotropic
variety, yellow arsenic Asp obtained by subliming arsenic in a current
of CO, in the dark and condensing the vapours on a surface cooled to
0° ; yellow arsenic has an onion-like odour, is soluble in CS2, which
solution, on evaporation, leaves it in rhombohedral dodecahedrons isomor-
phous with crystals of white phosphorus; it is rapidly changed with
evolution of heat into ordinary amorphous arsenic. Metallic arsemic
is probably not poisonous, but may be changed by the animal fluids
into soluble compounds, and then exert toxic effects—volatilised metallic
arsenic is easily transformed in the presence of air into arsenious acid,
and is therefore intensely poisomous.
§ 708. Arsenious Anhydride—Arsenious Acid—White Arsenic—
Arsenic, As2O3= 198; specific gravity of vapour, 13.85; specific gravity
* Fresenius has pointed out that Sulphur may mask Small quantities of arsenic,
antimony, tin, etc., and he recommends that the turbid liquid in which apparently
nothing but sulphur has separated should be treated as follows:—A test-tube is half
filled with the liquid, and then a couple of c.c. of petroleum ether or of benzene added,
the tube closed by the thumb, and the contents well shaken. The sulphur dissolves,
and is held in solution by the solvent, which latter forms a clear upper layer. If
traces of a metallic sulphide were mixed with the sulphur, thin coloured films
are seen at the junction of the two layers, and the sulphides may also coat the
tube above the level of the liquid with a slight faintly-coloured pellicle (Chem.
News, Jan. 4, 1895).
546
§ 708.] ARSENIC. * 547
of opaque variety, 3-699; specific gravity of transparen, , riety, 3.7385.
Composition in 100 parts, As 75-75, O 24:25; therefore one part of
metallic arsenic equals 1-32 of As2O3. It is entirely volatilised at a
temperature of 204'4”.
In analysis it is obtained in brilliant octahedral crystals as a sublimate
on discs of glass, or within tubes, the result of heating a film of metallic
arsenic with access of air. It is obtained in commerce on a very large
scale from the roasting of arsenical pyrites. As thus derived, it is
usually in the form of a white cake, the arsenious acid existing in four
forms—an amorphous, a vitreous, and two crystalline—the cake being
generally opaque externally, whilst in the centre it is transparent.
According to Kruger, this change from the crystalline to the amorphous
condition is dependent upon the absorption of moisture, no alteration
taking place in dry air. The conditions under which three of the
forms of arsenic are produced are well shown by an experiment of
Debray's ; a sealed tube of As2O3 is heated in a sand bath in such a
manner as to heat the lower part to 400° C, the upper to 200° C. On
cooling, vitreous arsenic is found in the lower part, octahedral crystals
in the upper part, and in the middle prismatic crystals. The varieties
of arsenious anhydride are acid to test-paper.
The solubility of arsenious acid is often a question involving chemical
legal matters of great moment. Unfortunately, however, no precisely
definite statement can be made on this point, the reason being that the
varieties of arsenic º in very different proportions in different samples.
The amorphous and crystalline varieties having very unequal solubilities,
every experimenter in succession has given a different series of figures,
the only agreement amid the general discrepancy being that arsenic is
very sparingly soluble in water. -
The statement of Taylor may, however, be accepted as very near the
truth, viz., that an ounce of cold water dissolves from half a grain to a
grain. According to M. L. A. Buchner,” one part of crystalline arsenious
acid dissolves after twenty-four hours’ digestion in 355 parts of water at
15°; and the amorphous, under the same condition, in 108 of water. A
boiling solution of the crystalline acid, left to stand for twenty-four
hours, retains one part of acid in 46 of water; a similar solution of the
amorphous retains one of arsenic in 30 parts of water; i.e., 100 parts of
water dissolve from 2:01 to 3-3 parts of As,0s.
Boiling water poured on the powdered substance retains in cooling
a grain and a quarter to the ounce; in other words, 100 parts of water
retain 14. Lastly, arsenious acid boiled in water for an hour is dis-
solved in the proportion of 12 grains to the ounce ; i.e., 100 parts of water
retain 2-5.
* Bull. de la Société Chim. de Paris, t. xx. 10, 1873.
548 POISONS : THEIR EFFECTS AND DETECTION. [$ 709.
K. Chodomisky “ has investigated the solubility of recrystallised
arsenious acid in dilute acids, and his results are as follows:–100 c.c.
of 1:32 per cent, hydrochloric acid dissolves 1:15 grim. As,0s at 18:5°.
100 c.c. of 6 per cent. hydrochloric acid dissolves 1:27 grnm. at 18:5°.
100 c.c. of pure hydrochloric acid of the ordinary commercial strength
dissolves 1:45 grnm. As, Os: 100 c.c. of dilute sulphuric acid at 18°
dissolves about 0.54 grm. ; at 18:5° from 0-65 to 0-72 grn. ; and at
80° from 1:09 to 1:19 grim.
§ 709. Arsine—Arseniuretted Hydrogen, HaAs.--Mol. weight, 78;
vol, weight, 39; specific gravity, 2-695; weight of a litre, 3:4944 grammes;
percentage composition, 95-69 As, 4.31 H; volumetric composition, 2 vol.
HaAs = half vol. As + 3 vol. H. A colourless inflammable gas, of a foetid,
alliaceous odour, coercible into a limpid colourless liquid at ordinary
pressure of — 120”; it solidifies at – 118'9", melts at – 113.5°, and boils at
–55°. The products of the combustion of arseniuretted hydrogen are
water and arsenious acid ; thus, 2H3As + 3O2 = 3H20+ As2O3. If sup-
plied with air in insufficient quantity, if the flame itself be cooled by (for
example) a cold porcelain plate, or if the gas pass through a tube any
portion of which is heated to redness, the gas is decomposed and the metal
separated. Such a separation may be compared with that of the deposit
of carbon from ordinary flames, when made to play upon a cooled surface.
It may also be decomposed by the electric spark; f e.g., if the gas is
passed slowly through a narrow tube 0-7 to 0.8 mm. internal diameter,
provided with wires 0.5 to 0-6 mm. apart, and a small induction coil
used connected with two large Bunsen's cells, them, under these conditions,
arsenic as a metal is deposited in the neighbourhood of the sparks. For
the decomposition to be complete, the gas should not be delivered at a
greater speed than from 10 to 15 c.c. per minute. The gas burns with
a blue-white flame, which is very characteristic, and was first observed
by Wackenroder. It cannot, however, be properly seen by using the
ordinary apparatus of Marsh, for the flame is always coloured from the
glass; but if the gas is made to stream through a platinum jet, and then
ignited, the characters mentioned are very noteworthy.
Oxygen (or air) and arsine make an explosive mixture. Chlorine
decomposes the gas with great energy, combining with the hydrogen,
and setting free arsenic as a brown cloud ; any excess of chlorine
combines with the arsenic as a chloride. Sulphur, submitted to
arseniuretted hydrogen, forms sulphuretted hydrogen, whilst first
arsenic and then sulphide of arsenic separate. Phosphorus acts in a
similar way. Arseniuretted and sulphuretted hydrogen may be evolved
at ordinary temperatures without decomposition; at the boiling-point of
* Chem. Centrbl., 1889, 569.
f N. Klobrikow, Zeit. Amal. Chem..., xxix. 129–133.
§ 7 Io, 71 I.] ARSENIC. - 549
mercury (350") they are decomposed, sulphide of arsenic and hydrogen
being formed ; thus, 3H,S+2As Ha = As,Sa-H 6H2, a reaction which is of
some importance from a practical point of view. Many metals have
also the property of decomposing the gas at high temperatures, and
setting hydrogen free. Metallic oxides, again, in like manner combine
with arsenic, and set water free ; e.g., 3CuO + 2H3AS = Cu3As, + 3H2O.
A solution of copper sulphate absorbs arsine completely, and arsenide
of copper is precipitated, 3SO,Cu + 2AsH3 = 3SO, H2 + As2Cus.
Arsine acts on solutions of the noble metals like phosphuretted
hydrogen, precipitating the metal and setting free arsenious acid ; for
example, nitrate of silver is decomposed thus—
2[AsAgs + 3NOAAg]+ 3H2O = 12Ag+ Assoa 4-6NOAH.
This reaction admits of valuable practical application to the estimation
of arsenic; for the precipitated silver is perfectly arsenic-free ; the
excess of nitrate of silver is easily got rid of by a chloride of sodium
solution, and the absorption and decomposition of the gas are complete.
In cases of poisoning by arsine, the blood when examined by the
spectroscope (a process the analyst should never omit where it is
possible), is of a peculiar inky colour, and the bands between D and C
are melted together, and have almost vanished. Such blood, exposed to
oxygen, remains unaltered.
§ 710. Arsine in the Arts, etc.—In the bronzing of brass, in the
desilverising of lead by zinc, and subsequent treatment of the silver zinc
with hydrochloric acid, in the tinning of sheet iron, and similar pro-
cesses, either from the use of acids containing arsenic as an impurity,
or from the application of arsenic itself, arsine is evolved.
§ 711. Effects on Animals and Man of Breathing Arsine.—The
most general effect on mammals is to produce jaundice, bloody urine,
and increase in the biliary secretion. In the course of numerous experi-
ments on dogs, Stadelmann” found that by making them breathe a dose
of arsine, which would not be immediately fatal, icterus was always pro-
duced under these circumstances, and could be always detected by the
appearance of the tissues. The bile is remarkably thickened, and the
theory is, that in such cases the jaundice is purely mechanical, the gall-
duct being occluded by the inspissated bile. Rabbits experimented upon
similarly showed increased biliary secretion, but no jaundice; while it
was proved that cats are not so sensitive to arsine as either rabbits or
dogs. There are not wanting instances of arsine having been breathed
by man—the discoverer of the gas, Gehlen, was in fact the first victim
on record. In order to discover a flaw in his apparatus he smelt
* “Die Arsenwasserstoff-Wergiftung,” Archiv f. caper. Path. w. Pharm., Leipzig,
1882.
55O POISONS : THEIR EFFECTS AND DETECTION. [$ 7 I I.
strongly at the joints, and died in eight days from the effects of the
inhalation.
Nine persons, workmen in a factory, were poisoned by arsine being
evolved during the treatment by hydrochloric acid of silver-lead con-
taining arsenic. Three of the nine died; their symptoms were briefly
as follows:—
(1) H. K., 22 years old ; his duty was to pour hydrochloric acid on
the metal. Towards mid-day, after this operation, he complained of
nausea, giddiness, and malaise. In the afternoon he felt an uncommon
weight of the limbs, and an oppression in breathing. His fellow-work-
men thought that he looked yellow. On going home he lay down and
passed into a marcotic sleep. Next morning he went to his work as
usual, but was not capable of doing anything; he passed bloody urine
several times throughout the day, and fell into a deep sleep, from which
he could scarcely be roused. On the third day after the accident, a
physician called in found him in a deep sleep, with well-developed
jaundice, the temperature moderately high, pulse 100. On the fifth
day the jaundice diminished, but it was several months before he could
resume his work.
(2) J. T., aged 19, suffered from similar symptoms after five and
a half hours' exposure to the gas. He went home, vomited, was
jaundiced, and suffered from bloody urine ; in six days became con-
valescent, but could not go to work for many months. -
(3) C. E. was very little exposed, but was unwell for a few days.
(4) L. M., 37 years old, was exposed two days to the gas; he
vomited, had bloody urine, passed into a narcotic sleep, and died in three
days from the date of the first exposure.
(5) J. S., aged 40, was exposed for two days to the gas; the
symptoms were similar to No. 4; there was suppression of urine, the
catheter drawing blood only, and death in eight days.
(6) M. E., 36 years old ; death in three days with similar symptoms.
(7), (8), and (9) suffered like Nos. 1 and 2, and recovered after
several months.
The chief post-mortem appearance was a dirty green colour of the
mucous membrane of the intestines, and congestion of the kidneys.
Arsenic was detected in all parts of the body.”
Two cases are detailed by Dr. Valette in Tardieu's Étude.f A
mistake occurred in a laboratory, by which a solution of arsenic (instead
of sulphuric acid) was poured on zinc to develop hydrogen. Of the two
* Trost, “Wergiftung durch Arsenwasserstoff bei der technischen Gewinnung
des Silbers,” Vierteljahrsschrift f. gericht. Med., xviii. Bd., 2 Heft, S. 6, 1873.
+ Ambroise Tardieu, Étude Médico-légale sur l'Empoisonmement, Obs, xxv. p.
449.
§ 712-714.] ARSENIC. 55 I
sufferers, the one recovered after an illness of about a week or ten days,
the other died at the end of twenty-eight days. The main symptoms
were yellowness of skin, vomiting, bloody urine, great depression, slight
diarrhoea, headache, and in the fatal case a morbiliform eruption. In a
case recorded in the British Medical Journal, November 4, 1876, there
were none of the usual symptoms of gastric irritation, but loss of
memory of recent acts, drowsiness, and giddiness.
§ 712. The Sulphides of Arsenic.—Of the sulphides of arsenic, two
only, realgar and orpiment, are of any practical importance. Realga",
As,S,-214; specific gravity, 3:544; composition in 100 parts, As 70-09,
S 29.91; average composition of commercial product, As 75, S 25.
Realgar is found native in ruby-red crystals, and is also prepared arti-
ficially by heating together 9 parts of arsenic and 4 of sulphur, or 198
parts of arsenious anhydride with 112 parts of sulphur, 2AS2O3 + 7S =
2As,S, +3S03. It is insoluble in water and in hydrochloric acid, but
is readily dissolved by potassic disulphide, by nitric acid, and by aqua
regia. It is decomposed by caustic potash, leaving undissolved a brown
sediment (AsiaS), which contains 96.5 per cent. of arsenic. The
dissolved portion is readily converted into arsine by aluminium.
§ 713. Orpiment, or Arsenic Trisulphide.—As,Ss – 246; specific
gravity, 3:46; composition in 100 parts, As 60.98, S 39:02; found
native in crystals, presents itself in the laboratory usually as a brilliant
yellow amorphous powder, on passing sulphuretted hydrogen through an
acid solution of arsenious acid or an arsenite. It is very insoluble in
water (about one in a million, Fresenius), scarcely soluble in boiling con-
centrated hydrochloric acid, and insoluble generally in dilute acids. Red
fuming nitric acid dissolves it, converting it into arsenic and sulphuric
acids; ammonia and other alkaline sulphides, the alkalies themselves,
alkaline carbonates, bisulphide of potassium, and aqua regia, all dissolve
it readily. In the arts it is used as King's yellow (see p. 555). Tanners
also formerly employed a mixture of 90 parts of orpiment and 10 of
quicklime, under the name of Rusma, as a depilatory; but the alkaline
sulphides from gasworks are replacing this to a great extent.
§ 714. Haloid Arsenical Compounds.-The Chloride of Arsenic,
AsCls= 1815; specific gravity liquid, 0° 2'205; boiling-point 134°
(273.2° F.), is a heavy, colourless, oily liquid, which has been used as
an escharotic in cancerous affections (principally by quacks). In one
process of detecting and estimating arsenic, the properties of this sub-
stance are utilised (see p. 54). It is immediately decomposed by water
into arsenious and hydrochloric acids.
The Iodide of Arsenic (Asſa) is used occasionally in skin diseases, but
is of little interest to the analyst; it is commonly seen in the form of
brick-red brilliant flakes.
552 POISONs: THEIR EFFECTS AND DETECTION. [$ 715, 716.
§ 715. Arsenic in the Arts.—The metal is used in various alloys;
for example, speculum metal is made of tin, copper, and a little arsenic ;
white copper is an alloy of copper and arsenic; shot is composed of 1000
parts of lead mixed with 3 of arsenic ; the common Britannia metal used
for teapots, spoons, etc., often contains arsenic ; and brass is bronzed
with a thin film of arsenic. It was formerly much employed in the
manufacture of glass, but is being gradually superseded. It is also now
used to some extent in the reduction of indigo blue, and in that of nitro-
benzole in the manufacture of aniline.
In cases of suspected poisoning, therefore, and the finding of arsenic
in the stomach, or elsewhere, it may be set up as a defence that the
arsenic was derived from shot used in the cleansing of bottles, from the
bottles themselves, or from metal vessels, such as teapots, etc.
The arsenic in all these alloys being extremely insoluble, any solution
to a poisonous extent is in the highest degree improbable. It may, how-
ever, be necessary to treat the vessels with the fluid or fluids which have
been supposed to exert this prejudicial action, and test them for arsenic.
The treatment should, of course, be of a severe and exhaustive character,
and the fluids should be allowed to stand cold in the vessels for twenty-
four hours; then the effect of a gentle heat should be studied, and,
lastly, that of boiling temperatures. The analysis of the alloy itself, or
of the glass, it would seldom be of value to undertake, for the crushed
and finely divided substance is in a condition very different from that of
the article when entire, and inferences drawn from such analytical data
would be fallacious.
Arsenious anhydride is also used for the preservation of wood, and
is thrown occasionally into the holds of vessels in large quantities to
prevent vegetable decomposition. In India, again, a solution of
arsenic is applied to the walls as a wash, in order to prevent the attacks
of insects.
§ 716. Pharmaceutical, Non-officinal, and other Preparations of
Arsenic.—(1) Pharmaceutical Preparations.—The Liquor arsenicalis
(Fowler's solution), or solution of arsenic of the pharmacopoeia, is
composed of:—
Carbonate of Potash, g * g 87 grains (5'64 grms.)
Arsenious Acid, ſº & wº e 87 , , (5:64 , , )
Compound Tincture of Lavender, . e 5 drachms (1772 c.c.)
dissolved in 1 pint (567.9 c.c.) of water; every ounce, therefore, con-
tains 4:3 grains of arsenious acid (or 100 c.c. = 9As,Os); the strength
is therefore nearly 1 per cent. Chemically, it is a mixture of two
arsenites, As Og|K&H and 2KAsO2 + As2O3.
Liquor Ammonii Arsenitis (not officinal) is made of the same
strength, ammonium carbonate being substituted for potassic carbonate.
§ 716.] ARSENIC. 553
The hydrochloric solution of arsenic is simply arsenious acid dis-
solved in hydrochloric acid; its strength should be exactly the same as
that of Fowler's solution.
A solution of arseniate of soda * contains the anhydrous salt in the
proportion of 4 grains to the ounce (.9 in 100 c.c.) of water.
Liquor Arsenii et Hydrargyri Iodidi (Donovan's Solution of
Arsenic).-This is not officinal, but is used to some extent in skin
diseases; it is a solution of the iodides of mercury and arsenic ; strength
about 1 per cent. of each of the iodides. re
Arseniate of Iron, Fegas,Cs, is an amorphous green powder, used to
some extent in medicine. It should contain 33.6 per cent. of metallic
arsenic.
Clemen's Solution.—A solution of the bromide and arseniate of
potassium ; strength equal to 1 per cent. arsenious acid. Officinal in
U.S., France, and Norway.
Pilula Asiatica (not officinal) is composed of arsenious acid, extract
of gentian, and black pepper. There is #3th of a grain (5:4 milligrams)
of arsenious acid in each pill.
Dr. De Valanguis’ Solutio solventes mineralis is composed of 30
grains of As2Os dissolved by 90 minims of HCl in 20 oz. of water;
strength = 0.034 per cent. As,0s.
(2) Veterinary Arsenical Medicine.—Common veterinary prepara-
tions containing arsenic are:—A ball for worms, containing in parts—
Calomel, . * e e g tº 1°3 per cent.
Arsenious Acid, . & § g & 1°3 , ,
Tin Filings, g p * º e 77-9 ,,
Venice Turpentine,t . g * e 19°5 3 3
A common tonic ball: i-
Arsenious Acid, . ſº 5 to 10 grains (324 to 648 grim.)
Aniseed, tº * * # oz. (14°1744 grms.)
Opium, . e ſe º 30 grains ( 1.94 » )
Treacle, . ë ſe e Q. S.
An arsenical ball, often given by grooms to horses for the purpose
of improving their coats, contains in 100 parts:—
Arsenious Acid, . e º ſe * 2°5 per cent.
Pimento, . • * * te te 19:2 ,
Extract of Gentian, . te & * 78-3 ,,
Another ball in use is composed of arsenic and verdigris (acetate of
* The formula for arseniate of soda is Na2HAsO47H2O, but it sometimes contains
more water.
t The Venice turpentine is rarely found in ordinary commerce, what is sold
under that name consisting of black resin and oil of turpentine,
# A similar preparation in common use has the addition of sulphate of zinc.
554 POISONS : THEIR EFFECTS AND DETECTION. [$ 716.
copper), of each 8 grains (518 grnm.); cupric sulphate, 20 grains (1-3
grm.); q. S. of linseed meal and treacle.
(3) Rat and Fly Poisons, etc.—An arsenical paste sold for rats has
the following composition :- -
*. -
Arsenious Acid, . . . º - 5'0 per cent.
Lampblack, . e e e - •6 2 3 .
Wheat Flour, * º tº * - 46°3 3 2
Suet, . -> • º 46 °3 2 3
Oil of Aniseed, a small quantity.
Another rat poison is composed as follows:—
White Arsenic, . e e g e 46.8 per cent.
Carbonate of Baryta, . º e - 46-8 , ,
Rose-pink,” . * º -> e º 5'8 ,,
Oil of Aniseed, . º o e e ‘2 , ,
Oil of Rhodium, . e e - º ‘2 , ,
Various arsenical preparations are used to kill flies; the active
principle of the brown “papier moure” is arsenious acid. A dark grey
powder, which used to be sold under the name of fly-powder, consisted
of metallic arsenic that had been exposed some time to the air.
Fly-water is a strong solution of arsenious acid of uncertain
strength, sweetened with sugar, treacle, or honey. Another fly-poison
consists of a mixture of arsenious acid, tersulphide of arsenic, treacle,
and honey. - -
(4) Quack and other Nostrums.-The analyst may meet with
several quack preparations for external use in cancer. A celebrated
arsenical paste for this purpose is composed of:—
Arsenious Acid, . tº º * º 8 per cent.
Cinnabar, . ſo º º e º 70 , ,
Dragon's Blood, . g - e e 22 $ 3
Frères Come's Cancer Paste is composed of arsenious acid, 1 ;
charcoal, 1 ; red mercury sulphide, 4 ; water, q. S. -
The tasteless “ague drops” formerly used in malarious districts are
simply a solution of arsenite of potash.
Davidson's Cancer Remedy consists, according to Dr. Paris, of equal
parts of arsenious acid and powdered hemlock.
In India, arsenic given as a medicine by native practitioners, or
administered as a poison, may be found coloured and impure, from
having been mixed either with cow's urine, or with the juice of leaves,
etc.t
Arsenious acid is used by dentists to destroy the nervous pulp of
decayed and painful teeth, about the twenty-fifth of a grain (2.5 mgrms.)
* Alum and carbonate of lead coloured with Brazil and peach woods.
+ Chever, Med. Jurisprudence for India, p. 116.
§ 716.] ARSENIC. 555
being placed in the cavity. A common formula is arsenious acid, 2.;
sulphate of morphine, 1 ; creasote, q. S. to make a stiff paste. There is
no record of any accident having resulted from this practice hitherto;
but since the dentist seldom weighs the arsenic, it is not altogether free
from danger.
(5) Pigments, etc.—King's yellow should be As,Ss, the trisulphide
of arsenic or orpiment. It is frequently adulterated with 80 to 90 per
cent. of arsenious acid, and in such a case is, of course, more poisonous.
King's yellow, if pure, yields to water nothing which gives any arsenical
reaction. -
A blue pigment, termed mineral blue, consists of about equal parts
of arsenite of copper and potash, and should contain 38.7 per cent. of
metallic arsenic (= to 51-084 As2O3H) and 15:6 of copper.
Schweinfurt green (Syn. Emerald-green), (CuAs,O.),Cu(C.H.O.), is
a cupric arsenite and acetate, and should contain 25 per cent. of copper
and 58.4 per cent. of arsenious acid. In analysis, the copper in this
compound is readily separated from the arsenic by first oxidising with
nitric acid, and then adding to the nitric acid solution ammonia, until
the blue colour remains unchanged. At this point ammonium oxalate
is added in excess, the solution is just acidified by hydrochloric or nitric
acid, and, on standing, the copper separates completely (or almost so) as
oxalate, the arsenic remaining in solution.
Another method is to pass SH, to saturation, collect the sulphides on
a filter, and, after washing and drying the mixed sulphides, oxidise with
fuming nitric acid, evaporate to dryness, and again treat with nitric acid.
The residue is fused with soda and potassic nitrate, the fused mass is
dissolved in water, acidulated with nitric acid, and the copper is pre-
cipitated by potash; the solution is filtered, and in the filtrate the
arsenic is precipitated as ammonio-magnesian arseniate or as tri-
sulphide.* -
Scheele's green (CuPIASOs) is a hydrocupric arsenite, and contains
52.8 per cent. of arsenious anhydride and 33.8 per cent. of copper.
(6) External Application of Arsenic for Sheep, etc.—Many of these
are simply solutions of arsenic, the solution being made by the farmer.
Most of the yellow sheep-dipping compounds of commerce are made up
either of impure carbonate of potash, or of soda ash, arsenic, soft soap,
and sulphur. The French bain de tersier is composed of:-
Arsenious Acid, . * g o e g * 1:00 kgrm.
Ferrous Sulphate, gº tº º g * & 10:00 , ,
Peroxide of Iron, e tº º g g g 0:40 , ,
Gentian Powder, . * & * • & gº 0-20 ,,
This is to be added to 100 kgrms, of water. Another common applica-
* P. Gucci, Chem. Centröl., 1887, 1528.
556 POISONS: THEIR EFFECTS AND DETECTION. [$ 717. .
tion consists of alum and arsenic (10 or 12 to 1), dissolved in two or
three hundred parts of water.
(7) Arsenical Soaps, etc.—Arsenic is used in preserving the skins of
animals. One of the compounds for this purpose, known under the name
of Bécoeur's arsenical soap, has the following composition :-
Camphor, . g g & * e g 3'4 per cent.
Arsenic, . o e i.e. © * e º 20°2 5 3
Carbonate of Potash, . e º * tº tº 56.2 ,,
Lime,” & & * tº tº º e tº 2012 ,,
(8) Arsenical compounds used in pyrotechny:—
- Parts.
Blue fires—(1) Realgar, e o * tº * dº ſº 2
Charcoal, . g e 9. * º gº 3
Potassic Chlorate, e º º & ſº 5
Sulphur, . tº g º e ſº . 13
Nitrate of Baryta, tº re & º 77
(2) Sulphur, . g * tº & º . 40-9
Nitre, e ſº t º s ſº . 36'8
Sulphide of Antimony, tº * wº . 12°3
3 3 Arsenic, . º e * * 5
Charcoal, . g tº g * {* © 5
Green fires—Metallic Arsenic, * e e tº & 2
Charcoal, . e g ſº & tº ſº 3
Chlorate of Potash, . e * e & 5
Sulphur, . e e & & e . 13
Nitrate of Baryta, . ſº ſº e e 7
Light green fire—Charcoal, . e & e & ſº tº 1.75
Sulphide of Arsenic, . * {g º t 1.75
Sulphur, . * ſº • . . & . 10'50
Chlorate of Potash, ſº ſº g . 23°25
Nitrate of Baryta, tº º * • . 62°50
White fire—(1) Arsenious Acid, . •76
Charcoal, . iſ . e 1:63
Sulphide of Antimony, 12-27
Nitrate of Potash, 36 °59
Sulphur, 48°75
(2) Realgar, 6-1
Sulphur, 21-2
Nitrate of Potash, g e e g . 72.7
§ 717. Statistics.—During the twelve years 1892–1903 there were
registered in England and Wales 242 deaths from arsenic ; of these 58
were suicidal deaths; 79 were registered during 1900–1901 as due to
* The dust from the preserved skins of animals has caused, at least, one case
of poisoning. Ann. d’Hyg. Pub. et de Méd.-Lég., 2 sér., 1870, t. xxxiii. p. 314.
§ 718, 719.] ARSENIC. 557
arsenical beer; the remainder were accidental. The age and sex dis-
tribution of persons dying from accidental or suicidal arsenical poisoning
other than beer poisoning are detailed in the following table:—
DEATHS FROM ARSENIC DURING THE TWELVE YEARS 1892–1903.
AccIDENT OR NEGLIGENCE.
Ages, . tº º 1–5 5–15 15–25 25–65 65 and above Total
Males, . e º 3 7 6 28 4 48
Females, e e 5 6 3 42 I 57
Total, e e 8 13 9 70 5 105
SUICIDE.
Ages, . º e º 15–25 25–65 65 and above Total
Males, • * * 4 32 4 40
Females, e © º 3 15 0 18
Total, º o © 7 47 4 58
§ 718. Law Relative to the Sale of Arsenic.—By the 14th of Vict.
c. 12, every person selling arsenic is bound to keep a written record of
every particular relative to each transaction, such as the name, abode,
and calling of the purchaser, the purpose for which the poison is
required, and the quantity sold, etc. These particulars are to be signed
also by the purchaser. No person (sec. 2) is allowed to sell arsenic to
any one unknown to the seller, unless in the presence of a witness whom
the seller is acquainted with. The arsenic sold (sec. 3) is to be mixed
with soot or indigo in the proportion of half an ounce of indigo to a
pound of arsenic. It, therefore, follows that the coloured substance
should not contain more than 70 per cent. of arsenious acid. The Act
applies to all the colourless preparations of arsenic : but it is not to
affect chemists in making up prescriptions for medical men, or in
supplying medical men; nor is it to affect the wholesale dealers in
supplying arsenic to retail shops, etc. The penalty for conviction is
£20, or less.”
§ 719. Dose.—The smallest single dose of arsenic known to have
proved fatal to a human being is lö grim. (2% grains). Farriers and
grooms are in the habit of giving as much as 13 grim. (20 grains) a day
to a horse, so that the poisonous dose for this animal must be very large.
The maximum dose for the horned cattle appears to be from 32 to
'38 grm. (5 to 6 grains); that for a dog is 16 mgrms. (4 grain), and
even this may, in the smaller kinds, cause illness.
* Commercial arsenic is often much adulterated, especially with gypsum, chalk,
etc. These are most readily detected by subliming the arsenic. The sublimed
arsenic itself may not be entirely pure, sometimes containing arsenical sulphide
and antimonious oxide.
558 POISONs: THEIR EFFECTS AND DETECTION. [$ 720, 721.
The following may be considered as dangerous doses of arsenic :-13
grm. (2 grains) for an adult; 19 grim. (30 grains) for a horse; 64 grm.
(10 grains) for a cow; and 32 to 64 mgrms. (# to 1 grain) for a dog.
§ 720. Effects of Arsenious Acid on Plants.-If the root or stem
of a plant is immersed in a solution of arsenious acid, the hue of the
leaves soon alters in appearance, the green colour becomes of a whitish
or brownish hue, and the plant withers; the effect being very similar to
that produced by hot water. The toxic action may be traced from
below upwards, and analysis will detect minute quantities of arsenic in
all portions of the plant. - -
It has, however, been shown by Gorup-Besanez,” that if arsenious
acid be mixed with earth, and plants grown in such earth, they only take
up infinitesimal quantities of arsenic. Hence, in cases of cattle poison-
ing, any defence based upon the alleged presence of arsenic in the pasture
will be more ingenious than just. .
The influence of arsenical fumes as evolved from manufactories upon
shrubs and trees is in general insignificant. Pines and firs, five to six
years old, have been known to suffer from a disease in which there is a
shedding of the leaves, the more tender herbage being at the same time
affected. Whatever dangers the practice of steeping corn intended for
seed in a solution of arsenious acid, as a preventive of “smut,” may
possess, it does not appear to influence deleteriously the growth of the
future plant.
Superphosphate of manure is frequently rich in arsenic. Dr. Edmund
Davy asserts that plants to which such manure is applied take up
arsenic in their tissues, and M. Andonard has made a similar statement.
Tuson f has also undertaken some experiments, which confirm Andonard
and Davy's researches. The bearing of this with relation to the
detection of arsenic in the stomachs of the herbivora needs no comment.
§ 721. Effects on Animal Life—Animalcules.—All infusoria and
forms of animalcule-life hitherto observed perish rapidly if a minute
quantity of arsenious acid is dissolved in the water in which they exist.
Insects.-The common arsenical fly-papers afford numerous oppor-
tunities for observing the action of arsenic on ordinary flies; within a few
minutes (five to ten after taking the poison into their digestive organs)
they fall, apparently from paralysis of the wings, and die. Spiders and
all insects into which the poison has been introduced exhibit a similar
sudden death. It is said that in the neighbourhood of arsenical manu-
factories there is much destruction among bees and other forms of insect
life.
Annelids.-If arsenious acid is applied to the external surface of
* Annal. d. Chemie w. Pharmacie, Bd. cxxvii., H. 2, 243.
+ Cooley's Dictionary, Art. “Arsenic,”
§ 72 I.] ARSENIC. 559
worms or leeches, the part which it touches perishes first, and life is
extinguished successively in the others. If a wound is made first, and
the arsenious acid then applied to it, the effects are only intensified and
hastened. There is always noticed an augmentation of the excretions;
the vermicular movements are at first made more lively, they then
become languid, and death is very gradual.
Birds.—The symptoms with birds are somewhat different, and vary
according to the form in which the poison is administered, viz., whether
as a vapour or in solution. In several experiments made by Eulenberg
on pigeons, the birds were secured under glass shades, and exposed to
the vapour of metallic arsenic vaporised by heat. It is scarcely neces-
sary to remark that in operating in this way, the poisoning was not
by metallic arsenic vapour, but by that of arsenious acid. One of these
experiments may be cited :-A pigeon was made to breathe an atmo-
sphere charged with vapour from the volatilisation of metallic arsenic.
The bird was immediately restless; in thirty minutes it vomited
repeatedly, and the nasal apertures were noticed to be moist ; after a
little while, the bird, still breathing the arsenious acid atmosphere, was
much distressed, shook its head repeatedly, and yawned ; in fifty minutes
the respiration was laboured, and in fifty-nine minutes there was much
vomiting. On removing the bird, after it had been exposed an hour to
the vapour (16 grm. of metallic arsenic having been evaporated in all),
it rapidly recovered.
Six days after, the pigeon was again exposed in the same way to the
vapour, but this time 56 grim. of metallic arsenic was volatilised. In
fifteen minutes there was retching, followed by vomiting. On taking it
out after an hour it remained very quiet, ate nothing, and often puffed
itself out ; the breathing was normal, movements free, but it had
unusual thirst. On the second and third day the excretions were
frequent and fluid ; the cardiac pulsations were slowed, and the bird was
disinclined to move. On the fourth day it continued in one place,
puffing itself out ; towards evening the respirations slowed, the beak
gaping at every inspiration. On attempting flight, the wings fluttered
and the bird fell on its head. After this it lay on its side, with slow,
laboured respiration, the heart-beats scarcely to be felt, and death took
place without convulsions, and very quietly. On examining the organs
after death, the brain and spinal cord were very bloodless; there were
ecchymoses in the lungs; but little else characteristic. The experiment
quoted has a direct bearing upon the breathing of arsenical dust ; as, for
example, that which floats in the air of a room papered with an easily
detached arsenical pigment. Other experiments on birds generally have
shown that the symptoms produced by arsenious acid in solution, or in
the solid form, in a dose insufficient to destroy life, are languor, loss of
56o POISONS : THEIR EFFECTS AND DETECTION. [$ 722.
appetite, and the voidance of large quantities of liquid excreta like
verdigris. With fatal doses, the bird remains quiet ; there are fluid,
sometimes bloody, excretions; spasmodic movements of the pharynx,
anti-peristaltic contraction of the Oesophagus, vomiting, general tremb-
ling of the body, thirst, erection of the feathers, and laboured respiration.
The bird becomes very feeble, and the scene mostly closes with
insensibility and convulsions.
Mammals, such as cats, dogs, etc., suffer from symptoms fairly iden-
tical with those observed in man; but the nervous symptoms (according
to P. Hugo) do not predominate, while with rabbits and guinea-pigs,
nervous symptoms are more marked and constant.* There are vomiting,
purging, and often convulsions and paralysis before death. It has been
noticed that the muscles after death are in a state of great contraction.
The slow poisoning of a dog, according to Lolliot,f produced an erythe-
matous eruption in the vicinity of the joints, ears, and other parts of the
body; there were conjunctivitis, increased lachrymal secretion, and
photophobia ; the hair fell off.
§ 722. Effects of Arsenious Acid on Man,—The symptoms produced
by arsenious acid vary according to the form of the poison—whether
solid, vaporous, or soluble—according to the condition of bodily health
of the person taking it, and according to the manner in which it is intro-
duced into the animal economy, while they are also in no small degree
modified by individual peculiarities of organisation and by habit, as, for
instance, in the arsenic-eaters.
Arsenic-Eaters.-In all European countries grooms and horse-dealers
are acquainted with the fact that a little arsenic given daily in the corn
improves the coat, increases, probably, the assimilation of the food, and
renders the horse plump and fat. On the Continent grooms have been
known to put a piece of arsenic, the size of a pea, in a little oatmeal,
make it into a ball, tie it up in a linen rag, and attach it to the bit ; the
saliva dissolves, little by little, the poison, while both the gentle irritation
and physiological action excite a certain amount of Salivation, and the
white foam at the mouth, and the champing of the horse, are thought
vastly to improve the appearance. Shot, which contains a small quantity
of arsenic, has been used for the same purpose, and from half a pound
to a pound of small shot has been given to horses. When a horse has
been for a long time dosed with arsenic, it seems necessary to continue
the practice; if this is not done, the animal rapidly loses his condition.
The explanation probably is, that the arsenic stimulates the various cells
and glands of the intestinal tract to a superaction, the natural termina-
tion of which is an enfeeblement of their secreting power—this especially
* Archiv f. exper. Path, w. Pharmakol., Leipzig, 1882.
+ Etude Physiol. d’Arsène, These, Paris, 1868.
§ 723.] ARSENIC. 561
in the absence of the stimulus. Turning from equine involuntary arsenic-
eaters, we find the strange custom of arsenic-eating voluntarily pursued by
the races of lower Austria and Styria, especially by those dwelling on the
mountains separating Styria from Hungary. In India also (and especially
in the Punjaub) the same practice prevails, and here it is often taken as
an aphrodisiac. The mountaineers imagine that it increases the respira-
tory power, nor is there wanting some evidence to show that this is
actually the fact, and medicinal doses of arsenic have been in use for
some time in cases of asthma and other diseases of the chest. The
arsenic-eaters begin with a very small dose, which is continued for several
weeks or months, until the system gets accustomed to it. The amount
is then slightly augmented until relatively large doses are taken with
impunity. In one case * it appears that a countryman, in good health,
and sixty years of age, took daily 4 grains of arsenious acid, a habit
which he had inherited from his father, and which he in turn bequeathed
to his son.
The existence of such a custom as arsenic-eating, in its literal sense,
has more than once been doubted, but all who have travelled over Styria
and other places where the habit prevails have convinced themselves
that the facts have not been overstated. For example, Dr. Maclagan, in
company with Dr. J. T. Rutter, f visited Styria in 1865, and having
carefully weighed 5 or 6 grains of arsenic, saw these doses actually
swallowed by two men. On collecting their urine, about two hours
afterwards, abundant quantitative evidence of its presence was found ;
but in neither of the men were there the slightest symptoms of poisoning.
It is obvious that the existence of such a habit might seriously complicate
any inquiry into arsenical poisoning in these regions.
§ 723. Manner of Introduction of Arsenic.—Arsenious acid exerts a
poisonous action, whether it is taken by the stomach, or introduced into
the system by any other channel whatever. The differences in the
symptoms produced by external application (as through a wound), and by
swallowing arsenious acid in substance or in solution, are not so marked
as might be expected. It was probably Hunter who first distinctly
recognised the fact that arsenic, even when introduced outwardly by
application to an abraded surface, exerts a specific effect on the mucous
membrane of the stomach. Brodie ; states, “Mr. Home informed me
that in an experiment made by Mr. Hunter himself, in which arsenic
was applied to a wound in a dog, the animal died in twenty-four hours,
and the stomach was found to be considerably inflamed. I repeated this
experiment several times, taking the precaution of always applying a
* Tardieu, op. cit.
† Edin. Med. Journ., April 1865; Brit, and For. Med. Chir. Journ., Oct. 1865.
# Phil. Trans., 1812.
36
562 POISONS : THEIR EFFECTS AND DETECTION. [$ 724.
bandage to prevent the animal licking the wound. The result was that
the inflammation of the stomach was commonly more violent and more
immediate than when the poison was administered internally, and that
it preceded in appearance the inflammation of the wound.”
§ 724. Cases of Poisoning by the External Application of Arsenic.
—A mass-poisoning by the external use of arsenical violet powder to
infants occurred in England some years ago. Two deaths from this
cause were established by coroners' inquests.” Dr. Tidy found the violet
powders used in the two cases to have the following composition:—
1. 2.
* Per cent, Per cent.
Arsenious Acid, . © ſº g e e 38°5 38-3
Starch (Potato), . º e e e t- 54-8 55-4
Magnesia, etc., º ſº º & e º 6-7 6:3 +
Although the children were poisoned by absorption through the skin
(unless it is allowed that some may have found its way in the form of
arsenical dust into the throat, or, what is still more probable, that the
infants may from time to time have seized the puff-ball and sucked it),
the large quantity of '421 grm. (6-5 grains) of arsenious acid was
separated in the one case, and 194 grn. (3 grains) in the other. In
these cases arose the question which is sure to recur in legal inquiries into
poisoning by absorption, viz., whether the poison lying on the surface
and folds of the skin could not have been mixed during the post-mortem
examination with the organs of the body? In these particular cases
special care appears to have been taken, and the answer was satisfactory.
It is not amiss, however, to call attention to the extreme precaution
which such instances necessitate.
A woman, aged 51, had used a solution of arsenious acid to cure
* “Gleanings in Toxology,” by C. Meymott Tidy, M. B.-Lancet, Aug. 21,
1878.
† Two recipes were handed in at the coroner's inquest which pretty fairly represent
the composition of ordinary commercial violet powder:—
First Quality, sold at 7s. per gross.
Starch Powder, - º & º e º g 28 lbs.
Magnesia, º e º º º * º º 1% lb.
Orris-root, º º tº & ſº & º g 1 lb.
Violet Perfume, . º e e e º & 1 oz.
Essence of Roses, . o e ſº * e g 5 drops.
Second Quality, sold at 6s. per gross.
Terra Alba (Sulphate of Lime), e e e 0. 14 lbs.
Potato Starch, o º * e • * * e 21 lbs.
Magnesia, º º - e - e e e 3 lbs.
Orris-root, . º º - e º e & 1% lb.
Violet Perfume, . º o º © º e 1% oz.
Essence of Roses, • 5 drops.
§ 724.] ARSENIC, z 563
the itch; erysipelas of the body, however, followed, and she died after a
long illness—one of the symptoms noted being trembling and paresis of
the limbs.” In a case recorded by Desgranges,f a young chambermaid
had applied to the unwounded scalp an arsenical ointment for the purpose
of destroying vermin. She also suffered from a severe erysipelas, and
the hair fell off. Quacks have frequently applied various arsenical pastes
to ulcers and cancerous breasts with a fatal result. Instances of this
abound; in one, a charlatan applied to a chronic ulcer of the leg an
arsenical caustic ; the patient showed symptoms of violent poisoning, and
died on the sixth day. In another, a lady suffering from some form of
tumour of the breast, applied to an unqualified practitioner, who made
from fifteen to twenty punctures with a lancet in the swelling, covered a
piece of bread with an arsenical compound, and applied the bread thus
prepared to the breast. Twelve hours afterwards symptoms of violent
gastric irritation commenced; and vomiting and a sanguinolent diarrhoea
followed, with death on the fifth day. Arsenic was found in all the
organs. § Such examples might be multiplied. Arsenic has been in
more than one case introduced criminally into the vagina with a fatal
result. || Foderé, e.g., has recorded the case of a maid-servant who
poisoned her mistress by intentionally administering several arsenical
enemata." Arsenious acid again has been respired in the form of vapour.
One of the best instances of this is recorded by Taylor, and was the sub-
ject of a trial at the York Lent Assizes, 1864. The prisoner placed some
burning pyrites at the doorway of a small room, in which there were
eight children, including an infant in the cradle. The other children
were removed speedily, but the infant was exposed to the vapour for an
hour; it suffered from vomiting and diarrhoea, and died in twenty-four
hours. There was slight inflammation of the stomach and intestines, the
brain and lungs were congested, and the lining membrane of the trachea
of a bright red colour. Arsenic was detected in the stomach, in the lungs,
and spleen. The pyrites contained arsenic, and the fatal fumes were in
effect composed of sulphurous and arsenious acids.
* Belloc, Méd.-Lég., t. iv. p. 124.
t Recueil de la Soc. de Méd. de Paris, t. vi. p. 22, An. vii.; also Tardieu, Étude
Méd.-Légale sur l'Empoisonnement, Obs. xxvii. p. 457.
# Mean, Bibliothèque Méd., t. lxxiv., 1821, p. 401.
§ Tardieu, op. cit., Obs. xxix. ; Dr. Vernois, Ann. d’Hyg. et de Méd.-Lég., t.
xxxvi., 1st Ser., p. 141, 1846.
| Ansiaulx, Clinique Chirurgicale. Mangor (Acta Societ. Reg. Hafniens, iii.
p. 178) gives the case of a man who poisoned his three wives successively with
arsenic—the last two by introducing into the vagina a powder composed of flour and
arsenic. Another similar case is related by Brisken. Mangor made experiments
on mares, showing that when arsenic is applied to the vagina, death may result
from inflammation.
*I Méd.-Légale, iv.
564 POISONs: THEIR EFFECTS AND DETECTION. [$ 725,726.
§ 725. Arsenic in Wall-Papers.—It is now an accepted fact that
arsenical colours on wall-papers cause illness. The symptoms are those
of chronic poisoning, and present nothing distinctive from the effects
produced from small doses of arsenic.
Kirschgasser * has described the symptoms in detail of twenty-six
cases. That arsenic is actually present in patients suffering is often
susceptible of proof, by examining skilfully and carefully a considerable
volume (from one to two days’ collection) of the urine; in most of
the cases thus examined arsenic has been discovered. This poisoning
is produced, sometimes from the dust, at others from diethylarsine
(C3H5)2AsH, a gas produced by moulds f such as Mucor mucedo,
Aspergillus glaucus, and others growing in a medium in which arsenic
is present. Gosio cultivated the Mucor mucedo on slices of potato
arsenic free, in bulbs having a constriction in the neck; in this con-
striction, four centimetres away from the slices of potato, was packed some
cottom wool impregnated with a weak solution of arsenic; in time the
mould crept up to and invaded the cotton wool. From this experiment
Gosio concluded that the mould could grow on the surface of the paper
turned to the wall, and that the mycellium could grow through the
pores of paper and attack the arsenical colours in the wall side of
the paper. Diethylarsine is a gas with a strong alliaceous odour; it
precipitates a hydrochloric acid solution of sublimate, forming crystals
of diethylarsime-chloro- mercurate, AsFI(C2H5), HgCl2; the crystals
fuse at about 240°. It also gives a precipitate with mercuric nitrate,
As H(C2H5)2(NO3), Hg ethyl-arsine-mercuric nitrate.
The gas appears to be readily enough produced by the action
of the common moulds upon organic matter in the presence of small
amounts of arsenic ; the moulds vary in this property: Mucor mucedo
and Aspergillus glaucus react well; on the contrary, Penicillium glaucum,
Mucor ramosus, and several others have either no action, or the action
is but slight. One mould, the Penicillium brevicaule, has quite a special
endowment in forming this peculiar arsenical compound ; so much so,
that Gosio has proposed its use as a reagent for arsenic, the garlic odour
being perceived when the fungus is made to grow in solutions containing
organic matter and only traces of arsenic.
§ 726. Forms of Arsenical Poisoning.—There are at least four dis-
tinct forms of arsenical poisoning, viz., an acute, subacute, a nervous,
and a chronic form.
Acute Form.—All those cases in which the inflammatory symptoms
are severe from the commencement, and in which the sufferer dies within
* Vierteljahr. f. gericht. Med., N. F., ix. 96.
† Gosio, Archives Italiennes de biologie, 1892. R. Abel and P. Buttenberg,
Zeit. f. Hygiene, 1899. -
§ 727.] ARSENIC. 565
twenty-four hours, may be called acute. The commencement of the
symptoms in these cases is always within the hour; they have been
known, indeed, to occur within eight minutes, but the most usual time
is from twenty minutes to half an hour. There is an acrid feeling in
the throat, with nausea; vomiting soon sets in, the ejected matters
being at first composed of the substances eaten ; later they may be
bilious or even bloody, or composed of a whitish liquid. Diarrhoea
follows and accompanies the vomiting, the motions are sometimes like
those met with in ordinary diarrhoea and English cholera, and some-
times bloody. There is coldness of the extremities, with great feeble-
ness, and the pulse is small and difficult to feel. The face, at first very
pale, takes a bluish tint, the temperature falls still lower; the patient
sinks in collapse, and death takes place in from five to twenty hours
after the taking of the poison.
"here can scarcely be said to be any clinical feature which distin-
guishes the above description from that of cholera ; and supposing that
cholera were epidemic, and no suspicious circumstance apparently
present, there can be little doubt that a most experienced physician
might mistake the cause of the malady, unless surrounding circum-
stances give some hint or clue to it. In the acute form diarrhoea may
be absent, and the patient die, as it were, from “shock.” This was
probably the cause of death in a case related by Casper,” that of Julius
Bolle, poisoned by his wife. He took an unknown quantity of arsenic
in solution at seven in the morning, and in about three-quarters of an
hour afterwards suffered from pain and vomiting, and died in little more
than three hours. There were no signs of inflammation in the stomach
and intestines, but from the contents of the stomach were separated
'0132 grm. of arsenious acid, and '00513 grnm. from pieces of the liver,
spleen, kidneys, lung, and blood. The dose actually taken is supposed
not to have been less than 388 grim. (6 grains).
§ 727. The Subacute Form.—The subacute form is that which is
most common ; it exhibits some variety of phenomena, and individual
cases vary much in the matter of time. The commencement of
symptoms is, as in the most acute form, usually within the hour, but
exceptions to this rule occur. In a case quoted by Taylor, t and re-
corded by M. Tommelier, the poison did not cause any marked illness for
eight hours; it was found, on post-mortem examination, that a cyst had
been formed in the stomach which sheathed the arsenic over, and in
some degree explained this delay. In another case, again, ten hours
elapsed, and this is considered to be the maximum period yet observed.
* Case 188 in Casper's Handbuch.
t Taylor's Principles and Practice of Jurisprudence, vol. i. p. 251 ; Flandin,
vol. i. p. 535.
566 POISONS: THEIR EFFECTS AND DETECTION. [$ 727.
As with the acute form, there is a feeling of nausea, followed by vomit-
ing, which continues although the stomach is quite empty; at first the
ejected matter is a watery fluid, but later it may be streaked with
blood. The tongue is thickly coated; there is great thirst, but the
drinking of any liquid (even of ice-cold water) increases the vomiting.
Nearly always pain is felt in the epigastrium, spreading all over the
abdomen, and extending to the loin (which is tense and tender on
pressure). Deglutition is often painful, and is accompanied by a sort
of spasmodic constriction of the pharyngeal muscles. Diarrhoea follows
the vomiting, and has the same characters as that previously described ;
occasionally, however, this feature is absent. In the case recorded by
Martineau,” a man, aged 25, was seized at 10 A.M. suddenly with vomit-
ing, which persisted all that day and the next, during which time the
bowels were obstinately confined. On the second day a purgative was
administered, whereupon diarrhoea set in, and continued until his death,
which occurred in about two days and sixteen hours from the com-
mencement of the symptoms. This case is also remarkable from the
absence of pain or tenderness of the abdomen.
In subacute cases the urine has several times been suppressed, and
it is generally scanty and red in colour. Irregularity of the heart's
action and feebleness are tolerably constant phenomena. As the end
approaches, there is excessive muscular weakness, the face is pale, the
eyes hollow ; the mucous membranes first, and then the skin, take a
bluish tint; the skin itself is covered with perspiration, and there has
been noticed a peculiar odour, which has been likened to arsine (arseniu-
retted hydrogen). The respiration is troubled, convulsive movements of
the limbs have been observed, and cramps in the calves of the legs;
death follows in a variable time—from twenty-four hours to several
days. In certain cases there is a curious remission after violent
symptoms, the patient rallies and seems to have recovered ; but the
appearance is deceptive, for the symptoms recur, and death follows.
Recovery may also take place partially from the primary effects, and
then inflammatory changes in the stomach, etc., set in, with fever and
the ordinary symptoms which are common in all internal inflammation.
A single dose of arsenious acid may cause a prolonged and fatal
illness, one of the best known examples being that of the suicide of the
Duc de Praslin, f who took, with suicidal intent, on Wednesday, August 18,
1847, a dose of arsenious acid. The exact time of the act could not be
ascertained, but the first effects appeared at 10 P.M.; there were the
usual signs of vomiting, followed on the next day by diarrhoea, fainting,
* Tardieu, op. cit., Obs, xix.
+ Tardieu, “Relation Médico-Légale de l’Assassinat de la Duchesse de Praslin,”
Amm. d’Hyg. Pub. et de Médico-Lég., 1847, t. xxxviii. p. 390; also op. cit., Obs. xi.
§ 728.] ARSENIC. 3. 567
and extreme feebleness of the pulse. On Friday there was a remission
of the symptoms, but great coldness of the limbs, intermittency and
feebleness of the heart's action, and depression. On Saturday there was
slight fever, but no pain or tenderness in the abdomen, vomiting, or
diarrhoea; on this day no urine was passed. On the Sunday he com-
plained of a severe constriction of the throat, and deglutition was
extremely painful; thirst was extreme, the tongue intensely red, as well
as the mucous membrane of the mouth and pharynx, and the patient
had a sensation of burning from the mouth to the anus. The abdomen
was painful and distended, the heat of the skin was pronounced, the
pulse frequent and irregular, -sometimes strong, at others feeble, the
bowels had to be relieved by injections, the urine was in very small
quantity; during the night there was no sleep. The duke died at
4.35 A.M. on Tuesday the 24th, the sixth day; intelligence was retained
to the last. As the end approached, the respiration became embarrassed,
the body extremely cold, and the pulse very frequent.
§ 728. In the nervous form the ordinary vomiting and purging are
either entirely suppressed, or present in but feeble degree ; and under
this heading are classed the rare cases in which, in place of the ordinary
symptoms, affections of the nervous system predominate. Narcotism,
paresis, deepening into paralysis, delirium, and even acute mania, as well
as epileptiform convulsions, have all been recorded. In short, the
symptoms show so much variety, that an idea of the malady produced
in this very rare form can only be obtained by studying the clinical
history of cases which have presented this aspect. In a case recorded
by Guilbert,” a man, thirty-five years of age, had swallowed a solution
of arsenic, half of which was immediately rejected by vomiting. A
little while afterwards his respiration became laborious; the eyes were
bathed with tears, which were so acrid as to inflame the eyelids and the
cheeks; the muscles of the face were from time to time convulsed; he
perspired much, and the perspiration had a foetid odour; there was some
diarrhoea, the urine was suppressed, and from time to time he was
delirious. Afterwards the convulsions became general, and the symptoms
continued with more or less severity for five days. On the sixth a
copious miliary eruption broke out, and the symptoms became less
severe. The eruption during fifteen days every now and again re.
appeared, and at the end of that time the patient was convalescent,
but weak, liable to ophthalmia, and had a universal trembling of the
limbs.
In one of Brodie's f experiments on rabbits, 7 grains of arsenious
* Journal de Van der Monde, 1756, t. iv. p. 353; Tardieu, op. cit., Obs. xiii.
p. 430.
+ “The Action of Poisons,” Phil, Trans., 1812.
568 POISONS: THEIR EFFECTS AND DETECTION. [$ 729, 730.
acid were inserted in a wound in the back; the effect of which was to
paralyse the hind legs. In other experiments on animals, paralysis of
the hind legs has been frequently noticed, but paralysis certainly is
rare in man; in the case, however, recorded by Barrier,” of the five
men who took by mistake a solution of arsenious acid, one of them
was found stretched on the ground with the inferior extremities
paralysed.
In a case of “mass” poisoning reported by Dr. Coqueret,i three
persons ate by mistake an unknown quantity of arsenious acid—two of
them only suffered slightly, but the third severely, vomiting occurring
almost immediately, and continuing with frequency until the end of the
fourth day. Two hours after swallowing the poison, the patient took
the hydrated oxide of iron as an antidote. On the sixth day there was
stupor and a semi-delirious state, with an eruption of a pustular
character compared to that of the small-pox. These symptoms con-
tinued more or less until the fifteenth day, when they diminished, and
ultimately the patient recovered. In a case related by Tardieuf, in
which a person died on the eleventh day from the effects of the poison,
towards the end, as a specially marked symptom, there was noted
hyperaesthesia of the inferior extremities, so that the least touch was
painful. .
§ 729. Absence of Symptoms.-In a few cases there have been a
remarkable absence of symptoms, and this both in man and animals.
Seven horses were fed with oats accidentally mixed with arsemiate of
soda. The first succumbed three hours after taking the poison, without
having presented any symptom whatever; he fell suddenly, and in a
short time expired.S. It is related by Orfilaſ that a woman, aged 27,
expired in about twelve hours from a large dose of arsenious acid; there
were the usual post-mortem appearances, but in life no sign of pain, no
vomiting, and but little thirst.
§ 730. Slow Poisoning.—Slow poisoning has been caused accidentally
by arsenical wall-paper, in the manufacture of arsenical pigments, by the
admixture of small quantities of arsenic with salt or other condiments,
and repeated small doses have been used for criminally producing a fatal
illness intended to simulate disease from matural causes. The illness
produced by small intermittent doses may closely resemble in miniature,
as it were, those produced by large amounts; but, on the other hand,
they may be different and scarcely to be described otherwise than as a
* Journ. de Médecine, 1783, p. 353; Tardieu, op. cit., Obs. xiv. p. 431.
t Journ. de Connaiss. Méd. Chirurg., 1839, p. 155; Tardieu, op. cit., Obs. xv.
p. 482.
† Op. cit., Obs. xvii. p. 434.
§ Bouley (Jeune), Amn. d’Hyg. et de Médico-Lég., 1834, t. xii. p. 393.
|| Tome i., Obs. iv. p. 314.
§ 73 I.] ARSENIC. 569
general condition of ill-health and malaise. In such cases there is loss
of appetite, feebleness, and not unfrequently a slight yellowness of the
skin. A fairly constant effect seen, when a solution of arsenious acid is
given continuously for a long time, is an inflammation of the con-
junctiva, as well as of the nasal mucous membrane—the patient com-
plains of “always having a cold.” This inflammatory action also affects
the pharynx, and may extend to the air-passages, and even to the lung-
tissue. At the same time there is often seen an exanthem, which has
received a specific name—“eczema arsenicale.” Salivation is present, the
gums are sore, at times lacerated. In chronic poisoning by arsenic,
nervous symptoms are almost constant, and exhibit great variety; there
may be numbness, or the opposite condition, hyperasthesia, in the ex-
tremities. In certain cases fainting, paresis, paralysis, and sometimes
convulsions occur; towards the end a sort of hectic fever supervenes,
and the patient dies of exhaustion.
§ 731. The Maybrick Case.*—The Maybrick case may be considered an example
of poisoning extending over a considerable' period of time —Mr. James Maybrick, a
Liverpool cotton-broker, aged 49, married Florence Elizabeth, an American lady,
aged 21. They had two children. The marriage proved an unhappy one. Some
two years before his death in May 1889 they had occupied two separate rooms.
Seven weeks before the husband’s death, Mrs. Maybrick went to London on a false
pretext, and lived for some days at an hotel, ostensibly the wife of another man.
Two days after her return, Mr. and Mrs. Maybrick attended the Grand National
race meeting, and there a serious quarrel arose between them respecting the man
with whom she had cohabited in London ; they returned from the race, each
separately, and she slept apart. Next day an apparent reconciliation took place
through the intervention of Dr. Fuller, the family medical attendant.
On or about April 12–19th, 1889, Mrs. Maybrick purchased arsenical fly-papers.
On April 13–20th Mr. Maybrick visited London, and consulted Dr. Fuller for dyspepsia,
who prescribed nux vomica, acids, and mild remedies (but no arsenic); in one bottle
of medicine, ostensibly made according to Dr. Fuller's prescription, arsenic was
subsequently found.
Up to Saturday, April 27th, Mr. Maybrick was in his usual health ; he was then
sick, numbed, and in pain, and had cramps; he told his clerk he had been an hour
in the water-closet, but whether for diarrhoea or constipation does not appear; he
ascribed the symptoms to an overdose of Fuller's medicine. About this date fly-
papers were found by the servants soaking in Mrs. Maybrick's bedroom in a sponge-
basin, carefully covered up. On the 29th she again purchased two dozen fly-papers
from another chemist. On April 28th Mr. Maybrick was sick and ill; at 11 A.M.
Dr. R. Humphreys was called in ; Mr. Maybrick complained of a peculiar sensation
about his heart, and said he was in dread of paralysis. He attributed his illness to
a strong cup of tea taken before breakfast. On the following day he was better, and
on the 30th still improving. On May 1st and 2nd Mr. Maybrick went to his office
and lunched, both days, off revalenta food, prepared at home and warmed at his office
in a new saucepan purchased for the occasion ; on one of these days the lunch was
forgotten, and was sent to Mr. Maybrick by his wife ; and on one of the two days,
* “The Maybrick Trial and Arsenical Poisoning,” by Thos. Stevenson, M.D.,
Guy’s Hosp. Rep., 1889.
57O POISONS: THEIR EFFECTS AND DETECTION. [$ 731.
it is not clear which, Mr. Maybrick complained that his lunch did not agree with
him, and he attributed it to inferior sherry put into his food.
In a jug found at the office, and in which food had been taken there, a trace of
the food still remained after Mr. Maybrick's death, and arsenic was found therein.
On May 3rd the last, fatal illness set in. It is uncertain what food he had after
breakfast; he went to the office, and returned home between 5 and 6 P.M. He had
been seen by Dr. Humphreys in the morning, and appeared then not quite so well;
he found him at midnight suffering from what he thought was severe sciatica; the
patient said he had been sick from revalenta. On May 4th he was continually sick,
nothing could be retained on the stomach, but the sciatic pain was gone; on May 5th
the vomiting continued, the patient complained of the sensation of a hair sticking in
the throat, and of a filthy taste in the mouth. The throat and fauces were only
slightly reddened, the tongue was furred. -
On May 6th there was less vomiting, but otherwise the condition was the same,
and Fowler's solution ordered, but only a quantity equal to a $o grain was actually
taken. -
May 7th the condition was improved, but there was no increase of power. Dr.
W. Carter was called in consultation. The vomiting was passing away, and diarrhoea
commencing. The throat was red, dry, and glazed ; there were incessant attempts
to cough up an imaginary hair. No cramps, no pain in the stomach or intestines,
nor conjunctivitis. On this day the first direct evidence of diarrhoea is recorded, the
medical men actually seeing a loose motion. The result of the consultation was that
Mr. Maybrick must have taken some irritant in his food or drink.
On the 8th a professional nurse took charge. During the 8th and 9th severe
tenesmus set in with diarrhoea, and blood was observed in the faeces. Now arsenic
was suspected, the urine was examined by Dr. Humphreys, and a rough analysis was
made of some Neaves’ food which the patient had been taking.
The patient died on the 10th, at 8.30 P.M.
The post-mortem appearances were as follows:–
The tongue was dark, the top of the gullet slightly red, but otherwise healthy,
save at the lower end, where the mucous membrane was gelatinous, and was dotted
over with black dots, like frogs’ spawn.
There was a small shallow ulcer in the mucous membrane of the larynx at the back
of the epiglottis. The free margin of the epiglottis was rough and eroded ; and on
the posterior aspect of the cricoid cartilage there were two small red patches. In the
stomach were from 5–6 ozs. of brownish fluid. At the cardiac end there was a large
vermilion-red patch, interspersed here and there with small dark ecchymoses (spoken
of by Dr. Humphreys as a flea-bitten appearance); to this followed a non-inflamed
space, and near the pyloric orifice, and extending 2 inches from it, was another red
inflamed portion of mucous membrane. In the Small intestine the mucous membrane
was red and inflamed, from 3 inches below the pylorus to about 3 feet downwards.
About 18 or 20 feet lower down, i.e., a little below the ileo-caºcal valve, the mucous
membrane was again inflamed to a less extent over a space of about two feet; the
lower end of the rectum was also red and inflamed. No arsenic was found in the
stomach or its contents, or in the spleen. Arsenic was present in the liver, in the
intestines, and in the kidneys. The quantity separated altogether amounted to over
0-1 grain. The liver weighed 48 ozs., and from 12 ozs. of the liver 0.076 grain of
arsenic, reckoned as As2O3, was separated.
The whole course of the symptoms and the post-mortem examination showed that
the deceased died from an irritant poison ; and from the fact of a small quantity of
arsenic having been found in the body, there can be little doubt but that the poison
was arsenic. The symptoms were somewhat anomalous, but not more so than in
other recorded cases of undoubted arsenical poisoning. The facts that tended to
connect the accused with the death were as follows:–On the night of either May
§ 73 IA.] ARSENIC, 57 I
9th or the 10th Mrs. Maybrick was observed to remove from the table an opened
bottle of Valentine's meat juice, and take it into an inner dressing-room, and then
replace it—the acts being surreptitious. In replacing it, she was observed to take it
either from the pocket of her dressing-gown or from an inner pocket. The lining of
this pocket was found to be impregnated with As2O3. The juice was found to contain
0.5 grain As2O3, and the liquid was of lower gravity than commercial juice; it had
probably, therefore, been diluted.
The following is a list of things containing arsenic :—-
1. Mrs. Maybrick's dressing-gown.
2. 2 3 apron.
3. A handkerchief wrapped around a bottle.
4. Packet of arsenic “for cats.” (Arsenious acid mixed with charcoal.)
Tumbler containing milk, with handkerchief soaking in it ; at least
20 grains of As2O3 in the tumbler mixed with charcoal.
. A portion of a handkerchief.
6. A bottle containing a strong solution of arsenious acid and several grains of
- undissolved arsenious acid.
7. A bottle containing from 15–20 grains of solid arsenic and a few drops of
solution.
8. A saturated solution of arsenious acid and some solid arsenious acid.
9. Valentine's meat juice.
10. Price's glycerin ; 3 grain in the whole bottle.
11. A bottle containing 0-1 grain of arsenious acid.
12. A bottle from Mr. Maybrick's office containing a few drops of medicine pre-
scribed by Dr. Fuller (decidedly arsenical).
13. Jug from the office with remains of food.
14. Sediment from trap of w.c. and lavatory drain containing AS,03.
Mrs. Maybrick was convicted, but afterwards the sentence was commuted to
penal servitude for life. -
§ 731A. Poisoning by Arsenical Beer. —The mass poisoning by arsenical beer,
due in the first place to the use of arsenical glucose, which occurred in Lancashire
and the Midland counties in 1890, gives excellent material for the study of the
effects of chronic poisoning by arsenic, the more especially since the doses were small,
but continued daily for months; it may be objected that the symptoms and patho-
logical changes cannot be ascribed entirely to the effects of arsenic, but are mixed up
and confused with those produced by alcohol. This is true with regard to a proportion
of the cases, but the curious fact has been put on record that the peripheral neuritis
observed was confined to the beer drinkers. Heavy drinkers of spirits in the same
locality and in the same class of life, so long as they did not drink beer, were
unaffected.
The chief feature of the outbreak was peripheral neuritis. A severe case
recorded by Dr. Kelynack and Mr. Kirby * may be considered as typical of a large
number.
The patient, a woman of 39, had been in the habit of drinking at least
one pint of beer daily, and occasionally two pints; the beer was found to contain
++n grain of As2O5 per pint. For some time she had noticed a watery discharge from
the nose and eyes; about six weeks after this she became aware of a brown dis-
coloration of the left side of the neck and left shoulder ; this subsequently extended
over the whole body; the skin peeled off the forearm and hands In about twelve
weeks she felt tenderness and pain in the soles of the feet, with sensations of “ pin-
and needles.” Walking became painful; gastric symptoms then developed; there
was vomiting and some diarrhoea ; in about 5% months she became too weak to leave
5
* Arsenical Poisoming in Beer Drinkers. London, 1901.
572 POISONS: THEIR EFFECTS AND DETECTION. [$ 732.
her bed, and had hoarseness of voice and troublesome cough ; the nails were thickened,
and there was considerable general branny desquamation.
In a good many other cases with or without pigmentation there were herpetic
erythematous papular or vesicular eruptions. In some there was quite an extra-
ordinary thickening of the cuticle of the hands and feet. Nervous symptoms were
mostly prominent, and in bad cases complete paralysis occurred.
It was, however, specially observed that in the majority of the patients there
was no conspicuous gastro-intestinal derangement. Hence the only evidence of
arsenical poisoning was peripheral neuritis, with pigmentation or other affections of
the skin. •
During the epidemic the urine of many of the patients was examined ; in a few
cases only was arsenic found. On the other hand, the hair and scales from the skin
when examined yielded evidence of arsenic.
§ 732. Post-mortem Appearances in Animals.--P. Hugo * has
made some researches as to the pathological appearances met with
in animals. His experiments were made on seven dogs, eight
guinea-pigs, five rabbits, two pigeons, and five cats—all poisoned
by arsenious acid. According to Hugo, so far as these animals
were concerned, changes were more constant in the intestine than
in the stomach. -
Stomach.-Changes in the mucous membrane were especially
noticed in the great curvature and towards the pylorus; the pylorus
itself, and a part of the cardiac portion, remained unchanged. The
mucous membrane in dogs and cats was red, with a tinge of blue—
in many cases the redness was in streaks, with injection of the
capillaries. The stomach of plant-eaters was less altered, and a
microscopical examination of the mucous tissues did not show any
fatty change.
The Intestines.—In dogs and cats changes were evident ; in rabbits
and guinea-pigs they were not so marked, but the intestines of the last
were extremely tender and brittle, very moist, and filled with a slimy,
serous, grey-white fluid ; nevertheless, the changes in all these animals
appear to be of essentially the same nature. The most striking effect is
the shedding of a pseudo-membrane; in quite recent cases there is a
layer of from 1 to 1% mm. wide of a transparent, frog-spawn-like jelly
streaking the intestine. In later stages it becomes thicker, while
occasionally it resembles a diphtheritic exudation. The mucous
membrane itself is deep purple-red, showing up by the side of the
pseudo-membrane. With regard to the villi, the epithelial layer is
detached, and the capillary network filled with blood and enlarged.
The Liver.—Hugo met only occasionally with fatty degeneration of
the liver, but there was marked steatosis of the epithelium of the gall-
bladder of dogs. A fact not prominently noticed before, is (at all events,
in dogs) a serous transudation into the pleural sac and Oedema of
* Archiv f. eaſper. Pathol. w Pharmakol., Leipzig, 1882.
§ 733.] ARSENIC, 573
the lungs; the exudation may be excessive, so that more than 100 c.c.
of serous fluid can be obtained from the thorax; there is also usually
much fluid in the pericardium. In two of Hugo's experiments there
was fluid in the cerebral ventricles; and in all there was increased
moisture of the brain substance with injection of the capillary vessels,
especially of the pia.
§ 733. Post-mortem. Appearances in Man.—A remarkable preserva-
tion of the body is commonly, but not constantly, observed. When it
does occur it may have great significance, particularly when the body is
placed under conditions in which it might be expected to decompose
rapidly. In the celebrated Continental case of the apothecary Speichert
(1876), Speichert's wife was exhumed eleven months after death. The
coffin stood partly in water, the corpse was mummified. The organs
contained arsenic, the churchyard earth no arsenic. R. Koch was
unable to explain the preservation of the body, under these conditions,
in any other way than from the effect of arsenic ; and this circumstance,
with others, was an important element which led to the conviction of
Speichert.
When arsenious acid is swallowed in substance or solution, the most
marked change is that in the mucous membrane of the stomach and
intestines; and, even when the poison has been absorbed by the skin
or taken in any other way, there may be a very pronounced inflammatory
action. On the other hand, this is occasionally absent. Orfila * relates
a case in which a man died in thirteen hours after having taken 12 grns.
of arsenious acid:—“The mucous membrane of the stomach presented
in its whole extent no trace of inflammation, no redness, and no altera-
tion of texture.” Many other similar cases are on record ; and, according
to Harvey's statistics, in 197 cases, 36 (about 18.2 per cent.) presented
no lesion of the stomach.
The usual changes produced by arsenious acid may be studied in
the museums of the London hospitals. In Guy's Hospital Museum
there are three preparations. In preparation 1798% is seen a large
stomach with the mucous membrane at certain points abraded, and at
the great curvature the whole coats are thinned; it is also somewhat
congested. In preparation 1798% is a portion of coagulated lymph,
from the stomach of a lad, aged 14, who had taken accidentally a piece
of cheese charged with arsenious acid, prepared for the purpose of
destroying rats. He lived twenty-eight hours, and presented the
ordinary symptoms. The lymph has a membranous appearance, and
the rugae of the stomach are impressed upon it. It is said when recent
to have presented numerous bright bloody spots, although there was no
visible breach of substance on the surface of the stomach. The mucous
* Tome i. Obs. v.
574 POISONs: THEIR EFFECTS AND DETECTION. [$ 734.
membrane of the stomach is stated to have been injected, and there was
also diffuse injection of the duodenum. Preparation 1798* is the
stomach of a person who survived thirteen hours after taking a fatal
dose of arsenious acid; and in the same museum there is a wax model
of the appearances which the fresh preparation exhibited, showing a
large oval patch coated with mucus and the poison. The stomach was
intensely inflamed, the caecum injected. The rest of the intestine was
healthy.
In the museum of University College there are two preparations,
one * exhibiting intense swelling and congestion of the gastric mucous
membrane, which is of a perfectly vermilion colour. Another pre-
paration (No. 2868) shows the effect of a small dose of arsenic on the
..stomach; there are spots of arborescent extravasation, and slight con-
gestion of the summits of the rugae, but in other respects it is normal.
There is also a cast of Peyer's patches from the same case, showing
great prominence of the glands, with some injection of the intestinal
mucous membrane. -
In St Thomas' Hospital there is an interesting preparation (No. 8)
showing the gastric mucous membrane dotted all over with minute
ulcers, none of which have an inflammatory zone.f The writers have
not, however, seen in any museum a preparation of the curious emphyse-
matous condition of the mucous membrane, which has more than once
been met with. For example, in a case related by Tardieu, ; Schwann,
a labourer, died from the effects of arsenic in thirty-six hours. The
autopsy showed that the mucous membrane of the stomach and small
intestine was covered with a pasty coating, and was elevated in nearly
its whole extent by bullae filled with gas, forming true emphysematous
swellings which encroached upon the diameter of the intestine. There
was neither redness nor ulceration, but the mucous membrane was
softened.
The senior author saw, many years ago, at Barnard Castle, an
autopsy made on a gentleman who died from arsenic. In this case
the mucous membrane of the stomach presented a peculiar appear-
ance, being raised here and there by little blebs, and very slightly
reddened.
§ 734. The inflammatory and other changes rarely affect the gullet.
Brodie Ś never observed inflammation of the oesophagus as an effect
of arsenic ; but, when arsenic is swallowed in the solid state, as in the
* This preparation at the time of visit had no number.
+ In a case related by Orfila, t. i. Obs. xv., death resulted from the outward
application of arsenic ; the mucous membrane of the stomach was natural in colour,
but there were four ulcers, one of which was 50 centimetres in diameter.
† Op. cit., Obs. i. p. 468. § Phil. Trans., 1812.
§ 734.] ARSENIC. 575
suicide of Soufflard, graphically described by Orfila,” it may be affected.
In Soufflard's case there was a vivid injection of the pharynx and
gullet.
In many instances, when the arsenic has been taken in the solid form,
the crystals with mucus and other matters adhere to the lining membrane.
One of the authors has seen in the stomach of a horse, poisoned by an ounce
of arsenic, an exquisite example of this. The inflammatory changes may
be recognised many months after death owing to the antiseptic properties
of arsenic ; nevertheless, great caution is necessary in giving an opinion,
for there is often a remarkable redness induced by putrefactive changes
in healthy stomachs. Casper, f on this point, very justly observes:—“If
Orfila quotes a case from Lepelletier, in which the inflammatory redness
of the mucous membrane of the stomach was to be recognised after nine
months' interment, and if Taylor cites two cases in which it was observed
nineteen and twenty-one months after death respectively, this is in
contradiction of all that I, on my part, have seen in the very numerous
exhumed corpses examined by me in relation to the gradual progress
of putrefaction and of Saponification, and I cannot help here suspect-
ing a confusion with the putrefactive imbibition redness of the mucous
membrane.”
If examined microscopically, the liver and kidneys show no change
save a fatty degeneration and infiltration of the epithelial cells. In the
muscular substance of the heart, under the endocardium, there is almost
constantly noticed ecchymosis. In the most acute cases, in which a
cholera-like diarrhoea has exhausted the sufferer, the blood may be
thickened from loss of its aqueous constituents, and the whole of the
organs will present that singularly dry appearance found in all cases in
which there has been a copious draining away of the body fluids. In
the narcotic form of arsenical poisoning, the vessels of the brain have
been noted as congested, but this congestion is neither marked nor
pathognomonic. Among the rare pathological changes may be classed
glossitis, in which the whole tongue has swollen, and is found so large
as almost to fill the mouth. This has been explained, in one case, as
caused by solid arsenious acid having been left a little time in the mouth
before swallowing it. On the other hand, it has also been observed
when the poison has been absorbed from a cutaneous application. When
arsenic has been introduced into the vagina, the ordinary traces of
inflammatory action have been seen, and, even without direct contact,
an inflammation of the male and female sexual organs has been recorded,
extending so far as gangrene. As a rule, putrefaction is remarkably
retarded, and is especially slow in those organs which contain arsenic ;
so that, if the poison has been swallowed, the stomach will retain its
* T. i. p. 319. t Handbuch, vol. ii. p. 420.
576 POISONS: THEIR EFFECTS AND DETECTION. [$ 735.
form, and, even to a certain extent, its natural appearance, for an
indefinite period. In corpses long buried of persons dying from arsenical
poisoning, the ordinary process of decay gives place to a saponification,
and such bodies present a striking contrast to others buried in the
same graveyard. This retardation of putrefaction is what might, a
priori, be expected, for arsenic has been long in use as a preservative of
organic tissues. .
§ 735. Physiological Action of Arsenic.—The older view with
regard to the essential action of arsenic was, without doubt, that the
effects were mainly local, and that death ensued from the corrosive
action on the stomach and other tissues—a view which is in its entirety
no longer accepted; nevertheless, it is perfectly true that arsenic has a
corrosive local action ; it will raise blisters on the skin, will inflame the
tongue or mucous membranes with which it comes in contact ; and, in
those rapid cases in which extensive lesions have been found in the
alimentary canal, it can hardly be denied that instances of death have
occurred more from the local than the constitutional action. In the vast
majority of cases, however, there is certainly insufficient local action to
account for death, and we must refer the lethal result to a more profound
and intimate effect on the nervous centres. The curious fact that, when
arsenic is absorbed from a cutaneous surface or from a wound, the
mucous membrane of the stomach inflames, is explained by the absorption
of the arsenic into the blood and its separation by the mucous membrane,
in its passage exerting an irritant action. The diarrhoea and hyperaemia
of the internal abdominal organs have been referred to a paralysis of
the splanchnic nerves, but Esser considers them due to an irritation of
the ganglia in the intestinal walls. Binz has advanced a new and
original theory as to the action of arsenious acid ; he considers that the
protoplasm of the cells of many tissues possesses the power of oxidising
arsenious acid to arsenic acid, and this arsenic acid is again, by the same
agency, reduced to arsenious acid. In this way, by the alternate oxidation
and reduction of the arsenious acid, the cells are decomposed, and a
fatty degeneration takes place. Thus arsenic causes fatty changes in
the liver, kidney, and other cells by a process analogous to the action of
phosphorus. T. Araki” also considers that both arsenic and phosphorus
lessen oxidation, and points out that lactic acid appears in the urine
when either of these poisons are taken, such acid being the result of
insufficient oxidation. A notable diminution of arterial pressure has
been observed. In an experiment by Hugo f :03 grim. of As2Os was
injected intravenously, the normal arterial pressure being 178 mm.
Ten minutes after injection the pressure sank to 47 mm. ; in sixteen
minutes it again rose to 127 mm. Accumulative action of arsenic
* Zeit, physiol. Chem..., xvii. 311-339. t Op. cit.
§ 736–738.] ARSENIC. 577
does not occur. Hebra has given, in skin diseases, during many months
a total quantity of 12 grims. without evil result.
§ 736. Elimination of Arsenic.—Arsenic is separated especially by
the urine,” then through the bile, and by the skin and hair. The
eruption often observed on the skin has been referred to the local
action of small quantities of arsenic in this way eliminated. It
is found in the urine first after from five to six hours, but the
elimination from a single dose is not finished till a period of from five
to eight days; it has often been looked for twelve days after taking it,
but very seldom found. According to Vitali, the arsenic in the urine
is not free, but probably displaces phosphorus in phospho-glyceric acid ;
possibly it may also replace phosphorus in lecithin.
§ 737. Antidote and Treatment.—In any case in which there is
opportunity for immediate treatment, ferric hydrate should be adminis-
tered as an antidote. Ferric hydrate converts the soluble arsenious
acid into the insoluble ferric arseniate, the ferric oxide being reduced
to ferrous oxide. It is necessary to use ferric hydrate recently
prepared, for if dried it changes into an oxyhydrate, or even if
kept under water the same change occurs, so that (according to
the experiments of Messrs. T. & H. Smith) after four months the
power of the moist mass is reduced to one-half, and after five
months to one-fourth.
It is obvious that ferric hydrate is not in the true sense of the word
an antidote, for it will only act when it comes in contact with the
arsenious acid; and, when once the poison has been removed from the
stomach by absorption into the tissues, the administration of the
hydrate is absolutely useless. Ferric hydrate may be readily prepared
by adding strong ammonia to the solution or tincture of ferric chloride,
found in every medical man's surgery and in every chemist's shop, care
being taken to add no caustic excess of ammonia : the liquid need not
be filtered, but should be at once administered. With regard to other
methods of medical treatment, they are simply those suggested by the
symptoms and well-known effects of the poison. When absorbed, the
drinking of water in excess cannot but assist its elimination by the
kidneys.
§ 738. Detection of Arsenic.—The analyst may have to identify
arsenic in substance, in solution, in alloys, in wall-papers, in earth, and
in various animal, fatty, resinous, or other organic matters.
* An old experiment of Orfila's has some practical bearings, and may be cited
here. A dog was treated by 12 grim. of arsenious acid, and supplied plentifully
with liquid to drink ; his urine, analysed from time to time during ten days, gave
abundant evidences of arsenic. On killing the animal by hanging on the tenth day,
no arsenic could be detected in any of the organs of the body ; it had been, as it
were, washed out.
37
578 POISONS : THEIR EFFECTS AND DETECTION. [$ 738.
Arsenious Acid in Substance.—The general characters of arsenious
acid have been already described, and are themselves so marked as to
be unmistakable. The following are the most conclusive tests:—
(1) A small fragment placed in the subliming cell (p. 260), and
heated to about the temperature of 137.7° (286° F.), at once sublimes
in the form of an amorphous powder, if the upper glass disc is cool ;
but if heated (as it should be) to nearly the same temperature as the
lower, characteristic crystals are obtained, remarkable for their brilliancy
and permanency, and almost always distinct and separate. The pre-
vailing form is the regular octahedron, but the rhombic dodecahedron,
the rectangular prism, superimposed crystals, half crystals, deep
triangular plates like tetrahedra, and irregular and confused forms, all
occasionally occur.
(2) A beautiful and well-known test is that of Berzelius:—A small
hard-glass tube is taken, and the closed end drawn out to the size of a
knitting needle. Within the extreme point of this fine part is placed
the fragment (which may be no more than a milligramme) and a
splinter of charcoal, fine enough to enter freely the narrow part, as
shown in the figure. The portion of the tube containing the charcoal
(e) is first heated until it glows, and then the extreme end ; if arsenic
is present, a mirror-like coating is easily obtained in the broader
portion of the tube (d). That this coating is really arsenical can be
established by the behaviour of metallic crusts of arsenic towards
solvents (as given at p. 583). The portion of the tube containing the
crust may also be broken up, put in a very short, wide test-tube (the
mouth of which is occupied by a circle of thin microscopic glass) and
heated, when the arsenic will sublime on to the glass disc, partly as a
metal and partly as crystalline arsenious acid. With minute films of
metallic arsenic it is, however, better by means of a small pointed
flame to draw out the tube on both sides of the arsenical ring, and seal
it ; the sealed tube is then heated in a bath of ordinary solder to about
400° C. The oxygen of the enclosed air unites with the arsenic at
once ; and crystals are formed without any possibility of loss.
(3) Arsenious acid, itself inodorous, when heated on charcoal, after
mixing it with moist oxalate of potash, evolves a peculiar garlic-like
odour. To this test oxide of antimony adulterated with arsenic will
respond, if there is only a thousandth part present. Simply projecting
arsenious acid on either red-hot charcoal or iron produces the same
odour,

§ 738.] ARSENIC, 579
(4) A little bit of arsenious acid, heated in a matrass with two or
three times its weight of acetate of potash, evolves the unsupportable
odour of kakodyl.
Arsenites and Arseniates, mixed with oxalate of soda and heated in
a matrass, afford distinct mirrors, especially the arsenites of the earths
and silver; those of copper and iron are rather less distinct.
Sulphides of Arsenic are reduced by any of the processes described
on p. 598 et seq.
In Solution.—An acid solution of arsenious acid gives, when treated
with SH, a canary-yellow precipitate, soluble in ammonia, carbonate of
ammonia, and bisulphite of potash, and also a metallic sublimate when
heated in a tube with the reducing agents in the manner described at
p. 599. By these properties the sulphide is distinguished and, indeed,
separated from antimony, tin, and cadmium.
The sulphides of tin and cadmium are certainly also yellow, but the
latter is quite insoluble in ammonia, while the former gives no metallic
sublimate when heated with reducing substances.
The sulphide of antimony, again, is orange, and quite insoluble in
potassic bisulphite, and scarcely dissolves in ammonia.
A small piece of sodium amalgam placed in a test-tube or flask con-
taining an arsenic-holding liquid, or the liquid made alkaline with soda
or potash and a little bit of aluminium added, produces in a short time
arsine, which will blacken a piece of paper, soaked in nitrate of silver,
and inserted in the mouth of the flask. This is a convenient test for
arsenic. No antimoniuretted hydrogen (stibine) is given off from an
alkaline solution and no SH2.
Gutzeit's test.—The principle of Gutzeit's test is the production
of a yellow or orange stain, according to quantity, produced by
arseniuretted hydrogen. When passed through filter-paper impreg-
nated with mercuric chloride the test is not affected by antimony,
selenium, or tellurium, and is capable of detecting less than #5 of a
mgrm. of As2O3.
The best way to perform the test is to place from 50 to 100 c.c. of
the liquid to be tested in a small flask; it is better for the liquid to be
free from organic matter, but not essential. In cases where the evolu-
tion of hydrogen causes frothing, the solution must be so altered in
physical characters by boiling with oxidising reagents that injurious
frothing ceases. The solution is acidified by adding from 5–10 c.c. of
arsenic-free hydrochloric acid and half a c.c. of a 15 per cent.
solution of cuprous chloride, and a rod of pure zinc inserted. The
gas is passed through a small absorption cell containing lead acetate
solution, and then passed over a short layer of dry cotton wool
and made to impinge on a small disc of filter-paper previously
58o POISONS: THEIR EFFECTS AND DETECTION. [$ 738.
impregnated with a 5 per cent. solution of mercuric chloride. The
disc should be capped on to the issuing tube, so that all the gas
passes right through the paper. It is well to plunge the flask into
cold water so as to keep the temperature down, otherwise the evolu-
tion of gas will be irregular.
Marsh's Original Test for Arsenic consisted in evolving nascent
hydrogen by zinc and sulphuric acid, and then adding the liquid to be
tested. The apparatus for Marsh's test, in its simplest form, consists
of a flask provided with a cork conveying two tubes, one a funnel reach-
ing nearly to the bottom of the flask; the other, a delivery tube, which
is of some length, is provided with a chloride of calcium bulb, * and to-
wards the end is turned up at right angles, the end being narrowed. By
evolving hydrogen from zinc and sulphuric acid, and then adding por.
tions of the liquid through the funnel, arseniuretted hydrogen in a dry
state is driven along the leading tube, can be ignited on its issue, and on
depressing a piece of cold porcelain, a dark metallic spot of arsenic is
obtained. Or, if any portion of the tube be made red-hot, the metal
is deposited in the same way as a ring. ->
Purification of the Zinc, Sulphuric Acid and Hydrochloric Acid.—
(For the Marsh-Berzelius apparatus and purification of materials, as
recommended by the Joint Committee of the Society of Public Analysts
and the Society of Chemical Industry, see Foods, 5th edition, p. 437.)
Zinc (Hehner's method as modified by Thorne f).—Commercially
pure zinc is melted in a crucible in a gas furnace, and when at or only
just above its melting-point sodium is mixed with it in the proportion of
about 1 grain to each pound of zinc. The crucible is then heated until
the zinc is completely fluid, and the zinc is poured into a second heated
crucible and back again into the first crucible to ensure thorough
melting. The crucible, with the lid on, is then put back into the
furnace and heated to a dull red heat, when the furnace and crucible
lids are both removed, and the heating is continued for one hour. A
scum rises to the top and forms a crust on the surface. This crust,
when the crucible has cooled a little, is pierced at one side and the
molten mass is poured into a second heated crucible and skimmed if
necessary. The crucible is then heated to bright redness, any scum
removed, them allowed to cool and the zinc granulated just before the
* Otto recommends the first half of the drying tube connected with the develop-
ment flask to be filled with caustic potash, the latter half with chloride of calcium
(Ausºnittelung der Gifte). Dragendorff approves of this, but remarks that it should
be used when arsenic alone is searched for, since caustic potash decomposes stibine.
The potash fixes SH2, and prevents the formation of chloride of arsenic ; on the other
hand, it absorbs some little AsFH3.
+ L. T. Thorne, “The Purification of Zinc and Hydrochloric Acid from Arsenic.”
Analyst, April 1906, p. 101.
§ 738.] ARSENIC. - - 581
solidifying point is reached. Arsenic-free zinc prepared in this manner,
and much of the commercial arsenic-free zinc, is often “insensitive,” i.e.,
it retains a certain amount of arsenic, so that qualitative results may
be too low or traces overlooked.
M. Blondlot,” several years ago, made the observation that if
Stannous chloride be added to the contents of the flask in the Marsh-
Berzelius process, the whole of the arsenic is given off even in the
presence of pure zinc and acid, and Chapman and Lawi have recently
found that 1 to 2 grammes of cadmium sulphate, lead acetate, or
stannous chloride, completely overcome the “insensitiveness” of the
pure materials. The same authors have shown that such salts as
palladium chloride, platinum chloride, nickel sulphate, and cobalt
sulphate cause, on the other hand, a retention of large quantities of
arsenic ; working also with alloys of zinc with iron, nickel, cobalt, copper,
silver, platinum, sodium, tin and cadmium, they found that all of these,
with the exception of tin and cadmium, caused retention of arsenic,
but in every case the “insensitiveness” was removed by the addition of
2 grammes of cadmium sulphate, lead acetate, or stamnous chloride,
except in the case of some metal alloys. *
Hydrochloric Acid.—Warious methods have been proposed for
freeing hydrochloric acid from traces of arsenic. Of these we will only
give two of the most recent and convenient.
Ling and Rendle's Method.:-This is based upon the fact observed
by H. Cantoni and J. Chautenis, Š that methyl arsenite is readily formed
and is very volatile, and that the Reinsch method as modified by Dr.
L. T. Thorne || may be used for the purification of hydrochloric acid.
To 1500 c.c. of commercial hydrochloric acid slightly above 1-1 sp. gr.
about 40 c.c. of redistilled commercial wood spirit are added. The
mixture is contained in a Wurtz flask of two litres capacity. About 5
to 10 grms. of arsenic-free granulated zinc are then added. The flask
is connected with a reflux condenser by an ordinary cork, in which is
fixed a glass rod supporting a coil of electrolytic copper foil, having
a surface of about 120 square inches. The side tube of the Wurtz
flask having been plugged, the condenser is connected with an ex-
* Blondlot, “Transformation de l’arsenic en hydrure solide par l’hydrogene
faissant Sous l’influence des composés nitreux,” Jour. de Pharm. et de Chim., 3e
sér., t. xliv. p. 486.
t A. C. Chapman and H. D. Law, “The Reducing Action of Hydrogen,”
Analyst, Jan. 1906, p. 3.
# Arthur R. Ling, and T. Rendle, “Note on the Removal of Arsenic from
Hydrochloric Acid for use in the Marsh-Berzelius Method,” Analyst, Feb. 1906,
p. 37.
§ Arch. Sc. Phys. Nat. Geneve (4), xix. 364.
| Proc. Chem. Soc., 1902, 118.
582 POISONS : THEIR EFFECTS AND DETECTION. [$ 738.
haust-pump, and the boiling commenced. The acid is digested for
about three hours, the copper being withdrawn and cleaned at least
once during that period. During the digestion a black tarry, fuming
liquid distils over, and the greater part of this is caught in a vessel
between the condenser and the pump. Another vessel containing water
is interposed to catch any hydrogen chloride which passes off.
Thorne and Jeffers’ Method.*—Redistilled hydrochloric acid is
diluted to a sp. gr. of a little under 11, and poured on to 2 to 3 grms.
of a copper-tin couple prepared as follows:–
Cuprous chloride is dissolved in excess of HCl, and a little granu-
lated tin added ; when the tin is dissolved, zinc dust is added, and the
copper and tin, which are precipitated as a gray spongy mass, washed
by decantation. The acid and couple are gradually heated, and boiled
gently for half an hour. The acid is then at once distilled from a flask
containing a small quantity of the couple and a little piece of 100-mesh
copper gauze. The distilled acid is free from arsenic.
Sulphuric Acid.—This acid may now be obtained free from arsenic,
but if it is found to be impure it may be freed from arsenic by diluting
with four volumes of water, adding a little sodium chloride, and distil-
ling. The first Tºth of the distillate contains all the arsenic, and is
rejected.
The precautions to be observed in Marsh's or Marsh-Berzelius process
3,I'ê –
(1) Absolute freedom of the reagents used from arsenic, antimony,
and other impurities.
(2) The sulphuric acid or hydrochloric acid should be diluted
with from four to five times its weight of water, and if freshly prepared
should be cooled before use. Strong acid must not be employed.
(3) The fluid to be tested should be poured in little by little.
(4) Nitrous compounds, nitric acid, chlorides, are all more or less
prejudicial. -
(5) The gas should come off regularly in not too strong a stream,
nor out of too small an opening.
(6) The gas should pass through the red-hot tube at least half an
hour before adding the substance to be tested ; if there is then no
stain, the liquid to be tested is run in gradually and the test run for
at least one hour.
(7) A solution of cadmium sulphate should be added to the contents
of the flask, to counteract the “insensitiveness” of the material.
The characteristics of the metallic stains which may occur either on
glass or porcelain in the use of Marsh's test, may be noted as under:-
* L. T. Thorne and E. H. Jeffers, “The Purification of Zinc and Hydrochloric
Acid from Arsenic,” Analyst, April 1906, 102.
§ 738.]
583
ARSENIC.
MIRROR OR CRUST of ARSENIC
Is deposited at a little distance
from the flame.
An arsenical stain is in two
portions, the one brownish, the
other a glittering black.
On heating, it is rapidly vola-
tilised as arsenious acid.
On transmission of a stream of
SH2, whilst immediately behind
the stain a gentle heat is applied,
the arsenic is changed to yellow
sulphide; * if dry ClFI is now
transmitted, the arsenical sulphide
is unchanged.
Chloride of lime dissolves the
arsenic completely.
Protochloride of tin has no
action on metallic arsenic.
The arsenic stain, dissolved in
aqua regia, or ClFI and chloride
of potash, and then treated with
tartaric acid, ammonia, and mag-
nesia mixture, gives a precipitate
of ammonia magnesian arseniate.f
MIRROR OR CRUST OF ANTIMONY
Is deposited close to the flame,
and on both sides of it, and is
therefore notched.
The stain is tolerably homo-
geneous, and usually has a tin-
like lustre.
Wolatilisation very slow ;
crystalline sublimate obtainable.
The same process applied in
the case of antimony produces the
orange or black sulphide ; and on
passing dry ClFI, chloride of anti-
mony volatilises without the appli-
cation of heat.
DO
Antimony not affected.
Dissolves slowly but completely
the antimony stain.
No precipitate with antimony.
The mirror or crust of arsenic is usually described and weighed
as being composed of the pure metal; but J. W. Rettgers has
investigated the matter, and the following is an abstract of his
results:—
There is no amorphous form of arsenic, the variety generally thus
* It is desirable to dissolve away the free sulphur often deposited with the
arsenical sulphide by bisulphide of carbon.
+ Schönbein has proposed ozone as an oxidiser of arsenical stains.
The substance
containing the stain, together with a piece of moist phosphorus, is placed under a
shade, and left there for some time ; the oxidisation product is, of course, coloured
yellow by SH2 if it is arsenious acid, orange if antimony. The vapour of iodine
colours metallic arsenic pale yellow, and later a brownish hue ; on exposure to the
air it loses its colour. Iodine, on the other hand, gives with antimony a carmelite
brown, changing to Orange.
An arsenical ring may be also treated as follows:—Precipitated zinc sulphide is
made into a paste with a little water, and introduced into the end of the tube; the
same end is then plunged into dilute sulphuric acid, and the ring heated, when the
arsenical sulphide will be produced.
584 POISONS : THEIR EFFECTS AND DETECTION. [$ 738.
called being crystalline. Two modifications can be distinguished : the
one being a hexagonal silver-white variety possessed of metallic lustre,
specifically heavier and less volatile than the second kind, which is
black in colour, crystallises apparently in the regular system, and
constitutes the true arsenic mirror. The former modification corre-
sponds to red hexagonal phosphorus (red phosphorus having been
recently proved by the author to be crystalline), and the latter to
yellow phosphorus, which crystallises in the regular system. Both
modifications of arsenic are perfectly opaque; deposits which are yellow
or brown, and more or less transparent, consist of the suboxide and
hydride, As2O and Ash. The brown spot on porcelain produced by
contact with a flame of arseniuretted hydrogen is not a thin film of
As, but one of the brown solid hydride Ash, formed by the decomposi-
tion of Ashis. This view is confirmed by the fact that arsenic sublimed
in an indifferent gas (e.g., CO3) is deposited in one or other of the
modifications described above, the brown transparent product being
obtained only in the presence of H or O. Moreover, pure arsenic is
insoluble in all solvents, whereas the film on porcelain (AsH) is soluble
in many solvents, including hydrocarbons of the benzene series (e.g.
xylene), warm methylene iodide, and hot caustic potash.
Hence quantitative results from weighing arsenical mirrors can
never be accurate, because the mirrors consist of mixtures of hydride
and suboxide. .
Reinsch's Test.—A piece of bright copper foil, boiled in an acid
liquid containing either arsenic or antimony, or both, becomes coated
with a dark deposit of antimony or arsenic, as the case may be. The
arsenical stain, according to Lippert, is a true alloy, consisting of 1
arsenic to 5 copper.” Properly applied, the copper will withdraw every
trace of arsenic or antimony from a solution.
Copper gauze or copper foil is oxidised in the air by heating in an
open tube to a gentle red heat. The film of black oxide is next dissolved
off by a few seconds’ immersion in strong nitric acid, leaving a bright
chemically-clean surface. The acid is removed from the copper by wash-
ing in a stream of water. A piece of copper thus prepared about 1 inch
x + inch is suspended by means of a thin platinum wire in from 50 to 100
c.c. of the liquid to be examined, the liquid acidified by HCl and gently
boiled for twenty minutes. Operating on organic liquids, the copper
is usually darkened in colour, even if arsenic-free. Any black stain
may be caused by sulphur, by organic matter, by arsenic, or by antimony.
The copper is washed with alcohol and then by water, and, lastly, by
absolute alcohol, and dried at a very gentle heat. It is then dropped
into a small tube and gently heated to a temperature just below a red
* Journ. f. prakt. Chem..., xiii. 168.
§ 739, 740.] ARSENIC. 585
heat. If arsenic is present the metal sublimes in the characteristic
crystals of arsenious acid.
Dr. John Clark (Journ. Chem. Soc., 1893) has proposed dissolving off
the black film by potash and hydrogen peroxide; the solution is boiled
and any copper hydrate filtered off. Should arsenic be present, it now
exists as potassic arsenate; if antimony be present, it exists as potassic
antimonate. If both arsenic and antimony are present, the potassic salts
of both are formed. The arsenate may be decomposed and reduced by
ferrous chloride and strong hydrochloric acid and distilled into water,
the arsenic being recognised in the distillate by sulphuretted hydrogen.
Any antimony left in the flask is precipitated by SH, ; should a dark
black precipitate form, this means contamination by copper; on treatment
with caustic soda and boiling, copper sulphide may be filtered off and
pure antimony sulphide obtained by acidifying the solution and again
treating with SH3.
§ 739. Arsenic in Glycerin.—Arsenic has been frequently found in
commercial glycerin, the quantity varying from 0-1 to 1 mgrm. in 100 c.c.
The best method to detect the presence of arsenic in glycerin is as
follows:—A mixture of 5 c.c. of hydrochloric acid (1 : 7) and 1 grnm. of
pure zinc is placed in a long test-tube, the mouth of which is covered
with a disc of filter-paper previously moistened with one or two drops of
mercuric chloride solution, and dried. If arsenic is present, a yellow
stain is produced upon the filter-paper within fifteen minutes, and it
subsequently becomes darker.*
§ 740. Arsenic in Organic Matters.—Orfila and the older school of
chemists took the greatest care, in searching for arsenic, to destroy the
last trace of organic matter. Orfila's practice was to chop up the sub-
stance and make it into a paste with 400 to 700 grms, of water; to this
'010 grim. KHO in alcohol was added, and 020 grin. of potassic nitrate.
The substances were heated up to from 80° to 90° for some time, until
they were pretty well dissolved; the organic matter was then burnt off
in a Hessian crucible heated to redness, on which small quantities of the
matters were placed at a time. When the whole had thus been sub-
mitted to red heat, the melted mass was run into an almost red-hot
porcelain basin, and allowed to cool. Afterwards it was again heated
with concentrated sulphuric acid, until all nitric and nitrous fumes were
dissipated; on dissolving and filtering in water, the liquid was intro-
duced into a Marsh's apparatus. Orfila never seems to have failed in
detecting arsenic by this process. For an organ like the liver he con-
sidered that 100 grms. of potash and 86 of strong sulphuric acid were
necessary in order to destroy the organic matters.
* “Arsenic in Glycerin,” by Dr. H. B. H. Paul and A. J. Cownley, Pharm.
Journ., Feb. 24, 1894.
586 POISONs: THEIR EFFECTS AND DETECTION. [$ 740.
Distribution of Arsenic in the Body.—In searching for arsenic
in the fluids or tissues of the body, the analyst is generally at the
mercy of the pathologist, and sometimes the work of the chemist
leads to a negative result, solely from not having the proper organ
sent to him.
Brodie long ago stated that when arsenious acid had been given in
solution to any animal capable of vomiting, no arsenic could be detected
in the stomach ; this statement is too absolute, but in the majority of
CaseS true. -
In all cases the chemist should have portions of the brain, spinal
cord, liver, kidneys, lungs, and muscular tissue, as well as the stomach
and its contents.
According to the experiments of Scolosuboff,” arsenic is generally
greatest in the marrow, then in the brain, next in the liver, and least in
the muscles, the following being the proportion if muscle be taken as 1:—
Muscles, . * º e & g e & e ſº 1
Liver, . & º º ū * º e º * 10 '8
Brain, e g g g * § e tº 36 °5
Spinal Marrow, { } & o * § e g tº 37-3
But Ludwig's t experiments and conclusions are entirely opposed to
this, since both in acute and chronic cases he found as follows (per cent.
As2O3):—
Brain, . e e º © tº e e g e •0002
Liver, . tº º e e * te & * º •001
Kidney, . e © e g e º © gº te *0004
Muscle, . & † g wº e e * e e •00025
So that he detected in the liver five times more than in the brain.
M. P. Hamberg has also confirmed the fact, that more is found in the
liver and kidneys than in the nervous tissues.
Chittenden ; found in a body the following quantities of arsenic
estimated as arsenious acid:—
Grain.
Stomach and gullet, e º & o e g e 0-158
Intestines, * g º * tº & & & tº 0 °314
Liver, . g $ tº tº & & * g ſº 0 °218
Kidney, . & & e te § ſº e & ū 0 °029
Lungs and Spleen, . * e e & e * & 0-172
Heart, . g $ e º * * e e & 0-112
Brain, . tº wº g & * º te * e 0-075
Diaphragm, . tº e tº º º º e © 0 °010
The whole arsenic present was estimated as equal to 3-1 grains of
* Bull. Soc. Chim, (2), xxiv. p. 124.
t “Ueber die Verhaltung des Arsens im thierischen Organismus nach Einver-
leibung von arseniger Säure,” Med. Jahrbuch, 1880.
# American Chemical Journal, v. 8.
§ 741.] ARSENIC. 587
arsenious acid, viz., 2-628 grains absorbed, and 0-472 unabsorbed; of the
absorbed portion 8.3 per cent. was found in the liver.
With regard to the preliminary treatment of the stomach and fluids
submitted to the analyst, the careful noting of appearances, the decanta-
tion, washing and examination * (microscopical and chemical) of any
deposit, are precautions so obviously dictated by common sense, that
they need only be alluded to in passing. Of some considerable moment
is the question which may be put to the analyst in court, in reference
to the possible entrance of arsenic into the living body by food, by acci-
dental and, so to speak, subtle means. A. Gautier and Clausmann
believe that people take daily in their food only +}#g mgrm. of arsenic,
therefore yearly 7-66 mgrms. ; so that should fºr mgrm. of arsenic be
found in the corpse there is a fair presumption of poisoning. Other
sources of arsenic are the inhaling of the fumes from the burning of
arsenical candles,t and of emanations from papers (see p. 564), Í as well
as the possible entrance of arsenic into the body after death from various
Sources, such as arsenical earth, &c. §
§ 741. Imbibition of Arsenic after Death.-The arguments which
are likely to be used in favour of a corpse having become arsenical may
be gathered from a case related by Sonnenschein:—Certain bodies were
exhumed in two churchyards; the evidence went to show that they had
been poisoned by arsenic, and this substance was actually found in the
bodies, while at the same time it was discovered to exist also in traces in
the earth of the churchyard. The theory for the defence was, that
although the arsenic in the earth was in an insoluble state, yet that it
might combine with lime as an arsenite of lime; this arsenite would
become soluble by the action of carbonic acid set free by vegetation, and
filter down to the corpse. Sonnenschein suspended a quantity of this
* From some observations of Fresenius it would seem necessary to test all glass
vessels used; for it is difficult at present to purchase arsenic-free glass.
f See a case of poisoning (non-fatal) of a lady by the use of arsenical candles, Med.
Times and Gazette, vol. iii., 1876, p. 367.
# To solve this question, it has been at times considered necessary to analyse
an extraordinary number of things. In the “affaire Danval” (Journ. d’Hygiene,
2e sér., No. 108, July 1878), more than sixty different articles, comprising drugs,
drinks, perfumes, bed-curtains, wall-paper, and other matters, were submitted to the
experts.
§ The following important case is related by Sonnenschein:—
Nicholas Nobel and his wife, Jerome, were buried two metres from each other
in the churchyard at Spinal, the earth of which notoriously contained arsenic. A
suspicion of poisoning arose. The bodies were exhumed, and arsenic was found in
the stomach and intestines of Nobel, but not the slightest trace in the corpse of
the wife. The remains of the bodies were reinterred, and after six months, on a
fresh suspicion of poisoning arising, again exhumed. The corpse of the woman had
been put naked in the moist earth during a heavy shower, but this time also no
arsenic was detected in it.
588 POISONS: THEIR EFFECTS AND DETECTION. [$ 74I.
earth in water, and passed CO, through it for twelve hours; on filtering,
the liquid gave no evidence of arsenic. A similar result was obtained
when an artificial mixture of 1 grn. of arsenious acid and 1 pound of
earth were submitted to the same process.
The fact would appear to stand thus: oxide of iron in ordinary earth
retains arsenic, and requires treatment with a concentrated acid to dis-
solve it. It therefore follows that, if a defence of arsenical earth is
likely to be set up, and the analyst finds that by mere extraction of the
tissues by water he can detect arsenic, the defence is in all probability
unsound. The expert should, of course, deal with this question on its
merits, and without prejudice. According to Eulenberg,” in arsenical
earth—if, after having been crushed and washed, it lies for some time
exposed to the disintegrating action of the air—soluble arsenical salts are
formed, which may find their way into brooks and supplies of drinking
water. We may infer that it is hardly probable (except under very
peculiar circumstances) for a corpse to be contaminated internally with
an estimable quantity of arsenic from the traces of arsenic met with in
a few churchyards. .
It occasionally happens that an exhumation is ordered a very long
time after death, when no organs or parts (save the bones) are to be
distinguished. In the case of a man long dead, the widow confessing
that she had administered poison, the bones were analysed by Sonnen-
schein, and a small quantity of arsenic found. Comièrbe and Orfila have
both asserted that arsenic is a normal comstituent of the bones—a state-
ment which has been repeatedly disproved. Sonnenschein relates: f-
“I procured from a churchyard of this place (Berlin) the remnants of
the body of a person killed twenty-five years previously, and investigated
several others in a similar way, without finding the least trace of arsenic.
Similar experiments in great numbers were repeated in my laboratory,
but in no case was arsenic recognised.” The opinion of the expert
should he find arsenic in the bones, must be formed from the amount
discovered, and other circumstances.
A difficult case on which to form an opinion is one recorded by
William P. Mason, ; as follows:— -
The deceased, a farmer, bachelor, sixty-five years of age, and in good health, was
taken violently sick shortly after breakfast, with vomiting and distress in the
stomach. Although a physician was summoned, the symptoms increased in severity,
and a little after midnight death ensued. The funeral took place three days later.
Certain very damaging pieces of circumstantial evidence having been collected, the
housekeeper was arrested on the charge of murder, it having been shown, among
Other things, that on the day preceding the death she had purchased an ounce of
white arsenic. R
* Gewerbe Hygiene, p. 284. † Gericht!. Chem., p. 212.
# Chem. News, Feb. 23, 1894.
§ 741.] ARSENIC. 589
Thirty-five days after death (from March 20 to April 25) the body was exhumed,
and found in a state of remarkable preservation, and free from cadaveric Smell. The
stomach presented evidences of inflammation.
Portions sent for analysis were the stomach, portion of intestine, portion of liver,
one kidney, and the heart. Arsenic was found in all these parts. White octahedral
crystals were found in the contents of the stomach, which on separation gave
arsenical reaction.
The arsenic found was:—
Stomach and intestine, . º ſº tº 02376 grm.
Liver and kidney, ſº • º e 0-0032 ,,
Heart, . . . . . . . 0-0007 ,,
Total as metallic arsenic, ſº 0-2415 , ,
The amount of arsenic recovered and produced in court was in quantity sufficient
to produce death. Some time after the analytical report was made to the coroner, it
was learned that an embalming fluid, highly arsenical in character, had been used
upon the body by the undertaker at the time of preparation for burial. No injection
of this embalming fluid was practised, but cloths wrung out in the fluid were laid
upon the face and chest, and were kept constantly wet therewith during a period of
many hours. In all, about two quarts of embalming fluid were so used. Its com-
position appeared to be a strongly acidified solution of sodium arsenite and zinc sul-
phate. Only the arsenic and zinc were determined quantitatively, and they were
found to be : zinc (metallic), 1978 per cent., and arsenic (metallic), 1-365 per cent. by
weight. An amount of this fluid measuring 15-7 c.c. would thus contain a weight
of arsenic equal to that actually recovered from the body. -
Extended medical testimony was offered by the prosecution, tending to show that,
under the given circumstances, no fluid of any kind could have reached the stomach
through the nose or mouth after death—thus anticipating what the defence after-
wards claimed, that the undertaker was responsible for the arsenic discovered in the
remains.
In order to gather further light upon the possibility of cadaveric imbibition of
embalming fluid through the unbroken skin, test was made for zinc in the heart and
stomach, and distinct traces of the metal were found in each instance. That at
least a portion of the arsenic found in the body was due to post-mortem causes was
thus distinctly proven. A weighed portion (62 grims.) of the stomach and contents was
then most carefully analysed quantitatively for both zinc and arsenic, with the fol-
lowing results: arsenic, 0.0648 grm., and zinc, 0:0079 grim. Bearing in mind the
relative quantities of the two metals in the embalming fluid, it will be seen that the
arsenic found in the 62 grms. of the stomach was nearly twelve times larger than it
should have been to have balanced the zinc which was also present. This fact,
together with the discovery of crystals of white arsenic in the stomach, constituted
the case for the prosecution, so far as the chemical evidence was concerned.
The defence made an unsuccessful effort to show that the crystals of the tri-oxide
originated from the spontaneous evaporation of the embalming fluid. The prosecu-
tion met this point by proving that such fluid had been abundantly experimented
upon by exposure to a very low temperature during an interval of several months,
and also by spontaneous evaporation with a view of testing that very question, and
that the results had in every case been negative. Special importance was given thes
experiments, because of the well-known separation of octahedral crystals during the
spontaneous evaporation of a hydrochloric acid solution of the white oxide, it having
also appeared that, in the manufacture of the embalming fluid, the arsenic was used
as white arsenic.
A very strong point was finally raised for the defence by the inability of the
590 POISONS: THEIR EFFECTS AND DETECTION. [$ 742.
expert on the side of the prosecution to state positively whether or not an embalm-
ing fluid of the above composition would diffuse as a whole through dead tissue, or
its several parts would be imbibed at different rates of speed, the zinc portion becom-
ing arrested by albuminoid material and being therefore outstripped by the arsenic,
or vice versé. The prisoner was ultimately acquitted.
In a case which occurred in the Western States of America, there
was good reason for believing that arsenic had been introduced into the
corpse of a man after his decease. With regard to the imbibition of
arsenic thus introduced, Orfila” says:—“I have often introduced into
the stomach (as well as the rectum) of the corpses of men and dogs 2
to 3 grms. of arsenious acid, dissolved in from 400 to 500 grms. of
water, and have examined the different viscera at the end of eight, ten,
or twenty days. Constantly I have recognised the effects of cadaveric
imbibition. Sections of the liver or other organs which touch the
digestive canal, carefully cut and analysed, furnished arsenic, which
could not be obtained sensibly (or not at all) from sections which had
not been in contact with this canal. If the corpse remained long on
the back after arsenious acid had been introduced into the stomach, I
could obtain this metal from the left half of the diaphragm and from
the inferior lobe of the left lung, whilst I did not obtain it from other
portions of the diaphragm nor from the right lung.” Dr. Reece has
also made some experiments on the imbibition of arsenic after death.
He injected solutions of arsenious acid into the stomach of various
warm-blooded animals, and found at various periods arsenic, not alone
in the intestinal canal, but also in the spleen, liver, and kidneys.
§ 742. Analysis of Wall-Paper for Arsenic.—The separation of
arsenic from paper admits of great variety of manipulation. A quick
special method is as follows:–The paper is saturated with chlorate of
potash solution, dried, set on fire in a suitable plate, and instantly
covered with a bell-glass. The ash is collected, pulverised, and ex-
hausted with cold water, which has previously thoroughly cleansed the
plate and bell-glass; the arsenic in combination with the potash is dis-
solved, whilst oxides of chromium, copper, aluminium, tin, and lead
remain in the insoluble portion.f
Fresenius and Hintz i have elaborated a method for the examination
of wall-papers, fabrics, yarns, and similar substances, which, provided
the reagents are pure, is accurate and easy. Twenty-five grms. of the
substance are placed in a half-litre distilling flask or retort, and 250 c.c.
of HCl, specific gravity 1:19, added; after digestion for an hour, 5 c.c.
of a saturated solution of ferrous chloride are added, and the liquid
* Op. cit., t. i. p. 309.
+ Kapferschlaeger: Rev. Universelle des Mines, 1876.
+ Zeit, anal. Chem., xxvii. 179–182,
§ 743.] ARSENIC. 59 I
slowly distilled until frothing stops any further distillation. A further
quantity of 100 c.c. HCl is then added, and distilled over. The re-
ceiver, in each case, contains water, and must be kept cool. The united
distillates are diluted to 800 c.c. and saturated with SH3. The arsenious
sulphide is collected on an asbestos filter. After partial washing, it is
heated with bromine in HCl of 1:19 specific gravity, and the solution
again distilled with ferrous chloride. The distillate, on now being
treated with SH2, gives arsenious sulphide free from organic matter.
§ 743. Estimation of Arsenic.—Most of the methods for the quanti-
tative determination of arsenic are also excellent tests for its presence.
It may be regarded, indeed, as an axiom in legal chemistry, that the
precise amount of every substance detected, if it can be weighed or
estimated by any process whatever, should be accurately stated. In-
definite expressions, such as “a small quantity was found,” “traces were
detected,” etc., are most objectionable. The more perfect of the methods
of evolving arsine are now quantitative, because the arsenical ring can
be compared with standard rings produced under as nearly as possible
the same experimental conditions. Pure arsine, passed into nitrate
of silver solution, decomposes it in such a manner that, if either
the silver deposited or the free acid is estimated, the quantity of
arsenic can from such data be deduced. A very convenient method,
applicable in many cases, is to throw out the silver by hydrochloric
acid, alkalise the filtrate by bicarbonate of soda, and titrate with iodine
solution. The latter is made by dissolving exactly 12.7 grnms, of pure
dry iodine by the aid of 18 grns. of potassic iodide in one litre of water,
observing that the solution must take place in the cold, without the
application of heat. The principle of the titration is, that arsenious
acid, in the presence of water and free alkali, is converted into arsenic
acid—
As2O3 + 4I+ 2Na2O = Asg0s + 4NaI.
The end of the reaction is known by adding a little starch-paste to
the solution; as soon as a blue colour appears, the process is finished.
Another convenient way by which (in very dilute solutions of
arsenious acid) the arsenic may be determined, is a colorimetric method,
which depends on the fact that sulphuretted hydrogen, when arsenious
acid is present in small quantity, produces no precipitate at first, but a
yellow colour, proportionate to the amount of arsenic present. The
silver solution containing arsenious acid is freed from silver by hydro-
chloric acid ; a measured quantity of saturated SH, water is added to a
fractional and, if necessary, diluted portion, in a Nessler cylinder or
colorimetric apparatus, and the colour produced exactly imitated, by
the aid of a dilute solution of arsenious acid, added from a burette to a
592 POISONS : THEIR EFFECTS AND DETECTION. [$ 744.
similar quantity of SH, water in another cylinder, the fluid being
acidified with HCl. -
§ 744. Electrolytic Methods.—The method used in the Govern-
ment laboratory, as arranged by J. E. Thorpe,” requires the following
apparatus:—
A glass vessel of the shape shown in the figure is open at the bottom,
and at the top fitted with a ground glass stopper. Through this stopper
is passed the stem of the tap funnel ; it also carries the gas exit tube
on which there is a bulb. This tube is connected by means of a ground
glass joint with a drying tube. Through the glass cap is fused a stout
platinum wire for making the connection outside with the current and
within the vessel to the electrode.
The inner electrode forming the cathode is a cone of sheet platinum
provided with several perforations. It is suspended from a hook made

---
º
Thorpe's Apparatus.
2 —
~
on the end of the wire passing through the glass stopper, and is adjusted
so that when the stopper is inserted in the vessel the lower edge of the
electrode is one millimetre above the bottom of the vessel; it is then
securely attached to the wire by closing the hook. The porous vessel
is two or three times larger in diameter than the cylindrical portion of
the glass vessel. The glass vessel rests by its bulged-out shoulder on
the edge of the porous vessel, and is thus kept off the bottom.
The porous vessel is of unglazed highly-siliceous ware. The cell for
the anode consists of a stout glass vessel, upon the flat bottom of which
the porous vessel supporting the bulged glass vessel stands. The
anode consists of a band of platinum 2 cm. broad, passing loosely
round the porous cell and connected with the current by means of a
stout platinum wire. The apparatus, lastly, is put in a large dish con-
taining cold water, for, in action, the temperature should not exceed
* Journ. Chem. Soc. Trams., 1903, 974.
§ 744] ARSENIC. 593
50° C. The drying tube is prepared by inserting, first, cotton-wool, and
then granulated calcium chloride for about 5 cm.; another loose plug
of cotton-wool follows, then a roll of dried lead acetate paper. To the
end of the drying tube is fixed, by means of rubber, a hard Jena glass
tube, outside diameter 5 mm., inside 3-5 mm. ; a portion of this tube, 2 cm.
in length, 5 cm. from the end of the tube, is drawn out to a length of
7–8 cm., having at a distance of 1 cm. from the shoulder of the tube an
external diameter of 2 mm., a size to be maintained as nearly as possible
throughout the length of the constricted part. *
The tube is drawn out, cut off near the end of the drawn-out portion,
and the last cm. turned up at right angles.
A piece of platinum gauze 2 cm. square is wrapped round the hard
glass tube at the point where it is to be heated by a Bunsen flame. A
special small burner is recommended with slotted cone to receive the
tube. The current giving the best results is one of five ampères and
seven volts; this may be obtained in places where there is a continuous
supply of electricity from the mains by interposing suitable resistances,
such, for instance, as a rheostat of incandescent lamps.
The authors have used for some time a boron battery of four cells,
the exciting liquid being a sulphuric acid solution of potassic bichromate ;
the ampèrage and voltage are regulated by a sliding resistance.
The method of working is as follows:—After thoroughly cleansing
and connecting up, 30 c.c. of dilute sulphuric acid (1 : 7) are poured
into the anode cell and 20 c.c. into the cathode cell by means of
the stoppered bottle, the stem of which must be kept full of liquid.
The current is allowed to pass for about ten minutes to expel air,
and then the burner is lighted so as to heat the hard glass tube, and
the current passed for another fifteen minutes; if by the end of this
time no brown ring is seen, the testing liquids are presumed to be
pure. Two c.c. of amyl alcohol are run into the inner cell by means
of the tap funnel, and followed by the solution to be tested. The
solution, if quantitative results are to be obtained, should be con-
centrated down so as not to be more than from 30 to 50 c.c.
Obviously, no air must be admitted, and the stem must remain full
of liquid, the last portions of the liquid being rinsed into the flask by
distilled water.
The final operation is to preserve any ring formed in an atmosphere
of hydrogen, which is accomplished very simply as follows:—The
stopper of the funnel is opened, and a small pointed flame directed
against the narrow tube at a point 3 cm. from the deposit between
the deposit and turned-up end of the tube, and drawn off; the electric
current is now interrupted, and the tube, still full of hydrogen, heated
and drawn off near the shoulder.
38
594 POISONS : THEIR EFFECTS AND DETECTION. [$ 745.
Hy. Julius Salomon Sand and John Edward Hackford * have
modified the apparatus by replacing the platinum electrodes by
those of lead, and maintain that lead cathodes give better results than
platinum. A. C. Chapman and H. D. Law have also experimented
with various cathodes, and have obtained good results with lead, tin,
and cadmium.f
§ 745. Gautieri has also devised a process by which the most
minute quantity of arsenic can be separated ; the process is based on
the fact that iron oxide in precipitating from a solution carries down
with it any arsenic. Gautier uses a solution of ferrous sulphate, freed
from every trace of arsenic, as follows:—
100 grms. of ferrous sulphate are dissolved in 1% litres of water, and
after the addition of 25 grims. of pure sulphuric acid heated with SH,
any precipitate is filtered off; and the solution oxidised with 28 grms.
of arsenic-free nitric acid. The iron is now precipitated by ammonia,
the precipitate filtered, washed, and dissolved in the cold by means of
dilute sulphuric acid. Granulated zinc is added, and the solution heated
to boiling under diminished pressure for two days. The solution is
again oxidised with nitric acid, and again precipitated, washed, etc., and
finally dissolved in dilute sulphuric acid.
After destruction of organic matters in the way before indicated, to
the final solution in water so small a quantity of the iron solution is
added that, after such addition, there is no reaction with ferridcyanide;
the precipitate which forms contains no arsenic, and is filtered off. The
filtrate is now precipitated with 5 c.c. of the iron solution, and boiled.
Ammonia is added to neutral reaction. The resulting precipitate is
dissolved in a mixture of nitric and sulphuric acids, the nitric acid
expelled by boiling, and the final sulphuric acid tested for arsenic in the
modified Marsh apparatus already described.
The apparatus recommended by Gautier has been modified somewhat
by Gabriel Bertrand, and as, in essential principles, it is the same as
Gautier's apparatus slightly improved, it will suffice to describe here
only Bertrand's process.
The apparatus consists of a flask of 90 c.c. capacity, in which the
reduction of the arsenical compound is effected by zinc and sulphuric
acid. The flask is furnished with a long tube and cylindrical funnel, E,
to which is fixed by means of a cork the bulb tube, A, furnished with a
stop-cock. The gas passes through the tube, L, 30 c.c. long, charged
with highly dried cotton-wool; to this tube succeeds C, made of diffi-
cultly fusible glass—the internal diameter is 1 mm., and the walls
2 mm. thick. The tube is surrounded by asbestos, and heated by a
* Jowrm. Chem. Soc. Trams., 1904, 1018. t Analyst, 1906, 12.
# Compt. Rend., czzxvii. 158. -
§ 746.] ARSENIC. 595
“ramp” of gas for the length of 10 c.c.; 3 c.c. from the heated part a
small stream of cold water, dropping on a piece of filter-paper wrapped
around the tube, cools the issuing gas, which finally bubbles through
water at W.
The method of procedure with this apparatus is as follows:—10–20
grms. of granulated zinc are introduced into a flask, with 30 c.c. of
water and a few drops of a solution of platinum chloride. As soon as
the zinc is platinised, which is denoted by the bright surfaces becoming
of a dull grey black, the water is poured away, and, after washing the
zinc with a little distilled water, the zinc is transferred to the flask, F,
and the apparatus connected up. The air is now displaced by a current
of dry carbonic acid gas, and 10 c.c. of sulphuric acid (1 of acid to 4 of
water) added ; a brisk effervescence follows, and the carbonic acid gas
Gabriel Bertrand's Apparatus.
is expelled from the apparatus by the hydrogen; 10 cm. of the
capillary thick-walled tube is now brought to a dull red heat, and the
cooling arrangement adjusted. After ten to fifteen minutes the evolution
of gas has become somewhat slow, and the solution to be tested for
arsenic is introduced by means of the bulb funnel, little by little, into
the flask. The bulb is washed out at first with 20 c.c. of dilute
sulphuric acid (10 per cent.), and then with 10 c.c. of the 1 to 4 acid,
taking care that the acid only falls into the apparatus drop by drop.
The most suitable evolution of gas is found to be from 4 to 5 c.c. per
minute : a guess of the quantity evolved may be made by counting the
bubbles of gas escaping through the final water in W.
§ 746. Precipitation as Tersulphide. —- The advantages of the
processes described are great when dealing with minute quantities,
but the old method of precipitation with hydric sulphide SH, is

596 POISONS: THEIR EFFECTS AND DETECTION. [$ 746.
best for quantities of arsenic which admit of being directly weighed.
If this be used, it is well in most cases to pass sulphurous
anhydride through the liquid until it smells strongly of the gas, for
by this means any arsenic acid present is reduced; the sulphurous
anhydride is quickly got rid of by a current of carbonic anhydride,
and then the liquid is saturated with hydric sulphide. In the ordinary
way, much time is often wasted in saturating the liquid with this gas.
Those, however, who have large laboratories, and daily employ hydric
sulphide, possess (or should possess) a water saturated with the gas
under pressure ; such a liquid, added in equal volume to an arsenical
Solution, is able to convert the whole of the arsenic into sulphide in a
very few minutes. Those who do not possess this hydric sulphide water
can Saturate in an hour the liquid to be tested, by passing the gas in
under pressure. A convenient method is to evolve SH, from sulphide
of antimony and ClFI; the gas passes first into a wash-bottle, and then
into a strong flask containing the solution under trial. This flask is
furnished with a safety-valve, proportioned to the strength of the
apparatus; the two tubes dipping into the wash-bottle and the last flask
are provided with Bunsen's valves, which only allow the gas to pass
in one direction. The hydric sulphide is then driven over by heat,
and when sufficient gas has in this way passed into the liquid, the
flame is withdrawn, and the apparatus allowed to stand for some
hours, the valves preventing any backward flow of the liquid or gas.
When the precipitate has settled to the bottom, the supernatant fluid
is carefully passed through a filter, and the precipitate washed by
decantation in the flask, without transference to the filter, if it can
be avoided.
The impure sulphide is washed with water, then with alcohol, then
with carbon disulphide, then, after having got rid of the latter, again
with alcohol, and finally with water. It is then dissolved in ammonia,
the ammonia solution filtered, and the filtrate evaporated to dryness
on a sand-bath at a somewhat high temperature; in this way it is
freed from sulphur and, to a great extent, from organic matter. After
weighing, it may be purified or identified by some of the following
methods:–
(a) Solution in Ammonia and Estimation by Iodine.*—The filter
is pierced, the sulphide washed into a flask by ammonia water (which
need not be concentrated), and dissolved by warming, filtered from any
insoluble matter, and estimated by iodine and starch.
(b) 0xidation of the Sulphide and Precipitation as Ammonia
Magnesian Arseniate.—The tersulphide is dissolved in ammonia
(not omitting the filter-paper, which should be soaked in this
* P. Champion and H. Pellett, Bull. Soc. Chim, (2), xxvi. pp. 541–544.
§ 746.] ARSENIC. 597
reagent), the solution filtered, and evaporated to dryness. The dry
residue is now oxidised by fuming nitric acid, taking care to protect
the dish with a large watch - glass (or other cover) during the
first violent action; the dish is then heated in the water-bath until
all the sulphur has disappeared, and only a small bulk of the liquid
remains; it is then diluted and precipitated by “magnesia mixture.” “
The fluid must stand for several hours, and, if the arsenic is to be
determined as the usual ammoniacal salt, it must be passed through
a weighed filter, and washed with a little ammoniacal water (1 : 3).
The solubility of the precipitate is considerable, and for every 16 c.c.
of the filtrate (not the washings) 1 mgrm. must be allowed. The
precipitate, dried at 100°, 2(NH, MgAsO4)H2O, represents 39:47 per
cent. metallic arsenic.
The solubility of the magnesium arseniate itself, and the general dis-
like which chemists have to weighing in such hygroscopic material as a
filter, are, perhaps, the main reasons for the variation of this old method,
which has lately come into notice. Rose proposed some time ago the con-
version of the double Salt into the pyro-arseniate—a method condemned
by Fresenius and Parnell, but examined and pronounced a practicable
and accurate process by Remol, Rammelsberg, Thorpe, Fuller, Wittstein,
Emerson, Macivor, Wood, and Brauner. The modification of Rose's
process, recommended by Wood,i and still further improved by Brauner,
may be accepted.
The precipitation is effected by magnesia mixture, with the addition
of half its bulk of alcohol. The solution is allowed to stand for several
hours, until it is possible to decant the clear liquid from the precipitate ;
the latter is now dissolved in ClFI, reprecipitated as before, thrown on a
small filter, and washed with a mixture of one volume of ammonia, two
volumes of alcohol, and three of water.
The precipitate is now dried, and transferred as completely as
possible from the filter into a small porcelain crucible, included in
a larger one made of platinum, moistened with nitric acid, covered
and heated at first gently, lastly to a bright redness; the filter is
then treated similarly, and the crucible with its contents weighed.
Pyro-arseniate of magnesia (Mg,Asg0.) contains 48.29 per cent. of
metallic arsenic,
* Magnesia Mixture:—
Sulphate of magnesia, .
Chloride of ammonium,
Solution of ammonia, . ſº tº tº e e & º
Water, $ e e † e & tº tº § $ 8
Dissolve ; then allow to stand for several days; finally filter, and keep for use.
t Zeitschr, für anal. Chem., vol. xiv. p. 356.
# Ibid., xv.j. pp. 57, 58.
:
598 POISONS : THEIR EFFECTS AND DETECTION. [S 746.
(c) Conversion of the Trisulphide of Arsenic into the Arsenomo-
lybdate of Ammonia.-The purified sulphide is oxidised by nitric acid ;
the acid solution is rendered alkaline by ammonia, and then precipitated
by a molybdenum solution, made as follows:–100 grns. of molybdic
acid are dissolved in 150 c.c. of ordinary ammonia and 80 of water; this
solution is poured drop by drop into 500 c.c. of pure nitric acid and 300 c.c.
of water; it is allowed to settle, and, if necessary, filtered. The molybdic
solution must be mixed in excess with the liquid under treatment, the
temperature raised to 70° or 80°, and nitric acid added in excess until
a yellow coloration appears; the liquid is then passed through a tared
filter, and dried at 100°. It contains 5:1 per cent. of arsenic acid
[3-3 As].”
(d) Conversion of the Sulphide into Metallic Arsenic.—If there
should be any doubt as to the nature of the precipitated substances, the
very best way of resolving this doubt is to reduce the sulphide to metal;
the easiest method of proving this is to dissolve in potash and obtain
arsine by the action of aluminium; or if it is desired to evolve arsine
from an acid solution with zinc in the usual way, then by dissolving
a slight excess of zinc oxide in potash or soda, and dissolving in this the
arsenic sulphide; the zinc combines with all the sulphur, and converts
the sulpharsenite into arsenite ; the zinc sulphide is filtered off, and the
filtrate acidified and introduced into Marsh's apparatus. The original
process of Fresenius was to mix the sulphide with carbonate of soda
and cyanide of potassium, and place the mixture in the wide part of a
tube of hard German glass, drawn out at one end to a capillary fineness.
Carbonic anhydride, properly dried, was passed through the tube, and
the portion containing the mixture heated to redness; in this way the
arsenical sulphide was reduced, and the metal condensed in the capil-
lary portion, where the smallest quantity could be recognised. A more
elaborate and accurate process, based on the same principles, has been
advocated by Mohr.f
A convenient quantity of carbonate of soda is added to the sulphide,
and the whole mixed with a very little water and gently warmed. The
yellow precipitate is very soon dissolved, and then the whole is
evaporated carefully, until it is in a granular, somewhat moist, adhesive
state. It is now transferred to a glass tube, open at top and bottom,
but the top widened into a funnel; this tube is firmly held perpendicu-
larly on a glass plate, and the prepared sulphide hammered into a
compact cylinder by the aid of a glass rod, which just fits the tube.
The cylinder is now dried over a flame until no more moisture is to
be detected, and then transferred into a glass tube 4 or 5 inches long,
* Champion and Pellet, Bull. Soc. Chim., Jan. 7, 1877.
+ Mohr’s Toa'icologie, p. 57.
§ 746.] ARSENIC. 599
and with one end drawn to a point (the weight of this tube should be
first accurately taken). The tube is connected with the following
series:—(1) A chloride of calcium tube; (2) a small bottle containing
nitrate of silver solution; (3) a hydrogen-generating bottle containing
zinc and sulphuric acid. The hydrogen goes through the argentic
nitrate solution, leaving behind any sulphur and arsenic it may contain ;
it is then dried by chloride of calcium, and streams in a pure dry state
over the cylinder of prepared sulphide (no error with regard to impurities
in the gas is likely to occur; but in rigid inquiries it is advisable to
heat a portion of the tube, previous to the insertion of the cylinder, for
some time, in order to prove the absence of any external arsenical
source); when it is certain that pure hydrogen, unmixed with air, is
being evolved, the portion of the tube in which the cylinder rests is
heated slowly to redness, and the metallic arsenic sublimes at a little
distance from the source of heat. Loss is inevitable if the tube is too
short, or the stream of hydrogen too powerful.
The tube, after the operation, is divided; the portion soiled by the
soda thoroughly cleansed, and then both parts weighed; the difference
between the weight of the empty tube and the tube + arsenic gives the
metallic arsenic. This is the process as recommended by Mohr; it may,
however, be pointed out that the glass tube itself loses weight when any
portion of it is kept red-hot for some little time; and, therefore, unless
the crust is required in the original tube, it is better to divide it,
carefully weigh the arsenical portion, remove the crust, and then
re-weigh. The method is not perfectly accurate. The mirror is
not pure metallic arsenic, and if the white alkaline residue be
examined, arsenic will be detected in it, the reason being that the
arsenical sulphide generally contains pentasulphide of arsenic as well as
free sulphur. Now the pentasulphide does not give up metallic arsenic
when treated as before detailed; nor, indeed, does the trisulphide, if
mixed with much sulphur, yield an arsenical crust. It is, therefore, of
great moment to free the precipitate as much as possible from sulphur,
before attempting the reduction.
The development of a reducing gas from a special and somewhat
complicated apparatus is not absolutely necessary. The whole process
of reduction, from beginning to end, may take place in a single tube by
any of the following processes:—(1) The sulphide is mixed with oxalate
of soda (a salt which contains no water of crystallisation), and the dry
mixture is transferred to a suitable tube, sealed at one end. An
arsenical mirror is readily obtained, and, if the heat is continued long
enough, no arsenic remains behind—an excellent and easy method, in
which the reducing gas is carbonic oxide, in an atmosphere of carbonic
anhydride. (2) The sulphide is oxidised by aqua regia, and the solution
6OO Poisons: THEIR EFFECTS AND DETECTION. [$ 747, 748.
evaporated to complete dryness. The residue is then dissolved in a few
drops of water, with the addition of some largish grains of good wood
charcoal (which absorb most of the solution), and the whole carefully
dried. The mass is now transferred to a tube closed at one end, a little
charcoal added in the form of an upper layer, and heat applied first to
this upper layer, so as to replace the air with CO2, and then to bring
the whole tube gradually to redness from above downwards. In this
case also the whole of the arsenic sublimes as a metallic mirror.
There are various other modifications, but the above are trustworthy,
and quite sufficient.
2. ANTIMONY.
§ 747. Metallic Antimony.—Atomic weight, 120.3 (R. Schneider),
120-14 (Cook); specific gravity, 6'715; fusing-point about 621”
(1150°F.). In the course of analysis, metallic antimony may be seen
as a black powder thrown down from solutions; as a film deposited on
copper or platinum ; and, lastly, as a ring on the inside of a tube from
the decomposition of stibine. At a bright red-heat it is volatilised
slowly, even when hydrogen is passed over it ; chlorine, bromine, and
iodine combine with it directly. It may be boiled in concentrated
ClFI without solution ; but aqua regia, sulphides of potassium and
sodium, readily dissolve it. The distinction between thin films of this
metal and arsenic on copper and glass are pointed out at pp. 583
and 584. It is chiefly used in the arts for purposes of alloy, and enters
to a small extent into the composition of fireworks (vide pp. 556
and 604).
§ 748. Antimonious Sulphide.—Sulphide of antimony = 336; com-
position in 100 parts, Sb 71-76, S 28-24. The commercial article, known
under the name of black antimony, is the native sulphide, freed from
siliceous matter by fusion, and afterwards pulverised. It is a crystalline
metallic-looking powder, of a steel-grey colour, and is often much con-
taminated with iron, lead, copper, and arsenic.
The amorphous sulphide (as obtained by saturating a solution of
tartar emetic with SH3) is an orange-red powder, soluble in potash and
in ammonic, sodic, and potassic sulphides; and dissolving also in
hydrochloric acid with evolution of SH3. It is insoluble in water and
Very dilute acid, scarcely dissolves in carbonate of ammonia, and is
quite insoluble in potassic bisulphite. If ignited gently in a stream of
carbonic acid gas, the weight remains constant. To render it anhydrous,
a heat of 200” is required.
Several lamentable accidents have happened through mistaking the
sulphide of antimony for oxide of manganese, and using it with potassic
chlorate for the production of oxygen. The addition of a drop of
§ 749, 750.] ANTIMONY. 6OI
hydrochloric acid, it is scarcely necessary to say, will distinguish
between the two.
Antimony is frequently estimated as sulphide. An amorphous
tersulphide of mercury, containing a small admixture of antimonious
oxide and sulphide of potassium, is known under the name of Kermes
mineral, and has been employed in the vulcanising of india-rubber.
Prepared in this way, the latter may be used for various purposes, and
thus become a source of danger. It behoves the analyst, therefore, in
searching for antimony, to take special care not to use any india-rubber
fittings which might contain the preparation.
A pentasulphide of antimony (from the decomposition of Schleppe's
salt [NassbeS, +9FL,0], when heated with an acid) is used in calico-
printing.
§ 749. Tartarated Antimony, Tartrate of Potash and Antimony,
or Tartar Emetic, is, in a medico-legal sense, the most important of
the antimonial salts. Its formula is KSbC, H, O, H2O, and 100 parts,
theoretically, should contain 35.2 per cent. of metallic antimony. The
B.P. gives a method of estimation of tartar emetic not free from error,
and Professor Dunstan has proposed the following:—Dissolve 0.3 grim.
of tartar emetic in 80 c.c. of water, add to this 10 c.c. of a 5 per cent.
solution of sodium bicarbonate, and immediately titrate with a decinormal
solution of iodine, using starch as an indicator. One c.c. of TO iodine =
0.0166 grn. tartar emetic ; therefore, if pure, the quantity used by
0-3 grm. should be 18 c.c. Tartar emetic occurs in commerce in
colourless, transparent, rhombic, octahedral crystals, slightly efflorescing
in dry air.
A crystal, placed in the subliming cell (p. 260), decrepitates at 1933°
(380° F.), sublimes at 248.8° (480° F.) very slowly and scantily, and
chars at a still higher temperature, 287.7° (550°F.). On evaporating a
few drops of a solution of tartar emetic, and examining the residue by
the microscope, the crystals are either tetrahedra, cubes, or branched
figures. 100 parts of cold water dissolve 5 of tartar emetic, whilst the
same quantity of boiling water dissolves ten times as much, viz., 50.
The watery solution decomposes readily with the formation of algae; it
gives no precipitate with ferrocyanide of potassium, chloride of barium,
or nitrate of silver, unless concentrated.
$ 750. Metantimonic Acid, so familiar to the practical chemist from
its insoluble sodium salt, is technically applied in the painting of glass,
porcelain, and enamels; and in an impure condition, as antimony ash, to
the glazing of earthenware
6O2 POISONS : THEIR EFFECTS AND DETECTION. [$ 751.
§ 751. Pharmaceutical, Veterinary, and Quack Preparations
of Antimony.*
(1) Pharmaceutical Preparations:–
Oxide of Antimony (Sb,Os) is a white powder, fusible at a low red
heat, and soluble without effervescence in hydrochloric acid, the solution
responding to the ordinary tests for antimony. Arsenic may be present
in it as an impurity. Carbonate of lime appears also to have been found
in the oxide of commerce.
Antimonial Powder is composed of one part of oxide of antimony
and two parts of phosphate of lime; in other words, it ought to give
33.3 per cent. of Sb,0s.
Tartar Emetic itself has been already described. The preparations
used in medicine are—
The Wine of Antimony (Vinum antimoniale), which is a solution
of tartar emetic in sherry wine, and should contain two grains of the salt
in each ounce of the wine (0:45 grm. in 100 c.c.).
Antimony Ointment (Unguentum antimonii tartarati) is a mechani-
cal mixture of tartar emetic and lard, or simple ointment;i strength, 20
per cent. There is no recorded case of conviction for the adulteration of
tartar emetic ; cream of tartar is the only probable addition. In such a
case the mixture is less soluble than tartar emetic itself, and on adding
a small quantity of carbonate of soda to a boiling solution of the suspected
salt, the precipitated oxide at first thrown down becomes redissolved.
Solution of Chloride of Antimony is a solution of the terchloride in
hydrochloric acid; it is a heavy liquid of a yellowish-red colour, power-
fully escharotic ; its specific gravity is 1:47; on dilution with water, the
whitish-yellow oxychloride of antimony is precipitated. One drachm
(3-549 c.c.) mixed with four ounces (112 c.c.) of a solution of tartaric
acid (-25 : 4) gives a precipitate with SH2, which weighs at least 22
grains (1425 grm.). This liquid is used on very rare occasions as an
outward application by medical men; farriers sometimes employ it in
the foot-rot of sheep.
Purified Black Antimony (Antimonium nigrum purificatum) is the
purified native sulphide Sb2S3; it should be absolutely free from arsenic.
Sulphurated Antimony (Antimonium sulphuratum) is a mixture of
sulphide of antimony, Sb2S3, with a small and variable amount of oxide,
Sb,0,. The B.P. states that 60 grains (3888 grms.) dissolved in ClFI,
and poured into water, should give a white precipitate of oxychloride of
* The history of antimony as a drug is curious. Its use was prohibited in France
in 1566, because it was considered poisonous, one Besnier being actually expelled from
but faculty for transgressing the law on this point. The edict was repealed in 1650;
the in 1668 there was a fresh enactment, confining its use to the doctors of the faculty.
† Simple ointment is composed of white wax 2, lard 3, almond oil 3 parts.
§ 751.] ANTIMONY. 603
antimony, which (properly washed and dried) weighs about 53 grains
(3:444 grims.). The officinal compound pill of subchloride of mercury
(Pilula hydrargyri subchloridi composita) contains 1 grain (0648 grim.)
of sulphurated antimony in every 5 grains (324 grim.), i.e. 20 per cent.
(2) Patent and Quack Pills:–
Dr. J. Johnson’s Pills.—From the formula each pill should contain :-
Grains. Grm.
Compound Extract of Colocynth, . gº . 2°5 = 162
Calomel, e wº g º •62 = 039
Tartar Emetic, . * * & ſº & tº •04 = *002
Oil of Cassia, . º & g p ſe g '12 = .007
3°28 = 210
The oil of cassia can be extracted by petroleum ether; the calomel sublimed and
identified by the methods given in the article on “Mercury”; the antimony de-
posited in the metallic state on platinum or tin ; and the colocynth extracted by
dissolving in water, acidifying, and shaking up with chloroform. On evaporating
the chloroform the residue should taste extremely bitter; dissolved in Sulphuric acid
it changes to a red colour, and dissolved in Fröhde's reagent to a cherry-red. It
should also have the ordinary reactions of a glucoside.
Mitchell’s Pills contain in each pill:—
Grains. Grm.
Aloes, we ſº © wº * {} . . . 1 1 = -070
Rhubarb, . º tº º e & wº . l’6 = 103
Calomel, . tº & e ſe º e º *16 = •010
Tartar Emetic, . & & & * i- * *05 = 003
2'91 = 186
The mineral substances in this are easy of detection by the methods already given ;
the aloes by the formation of chrysammic acid, and the rhubarb by its microscopical
characters.
Dixon's Pills probably contain the following in each pill:—
Grains. GTm.
Compound Extract of Colocynth, . g . 2'0 = 1296
Rhubarb, . e e º & e . 1°0 = 0648
Tartar Emetic, * º º * * & *06 = -0038
3.06 = 1982
(3) Antimonial Medicines, chiefly Veterinary: *—
Liver of Antimony is a preparation formerly much used by farriers. It is a
* There has long prevailed an idea (the truth of which is doubtful) that antimony
given to animals improves their condition ; thus, the Encyclop. Brit., 5th ed., art.
“Antimony”:—“A horse that is lean and scrubby, and not to be fatted by any
means, will become fat on taking a dose of antimony every morning for two months
together. A boar fed for brawn, and having an ounce of antimony given him every
morning, will become fat a fortnight sooner than others put into the sty at the same
time, and fed in the same manner, but without the antimony.” Probably the writer
means by the term anti-mony the impure sulphide. To this may be added the un-
doubted fact, that in Brunswick the breeders of fat geese add a small quantity of
antimonious oxide to the food, as a traditional custom.
6O4 POISONS : THEIR EFFECTS AND DETECTION. [$ 752.
hu.
mixture of antimonious oxide, sulphide of potassium, carbonate of potassium, and
undecomposed trisulphide of antimony (and may also contain sulphate of potassium),
all in very undetermined proportions. When deprived of the soluble potash salts,
it becomes the washed saffron of antimony of the old pharmacists. A receipt for a
grease-ball, in a modern veterinary work, gives, with liver of antimony, cream of
tartar and guaiacum as ingredients.
Hind's Sweating-ball is composed of 60 grains (3.888 grms.) of tartar emetic and
an equal portion of assafoetida, made up into a ball with liquorice-powder and syrup.
The assafoetida will be readily detected by the odour, and the antimony by the
methods already recommended.
Ethiops of Antimony, very rarely used now, is the mechanical mixture of the
sulphides of antimony and mercury—proportions, 3 of the former to 2 of the latter.
The Flowers of Antimony is an impure oxysulphide of antimony, with variable
proportions of trioxide and undecomposed trisulphide.
Diaphoretic Antimony (calcined antimony) is simply antimoniate of potash.
Glass of Antimony is a mixture of sulphide and oxide of antimony, contaminated
with a small quantity of silica and iron.
A quack pill, by name, Ward's Red Pill, is said to contain glass of antimony and
dragon’s blood.
Antimonial Compounds used in Pyrotechny:—
Blue Fire :—
Antimonious sulphide, . e º º º º º e l
Sulphur, . º e o º º e tº º e 2
Nitre, . ſº º e º º o s º º º 6
This composition is used for the blue or Bengal signal-light at Sea. Bisulphide
of carbon and water are solvents which will easily separate the powder into its three
constituents.
Crimson Fire:—
Potassic Chlorate, . º e º º e º - 17:25
Alder or Willow Charcoal, . º º ſº tº & 4' 5
Sulphur, © º e º e e º L. 18 °
Nitrate of Strontia, e º © e e e - 55-
Antimonious Sulphide, . & ſº tº e & © 5' 5
The spectroscope will readily detect strontia and potassium, and the analysis
presents no difficulty. In addition to these a very great number of other pyro-
technical preparations contain antimony.
§ 752. Alloys.--Antimony is much used in alloys. The ancient Pocula emetica,
or everlasting emetic cups, were made of antimony, and with wine standing in them
for a day or two they acquired emetic properties. The principal antimonial alloys
are Britannia and type metal, the composition of which is as follows:–
Tin, Copper Antimony,
per cent. per cent. per cent.
Britannia Metal, Best, . {º . 92°0 1-8 6'2
Common, . . 92°1 2°0 5'9
For Castings, . 92°9 1-8 5-3
For Lamps, . . 94'0 1°3 4-7
Tea Lead, Antimony, Block Tin,
per cent. per cent. per cent.
(1) 75 20 5
Type Metal, . e e (2) 70 25 5
Metal for Stereotype, . e . 84'2 13°5 2°3
There is also antimony in brass, concave mirrors, bell-metal, etc.
§ 753–755.] ANTIMONY. 605
§ 753. Pigments.-Cassella and Naples yellow are principally composed of the
antimoniate of lead.
Antimony Yellow is a mixture of antimoniate of lead with basic chloride of
lead. •º
§ 754. Dose.—A medicinal dose of a soluble antimonial salt should
not exceed 97.2 mgrms. (1% grain). With circumstances favouring its
action, a dose of 129.6 mgrms. (2 grains) has proved fatal; * but this
is quite exceptional, and few medical men would consider so small a
quantity dangerous for a healthy adult, especially since most posological
tables prescribe tartar emetic as an emetic in doses from 64-8 to 194'4
mgrims. (1 to 3 grains). The smallest dose which has killed a child
appears to be 48.5 mgrms. (# grain).f The dose of tartar emetic for
horses and cattle is very large, as much as 5'832 grims. (90 grains)
being often given to a horse in his gruel three times a day. 3-8 grms.
(60 grains) are considered a full, but not an excessive, dose for cattle;
‘38 grn. (6 grains) is used as an emetic for pigs, and half this quantity
for dogs.
§ 755. Effects of Tartar Emetic and of Antimony Oxide on Animals.
—Large doses of tartar emetic act on the warm-blooded animals as on
man; whether the poison is taken by the mouth, or injected subcu-
taneously, all animals able to vomit : do so. The heart's action, at
first quickened, is afterwards slowed, weakened, and lastly paralysed.
This action is noticed in cold as well as in warm blooded animals. It is
to be ascribed to a direct action on the heart; for if the brain and
spinal cord of the frog be destroyed—or even if a solution of the salt be
applied direct to the frog's heart separated from the body—the effect is
the same. The weak action of the heart, of course, causes the blood-
pressure to diminish, and the heart stops in diastole. The voluntary
* Taylor, Guy's Hosp. Reports, Oct. 1857. t Op. cit.
# L. Hermann (Lehrbuch der experimentellen Toa'icologie) remarks that the
vomiting must be considered as a reflex action from the inflammatory excitement of
the digestive apparatus, especially of the stomach. It is witnessed if the poison is
administered subcutaneously or injected into the brain. Indeed, it is established
that (at least, so far as the muscles are concerned) the co-ordinate movements
producing vomiting are caused by excitement of the medulla oblongata. Giannussi
and others found that after section between the first and third vertebrae of dogs, and
subsequent administration of tartar emetic, no vomiting took place; and Grimm's
researches seem to show that the suspected vomit-centre is identical with the
respiratory centre, so that the vomiting movement is only an abnormal respiratory
movement. L. Hermann, however, considers the theory that when tartar emetic
is introduced into the vessels the vomit-centre is directly excited, erroneous, for (1)
in introducing it by the veins much larger doses are required to excite vomiting than
by the stomach ; and (2), after subcutaneous injection of the salt, antimony is found
in the first vomit. His explanation, therefore, is that antimony is excreted by the
intestimal tract, and in its passage excites this action. Majendie's well-known
experiment—demonstrating that, after extirpation of the stomach, vomiting move.
ments were noticed—is not considered opposed to this view.
6O6 POISONS : THEIR EFFECTS AND DETECTION. [$ 756.
muscles of the body are also weakened; the breathing is affected, partly
from the action on the muscles. The temperature of the body is
depressed (according to F. A. Falck’s researches) from 4'4" to 6'2".
The effect of small doses given repeatedly to animals has been
several times investigated. Dr. Nevin * experimented upon eleven
rabbits, giving them tartar emetic four times a day in doses of 32°4
mgrms. (4 grain), 64.8 mgrms. (1 grain), and 129.6 mgrms. (2 grains).
Five died, the first after four, the last after seventeen days; three
were killed after one, three, and four days respectively, two after an
interval of fourteen days, and one thirty-one days after taking the last
dose. There was no vomiting; diarrhoea was present in about half the
number ; one of the rabbits, being with young, aborted. The chief
symptoms were general dulness, loss of appetite, and in a few days
great emaciation. Four of the five that died were convulsed before
death ; and several of the animals exhibited ulcers of the mucous
membrane of the mouth, in places with which the powder had come in
contact. Caillol and Livon have also studied the action of small doses
of the white oxide of antimony given in milk to cats. A cat took in
this way in 109 days 628 grm. The animal passed gradually into a
cachectic state, diarrhoea supervened, and it died miserably thin and
exhausted.
§ 756. Effects of Tartar Emetic on Man, f—The analogy between
the symptoms produced by arsenic and antimony is striking, and in
some acute cases of poisoning by tartar emetic there is but little (if
any) clinical difference. If the dose of tartar emetic is very large,
there may be complete absence of vomiting, or only a single evacuation
of the stomach. Thus, in a case mentioned by Taylor, in which a
veterinary surgeon swallowed by mistake 13 grims. (200 grains) of
tartar emetic, vomiting after fifteen minutes could only be induced by
tickling the throat. So, again, in the case reported by Mr. Freer,
a man, aged 28, took 7-77 grims. (120 grains) of tartar emetic
by mistake for Epsom salts; he vomited only once ; half an hour
after taking the poison he had violent pain in the stomach and
abdomen, and spasmodic contraction of the abdomen and arms;
* Lever, Med. Chir. Journ., No. 1.
† Antimony occasionally finds its way into articles of food through obscure
channels. Dr. Page has recorded the fact of antimonial lozenges having been sold
openly by an itinerant vendor of confectionery. Each lozenge contained nearly a
quarter of a grain (16 mgrim.), and they caused well-marked symptoms of poisoning
in the case of a servant and two children. How the antimony got in was unknown.
In this case it appears to have existed not as tartar emetic, but as an insoluble oxide,
for it would not dialyse in aqueous solution.—“On a remarkable instance of Poison-
ing by means of Lozenges containing Antimony,” by David Page, M.D., Medical
Officer of Health, Lancet, vol. i., 1879, p. 699.
§ 757.] ANTIMONY. 6O7
the fingers were firmly contracted, the muscles quite rigid, and
there was involuntary aqueous purging. After six hours, during
which he was treated with green tea, brandy, and decoction of oak-
bark, he began to recover, but suffered for many nights from profuse
perspirations.
With more moderate and yet large doses, nausea and vomiting are
very prominent symptoms, and are seldom delayed more than half an
hour. The regular course of symptoms may therefore be summed up
thus:–A metallic taste in the mouth ; repeated vomitings, which are
sometimes bloody; great faintness and depression ; pains in the abdomen
and stomach ; and diarrhoea, which may be involuntary. If the case is
to terminate fatally, the urine is suppressed, the temperature falls, the
face becomes cyanotic, delirium and convulsions supervene, and death
occurs in from two to six days. Antimony, like arsenic, often produces
a pustular eruption. Solitary cases deviate more or less from the
course described — i.e. severe cramps affecting all the muscles,
haemorrhage from the stomach, kidney, or bowel, and death from collapse
in a few hours, have all been noticed. In a case recorded by Mr.
Morley,” a surgeon's daughter, aged 18, took by mistake an unknown
quantity of antimonial wine ; she soon felt sleepy and powerless, and
suffered from the usual symptoms in combination with tetanic spasms
of the legs. She afterwards had enteritis for three weeks, and on
recovery her hair fell off. Orfila relates a curious case of intense spasm
of the gullet from a large dose of tartar emetic.
§ 757. Chronic Antimonial Poisoning.—The cases of Palmer and
J. P. Cook, M. Mullen, Freeman, Winslow, Pritchard, the remarkable
Bravo case, and the Chapman case have given the subject of chronic
antimonial poisoning a considerable prominence. In the trials referred
to, it was shown that medical men might easily mistake the effects of
doses of antimony given at intervals for the action of disease—the
symptoms being great nausea, followed by vomiting, chronic diarrhoea,
alternating with constipation, small frequent pulse, loss of voice, great
muscular weakness, depression, with coldness of the skin and a clammy
perspiration. In the case of Mrs Pritchard, f her face was flushed, and
her manner so excited as to give an ordinary observer the idea that she
had been drinking; and with the usual symptoms of vomiting and
purging, she suffered from cramps in the hands. Dr. Pritchard tried to
make it appear that she was suffering from typhoid fever, which the
symptoms in a few respects only resembled.
According to Eulenberg, workmen, exposed for a long period to the
vapour of the oxide of antimony, suffer pain in the bladder and a burn-
* Brit. Med. Jowrm., 1879.
f Edin. Med. Journ., 1865.
6O8 POISONS : THEIR EFFECTS AND DETECTION. [$ 758.
ing sensation in the urethra, and continued inhalation even leads to
impotence and wasting of the testicles.*
§ 758. The Chapman Case.—Severino Kloswsti alias George Chapman
was a Russian Pole who had been apprenticed to a surgeon in Warsaw,
and had obtained the degree of “Faldscher.” Coming to England he
acted as a barber's assistant, and married a Luccz Paderssi in October
1889. This woman left him after a short time. He then took the
name of Chapman and lived with a woman, Mrs. Isabella Spint, who
passed as Mrs. Chapman. The couple went to live at Hastings, where
Chapman became more or less intimate with a chemist, from whom he
obtained about an ounce of tartar emetic. Leaving Hastings, he next
appears as the landlord of the “Prince of Wales” public-house, Bartholo-
mew Square, Finsbury. Mrs. Chapman now became ill, the chief symp-
tom being frequent vomiting, Chapman ascribing her illness to excessive
drinking. On Christmas Day, 1897, Mrs. Chapman was extremely ill,
and her husband gave her frequent doses of brandy, after each of which
the sickness increased. She died about midday. His next victim was
Elizabeth Taylor, who first appeared as barmaid, and was then per-
suaded to go through some form of marriage with Chapman in the
spring of 1899. In March they moved into the “Monument” public
house in Southwark, where the woman became ill, the symptoms being
the same as before. Dr. Stoker, who was called in on 1st January,
ascribed the illness to some obscure stomach disease, this opinion being
confirmed by two medical colleagues who were summoned. The case
ended fatally on 13th February.
In August, Maud Marsh appears as barmaid, and in October the
parents of this girl were deceived by a tale of a sudden marriage with
Chapman. The “Monument” public-house shortly after this being burnt
down, the couple moved to the “Crown,” where, owing to the attraction
of a new barmaid, Chapman's affection for Maud Marsh seems to have
waned, with the result that in July 1902 Maud began to feel unwell.
She had brandy administered to her by Chapman which always brought
on violent sickness. On 28th July she went to Guy's Hospital as an
in-patient for three weeks, where she was treated for inflammation of the
stomach and discharged cured. On returning to the “Crown’she at onee
became ill again, and in the beginning of October Dr. Stoker was again
called in, and, later, Dr. Grapell. On 22nd October Maud Marsh died,
and Dr. Stoker refused to give a certificate of death before holding a
post-mortem examination.
Dr. Stoker's preliminary examination revealed much inflammation
* In the first operations of finishing printers’ types, the workmen inhale a
metallic dust, which gives rise to effects similar to lead colic ; and probably in this
case the lead is more active than the associated antimony.
§ 759.] ANTIMONY. 609
of the stomach, but no signs of organic disease. He sent some portion
of the viscera to Mr. Bodmer, Public Analyst for Bermondsey, who found
in it arsenic in small quantity and a considerable quantity of antimony.
Chapman was now arrested, and his room at the “Crown" searched,
where the police found several medical works and some powders which,
upon analysis, proved to be tartar emetic.
A further post-mortem examination was made on the body of Maud
Marsh by Dr. Freyberger, pathologist to the London County Council,
and the organs submitted to Dr. Stevenson for analysis. The result of
these investigations left no doubt as to the cause of death, Dr. Stevenson
finding from 25 to 30 grains of tartar emetic in the stomach alone.
In the meanwhile the bodies of Bessie Taylor and Isabella Spint were
exhumed, and found to be in an astonishing state of preservation,
especially remarkable in the case of the latter who had been buried five
years. Dr. Stevenson found 1:37 grains of antimony in the organs of
Isabella Spint, and no less than 29' 12 grains in those of Bessie Taylor.
Chapman was found guilty, and hanged on 7th April 1903.
§ 759. Post-mortem Appearances.—The effect of large doses of
tartar emetic is mainly concentrated upon the gastro-intestinal mucous
membrane. There is an example in the museum of University College
Hospital of the changes which resulted from the administration of tartar
emetic in the treatment of pneumonia. These are ascribed in the cata-
logue, in part to the local action of the medicine, and in part to the
extreme prostration of the patient. In the preparation (No. 1052) the
mucous membrane over the fore border of the epiglottis and adjacent
part of the pharynx has been destroyed by sloughing; the ulceration
extends into the upper part of the oesophagus. About an inch below its
commencement, the mucous membrane has been entirely removed by
sloughing and ulceration, the circular muscular fibres being exposed.
Above the upper limit of this ulcer, the mucous membrane presents
several oval, elongated, and ulcerated areas, occupied by strips of mucous
membrane which have sloughed. In other places, irregular portions of
the mucous membrane, of a dull ashen-grey colour, have undergone
sloughing; the edges of the sloughing portion are of colours varying
from brown to black.
It is seldom that so much change is seen in the gullet and pharynx
as this museum preparation exhibits; but redness, swelling, and the
general signs of inflammation are seldom absent from the stomach and
Some parts of the intestines. On the lining membrane of the mouth,
ulcers and pustules have been observed.
In Dr. Nevin's experiments on the chronic poisoning of rabbits
already referred to, the post-mortem appearances consisted in congestion
of the liver in all the rabbits; in nearly all there was vivid redness of
39
6 IO POISONs: THEIR EFFECTS AND DETECTION. [$ 760–762.
the stomach ; in two cases there was ulceration ; in some, cartilaginous
hardness of the pylorus, while in others the small intestines presented
patches of inflammation. In two of the rabbits the solitary glands
throughout the intestines were prominent, yellow in colour, and loaded
with antimony. The colon and rectum were healthy, the kidneys
congested ; the lungs were in most congested, in some actually inflamed,
or hepatised and gorged with blood. Bloody extravasations in the chest
and abdomen were frequent.
Salkowsky,” in feeding animals daily with antimony, found invariably
in the course of fourteen to nineteen days fatty degeneration of the
liver, and sometimes of the kidney and heart. In the experiment of
Caillol and Livon also all the organs were pale, the liver had undergone
fatty degeneration, and the lung had its alveoli filled with large
degenerated cells, consisting almost entirely of fat. The mesenteric
glands also formed large caseous masses, yellowish-white in colour,
which, under the microscope, were seen to be composed of fatty cells, so
that there is a complete analogy between the action of arsenic and
antimony on the body tissues.
§ 760. Elimination of Antimony.—Antimony is mainly eliminated
by the urine. In 1840, Orfila showed to the Académie de Médecine
metallic antimony, which he had extracted from a patient who had
taken 12 grn. of tartar emetic in twenty-four 'hours. He also obtained
antimony from an old woman, aged 80, who twelve hours before had
taken 6 grm. (9% grains)—a large dose, which had neither produced
vomiting nor purging. In Dr. Nevin's experiments on rabbits, antimony
was discovered in the urine after the twelfth dose, and even in the urine
of an animal twenty-one days after the administration of the poison had
been suspended. According to Pouchet's f experiments on dogs and
rabbits, antimony in chronic poisoning accumulates in the digestive
tract and is found in only small quantities in the organs of the body.
§ 761. Antidotes for Tartar Emetic.—Amy infusion containing
tannin or allied astringent principles, such as decoctions of tea, oak-bark,
etc., may be given with advantage in cases of recent poisoning by tartar
emetic, for any of the salt which has been expelled by vomiting may in
this way be decomposed and rendered harmless. The treatment of acute
poisoning which has proved most successful, has been the encouraging
of vomiting by tickling the fauces, giving strong green tea and stimu-
lants. (See Appendix.)
§ 762. Effects of Chloride or Butter of Antimony.—Only a few
cases of poisoning by butter of antimony are on record : its action,
* Virchow's Arch. f. path. Amat., Bd. xxv.; also, Centralblatt f. Med. Wissen.,
No. 23, 1865.
+ Compt. Rend., 1901.
§ 763.] ANTIMONY. 6 II
generally speaking, on the tissues is like that of an acid, but there has
been considerable variety in the symptoms. Five cases are recorded
by Taylor; three of the number recovered after taking respectively
doses of 7-7 grims. (2 drachms) and 15.5 grns. (4 drachms), and two
died after taking from 56-6 to 113 grns. (2 to 4 ounces). In one of
these cases the symptoms were more like those of a narcotic poison, in
the other fatal case there was abundant vomiting with purging. The
autopsy in the first case showed a black appearance from the mouth to
the jejunum, as if the parts had been charred, and extensive destruction
of the mucous membrane. In the other case there were similar changes
in the stomach and the upper part of the intestines, but neither the lips
nor the lower end of the gullet were eroded. In a case recorded by
Mr. Barrington Cooke,” a farmer's wife, aged 40, of unsound mind,
managed to elude the watchfulness of her friends, and swallowed an
unknown quantity of antimony chloride about 1.30 P.M. Shortly after-
wards she vomited several times, and had diarrhoea ; at 2.30 a medical
man found her lying on her back insensible, and very livid in the face
and neck. She was retching, and emitting from her mouth a frothy
mucous fluid, mixed with ejected matter of a grumous colour; the
breathing was laboured and spasmodic ; the pulse could not be felt, and
the body was cold and clammy. She expired at 3.30, about one hour
and a half from the commencement of symptoms, and probably within
two hours from the taking of the poison. The autopsy showed no corru-
gation of the tongue or inner surface of the liming membrane of the
mouth, and no appearance of the action of a corrosive upon the lips,
fauces, or mucous membrane of the oesophagus. The whole of the
mucous membrane of the stomach was intensely congested, of a dark and
almost black colour; the rest of the viscera were healthy. Chemical
analysis separated antimony equivalent to nearly a grm. (15 grains) of
the chloride, with a small quantity of arsenic, from the contents of the
stomach.
§ 763. Detection of Antimony in Organic Matters. In acute
poisoning by tartar emetic it is not impossible to find a mere trace only
in the stomach, the greater part having been expelled by vomiting,
which nearly always occurs early, so that the most certain method is,
where possible, to analyse the ejected matters. If it should be suspected
that a living person is being slowly poisoned by antimony, it must be
remembered that the poison is excreted by the kidneys, and the urine
should afford some indication. The readiest way to test is to collect a
considerable quantity of the urine (if necessary, two or three days'
excretion), and test. In any case, whether the analyst operates on an
organic solid or liquid, the organic matter is destroyed by one or other of
* Lancet, May 19, 1883.
6I 2 POISONS : THEIR EFFECTS AND DETECTION, [$ 763.
the processes detailed at pp. 52–55; the acid solution ultimately obtained
is then concentrated and saturated with sulphuretted hydrogen. It is
important that the liquid should only just be acid; for Lang and Carson
have shown that antimony sulphide is soluble in HCl of sp. gr. 1:16,
and that it is generally much more soluble than arsenic sulphide. Any
precipitate of whatever colour is filtered off, washed, and digested with
ammonium sulphide.
The sulphides soluble in ammonium sulphide * are as follows:–
Colour of Sulphide.
Arsenic . * t e º e * , yellow.
Antimony . º & tº ve * º . Orange.
Stannous salts . g º * e d ... brown.
Stannic Salts . º t * e g . dirty yellow.
Germanium º & * w * * . white.
Selenium . & & * e e e . Orange.
Tellurium . * * tº * t e ... black.
Gold . * tº g g ſº * * . brownish black.
Platinum . * te ſº wº g * . brownish black,
Iridium . sº gº g º e & brownish black.
In a toxicological research, only arsenic or antimony or tin are
likely to be present, although, if platinum utensils have been used, we
have known the sulphides to be darkened by a small proportion of
platinum sulphide.
The sulphide or sulphides may now be separated and identified in
various ways.
(a) Dry Method.—The sulphides are dried and intimately mixed
with dry potassium cyanide and sodic carbonate, and submitted to the
reducing flame of the blowpipe on charcoal; an onion-like odour
indicates arsenic, a white coating slowly volatilising—antimony, and
ultimately tin, if present, may be obtained as small globules.
The dry process is, however, more applicable for the quantities met
with in mineral analysis than for toxicological research.
(b) Wet Processes.—The sulphides are treated with concentrated
hydrochloric acid and heated to about 70°. Antimony and tin sulphides
pass into solution ; arsenic sulphide, if present, remains, and may be
dissolved by ammonia and ammonium carbonate.
The solution of possible antimony and tin sulphides is placed in
a platinum dish, and a small strip of zinc foil immersed therein.
Antimony immediately causes a dark stain ; on removing the zinc
thus stained, and well washing, the zinc is treated with hot nitric
* Ammonium sulphide slightly dissolves copper sulphide, and since the liver
always contains copper, it is useful in researches in that organ to rather use sodium
sulphide which will not dissolve copper sulphide. Gold, platinum, and iridium
sulphides are very insoluble by themselves, but when in presence of the arsenic group
of Sulphides are somewhat soluble.
§ 763.] ANTIMONY. 613
acid. The nitric acid solution will respond to the special tests for
antimony (e.g. it may be tested with the caesium compound salt).
The strip of zinc freed from the antimony deposit may be replaced
in the original liquid ; if tin is present, tin in a metallic form will be
deposited.
Hyposulphite Method of Separation.—This excellent method of
obtaining a separation of the three sulphides has been already described
(see page 56).
Tartaric Acid Method.—The sulphide or sulphides are treated
with 15 c.c. of nitric acid, and the mixture evaporated to dryness.
The residue is dissolved in 100 c.c. of warm water. The arsenic acid
dissolves, and may be precipitated by magnesia mixture; antimony
and tin, if present, remain as insoluble oxides on treatment with
tartaric acid solution for an hour—antimony oxide dissolves, tin oxide
is left. The tartrate of antimony solution may be now feebly saturated
with hydric sulphide, adding a little HCl ; the sulphide collected is
converted into oxide by nitric acid and weighed as tetroxide.*
It will, however, be advisable to reserve a small portion of the
tartaric acid solution for a confirmatory test, such as the formation
of antimony caesium iodide.
Sodium Peroxide Method.—The sulphides are diluted and heated
with a little water in a porcelain basin, and caustic soda, in not too
great excess, added until no more of the precipitate seems to dissolve.
Three or four drops of ammonium sulphide solution are then added, and
the liquid boiled until free from odour of ammonia. The solution is
now diluted with warm water and filtered.
The filtrate contains the arsenic group, and, possibly, mercury. After
further dilution the filtrate is boiled, and sodium peroxide gradually
added until there is a permanent effervescence of oxygen ; any mercury
will go down as sulphide and can be filtered off-the filtrate contains
only sodium arsenate, antimoniate, and stannate.
Should tin be present, this is separated by adding ammonium chloride
in the proportion of three times the bulk of the sodium peroxide, and
boiling; the tin separates as a white gelatinous precipitate.
The filtrate is now first acidified with hydrochloric acid and warmed
until oxygen ceases to be evolved. It is them cooled and treated with
a rapid current of SH2, Antimony, if present, is at once precipitated
as an orange or golden-yellow sulphide; this is filtered off and confirmed.
To the filtrate, which ought to smell feebly of SH, a few drops of
sodium thiosulphate is added and the solution warmed until a pre-
cipitate begins to separate. The solution is then treated with SH,
If the precipitate is white, it consists merely of sulphur; if bright yellow,
* Wm. R. Lang, C. M. Carson, and J. C. Mackintosh—Soc. Chem. Ind., 1902.
614 POISONS: THEIR EFFECTS AND DETECTION. [$ 763A, 764.
it contains arsenious sulphide, which must be confirmed in the usual
manner.”
Antimony compounds dissolved in HCl (1:4) or dilute H,SO, (1:10)
and treated with a solution of potassium iodide and caesium chloride
(1 of KI to 3 of CsCl in 10 c.c. water), give the insoluble antimony
casium iodide in yellow or garnet-red hexagonal lamellae. This will
detect a thousandth of a milligramme of antimony in presence of 500
times its weight of arsenic.f Marsh's test (already described) may, if
antimony be present, reveal its presence by the character of the stain ;
practical chemists would not, however, in a special search for antimony
use Marsh's test, but proceed in the manner already detailed. The
characters of stibine are as follows:–
§ 763A. Stibine (antimony hydride, antimoniuretted hydrogen),
SbHg.—Molecular weight, 125. The gas contains 97.6 per cent. Sb,
2.4 per cent. H. The gas, by cooling with liquid air, has recently been
obtained in a pure state. The solidified gas melts at – 88° to a colour-
less liquid; the boiling-point at normal pressure is - 17°. The liquid
has a sp. gr. of 2:26 at – 25°, and 2.34 at – 50°.
At ordinary temperatures 1 volume of water dissolves 15 volumes
of the gas; 1 volume of alcohol dissolves also the same volume ; at 0°
1 volume of carbon disulphide dissolves no less than 250 volumes of the
gaS.
The dry gas is fairly stable, but the moist gas is unstable. In
presence of air or oxygen at ordinary temperatures it decomposes into
antimony, water, and a little hydrogen.S The gas passed into a solu-
tion of mercury and potassium iodides HgI2 + KI (HgIn KI, with n > 2)
gives a brown-black precipitate of SbFIgaſs; arsine acts similarly, and
phosphine gives, under the same circumstances, a yellow crystalline
solid.] When the gas is passed over sulphur, stibine is decomposed
according to the equation 2SbHs + 6S = Sb2S3 + 3SH2, and the sulphur
assumes a deep orange tint. The reaction takes place very slowly in
ordinary daylight, rapidly in sunshine. Given bright sunshine, this
reaction may be utilised as a test. The antimony sulphide may be
freed from sulphur by digestion in CS3. The distinctions between the
stains deposited by heating arsine or stibine have been already described.
Stibine, like arsine, is intensely poisonous; mice die in a few seconds if
exposed to air containing 1 per cent. of stibine.
§ 764. Quantitative Estimation.—The quantitative estimation of
antimony is best made by some volumetric process—e.g. the sulphide can
* James Walker, Journ. C.S., Trans., 1903.
f Georges Deniges, Compt. Rend., 1901.
† Stock and Doht, Ber., 1902. § Stock and Guttman, Ber., 1904.
| Paul Lemoult, Compt. Remd., 1904.
§ 765–77O.] CADMIUM. 615
be dissolved in HCl, some tartrate of soda added, and then carbonate of
soda to weak alkaline reaction. The strength of the solution of tartarised
antimony thus obtained can now be estimated by a decinormal solution
of iodine, the end reaction being indicated by the previous addition of a
little starch solution, or by a solution of permanganate of potash, either
of which should be standardised by the aid of a solution of tartar emetic
of known strength.
3. CADMIUM.
§ 765. Cadmium, Cd=112 ; specific gravity, 8:6 to 8-69 ; fusing-point, 227-8°
(442°F.); boiling-point, 860° (1580° F.).-Cadmium in analysis is seldom separated
as a metal, but is estimated either as oxide or sulphide.
§ 766. Cadmium Oxide, CdC) = 128–cadmium, 87°5 per cent. ; oxygen, 12.5 per
cent.—is a yellowish or reddish-brown powder, non-volatile even at a white heat;
insoluble in water, but dissolving in acids. Ignited on charcoal, it is reduced to
metal, which volatilises, and is then deposited again as oxide, giving to the charcoal
a distinct coat of an orange-yellow colour in very thin layers ; in thicker layers,
brown.
§ 767. Cadmium Sulphide, CdS=144–Cd, 77.7 per cent. ; S, 22.3 per cent.—
known as a mineral termed Greenockite. When prepared in the wet way, it is a
lemon-yellow powder, which cannot be ignited in hydrogen without loss, and is
insoluble in water, dilute acids, alkalies, alkaline sulphides, sulphate of soda, and
cyanide of potassium. The solution must not contain too much hydrochloric acid,
for the sulphide is readily soluble with separation of sulphur in concentrated hydro-
chloric acid. It may be dried in the ordinary way at 100° without suffering any
decomposition.
§ 768. Medicinal Preparations.—The Iodide of Cadmium (CdI2) occurs in white,
flat, micaceous crystals, melting at about 215'5° (419.9°F.), and at a dull red heat
giving off violet vapour. In solution, the salt gives the reactions of iodine and
cadmium. The ointment of iodide of cadmium (Ungwentwm cadmii iodidi) contains
the iodide in the proportion of 62 grains to the ounce, or 14 per cent.
Cadmium Sulphate is officinal in the Belgian, Portuguese, and French pharma-
copoeias.
§ 769. Cadmium in the Arts, etc.—Cadmium is used in various alloys. The
sulphide is found as a colouring ingredient in certain toilet soaps, and it is much
valued by artists as a pigment. The iodide of cadmium is employed in photography,
and an amalgam of metallic cadmium to some extent in dentistry.
§ 770. Fatal Dose of Cadmium.—Although no deaths from the use of cadmium
appear to have as yet occurred, its use in photography, etc., may lead to accidents.
There can be no question about the poisonous action of cadmium, for Marmé,” in
his experiments on it with animals, observed giddiness, vomiting, syncope, difficulty
in respiration, loss of consciousness, and cramps. The amount necessary to destroy
life can only be gathered from the experiments on animals. A strong hound died
after the injection of '03 grm. (.462 grain) subcutaneously of a salt of cadmium ;
rabbits are poisoned if from 19:4 to 38.8 mgrims. (.3 to “6 grain) are introduced into
the stomach. A watery solution of 5 grm. (7.5 grains) of the bromide administered
to a pigeon caused instant death, without convulsion ; the same dose of the chloride
killed a second pigeon in six minutes; 25 grm. (3-85 grains) of sulphide of cadmium
administered to a pigeon excited vomiting, and, after two hours, diarrhoea—it died
in eight days. Another pigeon died from a similar dose in fourteen days, and
* Zeitschr. f. rationelle Med., vol. xxix. p. 1, 1867.
616 POISONS: THEIR EFFECTS AND DETECTION. [$ 771, 772.
cadmium, on analysis, was separated from the liver. From the above cases it would
seem probable that 4 grns. (61.7 grains) would be a dangerous dose of a soluble salt
of cadmium for an adult, and that in a case of chronic poisoning it would most
probably be found in the liver.
§ 771. Separation and Detection of Cadmium.—If cadmium be in solution, and
the solution is not too acid, on the addition of SH2 there is precipitated a yellow
sulphide, which is distinguished from antimony and arsenical sulphides by its in-
solubility in ammonia and alkaline sulphides. Should all three sulphides be on the
filter (an occurrence which will seldom, perhaps never, happen), the sulphide of arsenic
can be dissolved out by ammonia, the antimony by sulphide of sodium, leaving the
sulphide of cadmium as the residue.”
The further tests of the sulphide are:–
(1) It dissolves in dilute nitric acid to a colourless fluid, with separation of
sulphur.
(2) The solution, filtered and freed from excess of nitric acid by evaporation, gives
with a solution of ammonic carbonate a white precipitate of carbonate of cadmium
insoluble in excess. This distinguishes it from zinc, which gives a similar white
precipitate, but is soluble in the excess of the precipitant.
(3) The carbonate thus obtained, heated on platinum foil, is changed into the
brown-red non-volatile oxide.
(4) The oxide behaves on charcoal as already detailed.
(5) A metallic portion can be obtained by melting the oxide with cyanide of
potassium ; it is between zinc and tin in brilliancy, and makes a mark on paper like
lead, but not so readily. There are many other tests, but the above are conclusive.
If cadmium in any case be specially searched for in the organs or tissues, the latter
should be boiled with nitric acid. The acid solution is filtered, saturated with
caustic potash, evaporated to dryness, and ignited ; the residue is dissolved in dilute
hydrochloric acid, and treated after filtration with SH2. Cadmium may also be
estimated volumetrically by digesting the sulphide in a stoppered flask with ferric
chloride and hydrochloric acid ; the resulting ferrous compound is titrated with
permanganate, each c.c. of a d.m. solution of permanganate='0056 grm. of cadmium.
II.-PRECIPITATE BY HYDRIC SULPHIDE IN HYDRO-
CHLORIC ACID SOLUTION.—BLACK.
Lead—Copper—Bismuth—Silver—Mercury.
1. LEAD.
§ 772. Lead, Pb = 207.-Lead is a well-known bluish-white, soft
metal—fusing-point, 325°; specific gravity, 11:36.
Oxides of Lead.—The two oxides of lead necessary to notice here
briefly are—litharge and minium.
Litharge or Oxide of Lead, PbO = 223—specific gravity, 9.2 to 9:5;
Pb 92.82 per cent., O 7:18—is either in crystalline scales, a fused mass,
or a powder, varying in colour (according to its mode of preparation)
from yellow to reddish-yellow or orange. When prepared below the
* It is unnecessary to state that absence of sulphur is presupposed.
§ 773–776.] LEAD. 617
temperature of fusion it is called “massicot.” It may be fused without
alteration in weight; in a state of fusion it dissolves silicic acid and
silicates of the earths. It must not be fused in platinum vessels.
Minium, or Red Lead, 2PbO, PbO2–specific gravity, 9:08—is a
compound of protoxide of lead with the dioxide. It is of a brilliant red
colour, much used in the arts, and especially in the preparation of
flint-glass.
§ 773. Sulphide of Lead, PbS = 239–Pb, 86-61 per cent. ; S, 13:39
per cent.—occurring in the usual way, is a black precipitate insoluble
in water, dilute acids, alkalies, potassium cyanide, and alkaline sul-
phides. It dissolves in strong nitric acid with separation of sulphur,
and in strong hydrochloric acid with evolution of SH3. Fuming nitric
acid does not separate sulphur, but converts the sulphide into
sulphate.
§ 774. Sulphate of Lead, PbSO, - 303—specific gravity, 6'3; PbO,
73-61 per cent. ; SOs, 26-39 per cent.—when produced artificially, is a
heavy white powder, of slight solubility in water, 22,800 parts of cold
water dissolving only one of lead sulphate ; and if the water contains
sulphuric acid, no less than 36,500 parts of water are required. Alkaline
acetates, the acetate, tartrate, and citrate of ammonia dissolve the sul-
phate without change; sodic hyposulphite dissolves lead sulphate,
changing it partly into sulphite. The sulphate can be readily changed
into the carbonate of lead by boiling it with solutions of the alkaline
carbonates. The sulphate of lead, fused with cyanide of potassium,
yields metallic lead; it may be also reduced on charcoal, and alone
it may be fused without decomposition, provided reducing gases are
excluded.
§ 775. Acetate of Lead, Sugar of Lead, Pb(C,E,O.),3OH, - 379,
is found in commerce in white, spongy masses composed of acicular
crystals. It may, however, be obtained in flat, four-sided prisms.
It has a sweet metallic taste, is soluble in water, and responds to the
usual tests for lead. The P.B. directs that 38 grains dissolved in
water require, for complete precipitation, 200 grain measures of the
volumetric solution of Oxalic acid, corresponding to 22.3 grains of
oxide of lead. -
§ 776. Chloride of Lead, PbCl, = 278—specific gravity, 5-8 ; Pb,
74°48 per cent. ; Cl, 25-52 per cent.—is in the form of brilliant crystalline
needles. It is very insoluble in cold water containing hydrochloric or
nitric acids. According to Bischof, 1635 parts of water containing nitric
acid dissolve one part only of chloride of lead. It is insoluble in absolute
alcohol, and sparingly in alcohol of 70 to 80 per cent. It fuses below
red heat without losing weight ; at higher temperatures it may be
decomposed.
618 POISONS: THEIR EFFECTS AND DETECTION. [$ 777
Carbonate of Lead.—The commercial carbonate of lead (according
to the exhaustive researches of Wigner and Harland *) is composed of a
mixture of neutral carbonate of lead and hydrate of lead, the best
mixture being 25 per cent. of hydrate, corresponding to an actual
percentage of 12.3 per cent. carbonic acid. The nearer the mixture
approximates to this composition the better the paint ; whilst samples
containing as much as 16:33 per cent., or as little as 10-39 per cent., of
CO2 are practically useless.
§ 777. Preparations of Lead used in Medicine, the Arts, etc.
(1) Pharmaceutical:—
Lead Plaster (Emplastrum plumbi) is simply a lead soap, in which
the lead is combined with oleic and margaric acids, and contains some
mechanically included glycerin.
Lead Iodide, PbTe, is contained in the Emplastrum plumbi iodidi
to the extent of 10 per cent., and in the Unguentum plumbi iodidi to
the extent of about 12-5 per cent.
Acetate of Lead is contained in a pill, a suppository, and an oint-
ment. The pill (Pilula plumbi cum opio) contains 75 per cent. of lead
acetate, and 12.5 per cent. of opium, the rest confection of roses. The
suppository (Suppositoria plumbi composita) contains 20 per cent. of
acetate of lead, and 6.6 per cent. of opium, mixed with oil of theobroma.
The ointment (Unguentum plumbi acetatis) contains 20.6 per cent. of
lead acetate, mixed with benzoated lard.
The solution of subacetate of lead (Liquor plumbi subacetatis) is the
subacetate, Pb(C.HsO3)2PbO, dissolved in water; it contains nearly 27
per cent. of subacetate.
A dilute solution of the stronger, under the name of Liquor
plumbi subacetatis dilutus, and commonly called Goulard water, is
prepared by mixing 1 part (by volume) of the solution and 1 part of
spirit, and 78 parts of distilled water; the strength is equal to 1:25
per cent.
There is an ointment, called the Compound Ointment of subacetate of
lead, which contains the subacetate in about the proportion of 2 per
cent. of the oxide, the other constituents being camphor, white wax, and
almond oil.
Carbonate of Lead.—The ointment (Unguentum plumbi carbonatis)
should contain about 12°5 per cent. of the carbonate, and the rest simple
ointment.
(2) Quack Nostrums, etc. :—
The quack medicines composed of lead are not very numerous.
Liebert's Cosmetique Infaillible is said to have for its basis nitrate of lead.
* “On the Composition of Commercial Samples of White Lead,” by G. W.
Wigner and R. H. Harland.—Analyst, 1877, p. 208.
§ 777.] LEAD. 619
One of “Ali Ahmed’s Treasures of the Desert,” viz., the antiseptic malagma,
is a plaster made up of lead plaster 37.5 per cent, frankincense 25 per cent., Salad
oil 25 per cent., beeswax 12'5 per cent.
Lewis' Silver Cream contains white precipitate and a salt of lead.
Goulard's Balsam is made by triturating acetate of lead with hot oil of
turpentine.
There are various ointments in use made up of litharge. Some herbalists in the
country (from cases that have come under the writers’ own knowledge) apply to
cancerous ulcers, etc., a liniment of linseed and other common oils mixed with
litharge and acetate of lead.
Acetate of lead may also be found as a constituent of various eye-waters.
(3) Preparations of Lead used in the Arts, etc. :—
Ledoyen's Disinfecting Fluid has for its basis nitrate of lead.
In various hair-dyes the following are all used:—Litharge, lime, and starch ;
lime and carbonate of lead ; lime and acetate of lead ; litharge, lime, and
potassic bicarbonate. The detection of lead in the hair thus treated is ex-
tremely easy; it may be dissolved out by dilute nitric acid.
Lead Pigments.—The principal pigments of lead are white, yellow, and red.
White Pigments:—
White Lead, Flake White Ceruse, Mineral White, are so many different names
for the carbonate of lead already described.
Newcastle White is white lead made with molasses vinegar.
Nottingham White.--White lead made with alegar (sour ale), often, however,
replaced by permanent white, i.e. sulphate of baryta.
Miniature Painters' White, White Precipitate of Lead, is simply lead
sulphate.
Pattison's White is an oxychloride of lead, PbCl,PbO.
Yellow Pigments:—
Chrome Yellow may be a fairly pure chromate of lead, or it may be mixed with
sulphates of lead, barium, and calcium. The pigment known as “Cologne yellow ’’
consists of 25 parts of lead chromate, 15 of lead sulphate, and 60 of calcic sulphate.
The easiest method of analysing chrome yellow is to extract with boiling hydro-
chloric acid in the presence of alcohol, which dissolves the chromium as chloride,
and leaves undissolved chloride of lead, sulphate of lead, and other substances in-
soluble in ClFI. Every grain of chromate of lead should yield 0:24 grain of oxide of
chromium, and 0'4 grain of chloride of lead.
Turner's Yellow, Cassella Yellow, Patent Yellow, is an oxychloride of lead
(PbCl27PbO) extremely fusible.
Dutch Pink sometimes contains white lead.
Red Pigments:—
Chrome Red is a bichromate of lead.
Red Lead or Minium is the red oxide of lead.
Orange Red is an oxide prepared by calcining the carbonate.
The chief preparations of lead which may be met with in the arts, in addition to
the oxides and the carbonate, are—
The Nitrate of Lead, much used in calico-printing.
The Pyrolignite of Lead, which is an impure acetate used in dyeing; and
The Sulphate of Lead is a by-product in the preparation of acetate of aluminium
for dyeing.
The alloys containing lead are extremely numerous; but, according to the ex-
periments of Knapp,” the small quantity of lead in those used for household purposes
has no hygienic importance.
* Dingl. Polytech. Journ., vol. ccxx. pp. 446–453.
62O Poisons: THEIR EFFECTS AND DETECTION, [$ 778, 779.
§ 778. Statistics of Lead-Poisoning.—During the ten years ending
December 1903, 926 persons died from the effects of lead; 754 males
and 165 females were registered as having died from accidental lead-
poisoning—6 males and 1 female used lead salts as a means of suicide
—but no case of murder was recorded.
§ 779. Lead as a Poison.—All the compounds of lead are said to be
poisonous; but this statement cannot be regarded as entirely correct,
for the sulphocyanide has been proved by experiment not to be so,”
and the sulphide is also probably inactive. In the treatment of cases
of lead-poisoning, the flowers of sulphur given internally appear to be
successful.i.
Lead-poisoning, either in its obscure form (producing uric acid in
the blood, and, as a consequence, indigestion and other evils), or in the
acute form (as lead colic and various nervous affections), is most frequent
among those who are habitually exposed to the influence of the metal in
its different preparations, viz., workers of lead, house-painters, artists,
gilders, workers of arsenic, workers of gold, calico-printers, colourists,
type - founders, type-setters, shot-founders, potters, faience makers,
braziers, and many others. In white-lead factories so large a number
of the employees suffer from poisoning that it has excited more than
once the attention of the Government. §
* Eulenberg, Gewerbe Hygiene, p. 712. + Mohr’s Toa'icologie, p. 78.
"f The attention which the use of lead in the arts has always excited is evident
from the fact that one of the oldest works on Trade Hygiene (by Stockhausen) is
entitled, De lithargyri fumo moa;io morbifico ejusque metallico frequentiori morbo
vulgo dicto hittenkatze, Gaslar, 1556.
Ś A departmental committee, appointed to inquire into the white lead and
allied industries, in a report presented to the Home Secretary stated:—
“8. (a) It is known that if lead (in any form), even in what may be called
infinitesimal quantities, gains entrance into the system for a lengthened period, by
such channels as the stomach, by swallowing lead dust in the saliva, or through the
medium of food and drink; by the respiratory organs, as by the inhalation of dust ;
or through the skin ; there is developed a series of symptoms, the most frequent of
which is colic. Nearly all the individuals engaged in factories where lead or its
compounds are manipulated look pale, and it is this bloodlessness and the presence
of a blue line along the margin of the gums, close to the teeth, that herald the other
symptoms of plumbism. (b) A form of paralysis known as wrist-drop or lead-palsy
occasionally affects the hands of the operatives. There is, in addition, a form of
acute lead-poisoning, most frequently met with in young girls from 18 to 24 years of
age, which is suddenly developed and is extremely fatal. In it the first complaint is
headache, followed sooner or later by convulsions and unconsciousness. Death often
terminates such a case within three days. In some cases of recovery from convulsions
total blindness remains.
‘‘9. There has been considerable doubt as to the channels by which the poison
enters the system. The committee have taken much evidence on this subject, and
have arrived at the conclusion (a) that carbonate of lead may be absorbed through the
pores of the skin, and that the chance of this is much increased during perspiration
and where there is any friction between the skin and the clothing ; (b) that minute
§ 779.] LEAD. 62 I
Lead, again, has been found by the analyst in most of the ordinary
foods, such as flour, bread, beer, cider, wines, spirits, tea, vinegar, sugar,
confectionery, etc., as well as in numerous drugs, especially those manu-
factured by the aid of sulphuric acid (the latter nearly always containing
lead), and those salts or chemical products which (like citric and tartaric
acids) are crystallised in leaden pans. Hence it follows that in almost
everything eaten or drunk the analyst, as a matter of routine, tests for
lead. The channels through which it may enter into the system are,
however, so perfectly familiar to practical chemists, that a few unusual
instances of lead-poisoning only need be quoted here.
A cabman suffered from lead colic, traced to his taking the first glass
of beer every morning at a certain public-house; the beer standing in the
pipes all night, as proved by analysis, was strongly impregnated with
lead.*
The employment of red lead for repairing the joints of steam-pipes
has before now caused poisonous symptoms from volatilisation of lead.i
The use of old painted wood in a baker's oven, and subsequent adherence
of the oxide of lead to the outside of the loaves, has caused the illness
of sixty-six people. }
Seven persons became affected with lead-poisoning through horse-hair
coloured with lead.S
The manufacture of American overland cloth creates a white-lead dust,
which has caused serious symptoms among the workmen (Dr. G. Johnson).
The cleaning of pewter pots, the handling of vulcanised rubber," the
wrapping up of various foods in tinfoil,” and the fingering of lead
counters covered with brine by fishmongers, have all caused accidents in
Iſle Il.
The lead in glass, though in the form of an insoluble silicate, is said
to have been dissolved by vinegar and other acid fluids to a dangerous
extent. This, however, is hardly well established.ti
The various glazes used in the pottery manufacture are largely com-
posed of lead compounds—litharge, white and red leads being used ;
some of the glazes are fused with siliceous materials (fritted), but few
portions of lead are carried by the hands, under and round the nails, etc., on to the
food, and so into the stomach ; (c) but that the most usual manner is by the inhala-
tion of lead dust. Some of this becomes dissolved in the alkaline secretions of the
mouth, and is swallowed by the saliva, thus finding its way to the stomach. Other
particles of dust are carried to the lungs, where they are rendered soluble and absorbed
by the blood.”—Report of Chief Inspector of Factories for 1893.
* Chem. News. f Eulenberg, op. cit., p. 708.
† Annales d'Hygiène, 1877, 307. § Hitzig, Studien über Bleivergiftung.
| Med. Gazette, xlviij. 1047. * Pharm. Journ., 1870, p. 426.
** Taylor, Prin. Med. Jurisprud., i.
ff See Aerztl. Intelligenzbl. f. Baiern, Jahrg., 1869; Buchner's Rep. Pharm.,
Bd. xix. p. 1; Med, Centrbl., Jahrg., 1869, p. 40.
622 POISONS: THEIR EFFECTS AND DETECTION. [$ 780.
of these silicates are absolutely insoluble in acids; hence acid vegetable
juices, especially if heated, are liable to dissolve out the lead from a
lead-glazed earthenware vessel. Dr. Campbell (Lancet, 1886) has re-
corded a series of cases of poisoning from home-made wine fermented in
lead-glazed earthenware pans. Thorpe * has investigated the composi-
tion of most of the lead silicates used as glazes, and has shown that the
primary factor governing solubility or otherwise in complex lead silicate
is the relation between the basic oxides and the acidic oxides. The
percentage weight of each oxide is divided by its molecular weight; the
quotient represents the relative number of that oxide present in a
definite weight of the silicate—adding all the quotients for the acidic
oxides gives the total number of acidic molecules, and similarly for
No. of acidic molecules
No. of basic molecules'
ratio is higher than or approximately equal to 2, the solubility of the
lead Thorpe found to be small, being for the most part below 2 per
cent. ; but when the ratio falls below 2, the quantity of lead dissolved
(in hydrochloric acid) begins rapidly to increase.
§ 780. Effects of Lead Compounds on Animals.—Orfila and the
older school of toxicologists made a number of experiments on the action
of sugar of lead and other compounds, but they are of little value for
elucidating the physiological or toxic action of lead, because they were, for
the most part, made under unnatural conditions, the gullet being ligatured
to avoid expulsion of the salt by vomiting. Harmack, in order to avoid
the local and corrosive effects of sugar of lead, used an organic compound,
viz., plumbic triethyl acetate, which has no local action. Frogs exhibited
symptoms after subcutaneous doses of from 2 to 3 mgrms., rabbits after
40 mgrms. ; there was increased peristaltic action of the intestines, with
spasmodic contraction rising to colic, very often diarrhoea, and death
followed through heart paralysis. Dogs given the ethyl compound
exhibited nervous symptoms like chorea. Gussermot has also made
experiments on animals as to the effects of lead, using lead phosphate,
and giving from 1-2 grm. to a rabbit and a dog daily. Rosenstein i and
Heubel $ used small doses of acetate, the latter giving dogs daily from 2
to 5 grm. The results arrived at by Gussermo were, mainly, that the
animals became emaciated, shivered, and had some paralysis of the hinder
extremities; while Rosenstein observed towards the end epileptiform con-
vulsions, and Heubel alone saw, in a few of his cases, colic. A consider-
able number of cattle have been poisoned from time to time with lead, and
So long as this
the basic molecules the ratio =
* Jowrm. Chem. Soc., Trams., 1901.
+ Virchow's Archiv f. path. Anat., vol. xxi. p. 443.
# Ibid., vol. xxxix. pp. 1 and 74.
§ Pathogenese w. Symptome der chromischen Bleivergiftwmg, Berlin, 1871.
§ 781.] LEAD. 623
one instance of this fell under the senior author's observation. A pasture
had been manured with refuse from a plumber's yard, and pieces of paint
were in this way strewn about the field in every direction; a herd of
fifteen young cattle were placed in the field, and in two or three days
they all, without exception, began rapidly to lose condition, and to show
peculiar symptoms—diarrhoea, loss of appetite; in two, blindness, the
retina presenting an appearance not unlike that seen in Bright's disease;
in three, a sort of delirium. Four died, and showed on post-mortem
examination granular conditions of the kidneys, which was the most
striking change observable. In the fatal cases, paralysis of the hind
extremities, coma, and convulsions preceded death. In another case *
seven cows and a bull died from eating lead paint; the symptoms were
loss of appetite, obstinate constipation, suspension of rumination, dry
muffle, quick breathing, and coma. In other cases a marked symptom
has been paralysis. Cattle i have also several times been poisoned from
eating grass which has been splashed by the spray from bullets, as in
pastures in the vicinity of rifle butts; here we must allow that the
intestinal juices have dissolved the metal, and transformed it into
compounds capable of being taken into the system.
§ 781. Effects of Lead Compounds on Man—Acute Poisoning.—
Acute poisoning by preparations of lead is not common, and, when it
does occur, is seldom fatal. With regard to the common acetate, it
would seem that a large single dose is less likely to destroy life than
smaller quantities given in divided doses for a considerable period. The
symptoms produced by a considerable dose of sugar of lead usually
commence within a few minutes; there is immediately a metallic
taste, with burning, and a sensation of great dryness in the mouth
and throat; vomiting, which occurs usually within fifteen minutes, is
in very rare cases delayed from one to two hours. The retching and
vomiting are very obstinate, and continue for a long time ; the matters
thrown up are sometimes streaked with blood; there is pain in the
abdomen of a colicky character—a pain relieved by pressure. The
bowels are, as a rule, constipated, but occasionally relaxed. The stools
at a later date are black from the presence of lead sulphide. The
urine, as a rule, is diminished. The breath has a foul odour, and the
tongue is coated; the skin is dry, and the pulse small and frequent.
The full development of the toxic action is completed by the appearance
of various nervous phenomena—headache, shooting pains in the limbs,
cramps in the legs, and local numbness. All the symptoms enumerated
are not present in each case; the most constant are the vomiting and
the colic. If the sufferer is to die, death occurs about the second or
* See a paper by Professor Tuson, Veterinarian, vol. xxxviii., 1861.
t Ibid.; also Taylor, op. cit.
624 POISONS : THEIR EFFECTS AND DETECTION. [$ 781.
third day. If the patient recovers, convalescence may be much
retarded, as shown in the case of two girls,” who had each swallowed
an ounce of lead acetate by mistake, and who suffered even after the
lapse of a year from pain and tenderness in the stomach and sickness.
There are “mass-poisonings” by acetate of lead on record, which
afford considerable insight into the varying action of this salt on
different individuals. A case (e.g.) occurred at Stourbridge in 1840, f
in which no less than 500 people were poisoned by thirty pounds of
lead acetate being accidentally mixed with eighty sacks of flour at a
miller's. The symptoms commenced after a few days—constriction of
the throat, cramping and twisting pains round the umbilicus, rigidity
of the abdominal muscles, dragging pains at the loins, cramps and
paralysis of the lower extremities. There was obstinate constipation;
the urine was scanty and of a deep red colour, and the secretions
were generally arrested; the pulse was slow and feeble; the countenance
depressed, often livid; and the gums showed the usual blue line. The
temperature of the skin was low. In only a few cases was there
sickness, and in these it soon ceased. It is curious that not one of
the 500 cases proved fatal, although some of the victims were extremely
ill, and their condition alarming. It was specially observed that, after
apparent convalescence, the symptoms, without any obvious cause,
suddenly returned, and this even in a more aggravated form. Remit-
tance of this kind is of medico-legal import ; it might, for example be
wrongly inferred that a fresh dose had been taken. In the 500 cases
there were no inflammatory symptoms; complete recovery took some
time. On examining the bread the poison was found so unequally
distributed that no idea could be formed as to the actual amount taken,
There is also recorded f an outbreak of lead-poisoning among 150
men of the 7th Infantry at Tione, in the Southern Tyrol. One case
proved fatal, forty-five required treatment in hospital. The symptoms
were pallor, a blue line in the gums, metallic taste in the mouth, a
peculiar odour of the breath, a loaded tongue with a bluish tint,
obstinate constipation with loss of appetite ; whilst all complained, in
addition, of dragging of the limbs and of the muscles of the chest, and
difficulty of breathing. In the severer cases there were tetanic spasms,
muscular tremors, and anaesthesia of the fingers and toes. The pulse
and temperature were normal, save in a few cases in which there were
fever and sweats at night. In none was there colic, but the constipation
was obstinate. In two of the worst cases there was strangury. Acute
cases occur occasionally from poisoning by the carbonate of lead. Dr.
* Prov. Med. Jowrmal, 1846.
+ Recorded by Mr. Bancks, Lancet, May 5, 1849, p. 478.
f Königschmied, Centralbl. Allg. für Gesundheitspflege, 2 Jahrg., Heft 1.
§ 782.] LEAD. 625
Snow recorded an instance (in 1844) of a child who had eaten a piece
as big as a marble, ground up with oil. For three days the child
suffered from pain in the abdomen and vomiting, and died ninety hours
after taking the poison. In another case, in which a young man took
from 19 to 20 grims. of lead carbonate in mistake for chalk as a remedy
for heartburn, the symptoms of vomiting, pain in the stomach, etc.,
commenced after a few hours; but, under treatment with magnesic
sulphate, he recovered.
The Chromate of Lead is still more poisonous (see art. “Chromium”).
§ 782. Chronic Poisoning by Lead.—Chronic poisoning by lead—
often caused by strange and unsuspected channels, more frequently an
incident, nay, almost a necessity, of certain trades, and occasionally
induced by a cunning criminal for the purpose of simulating natural
disease—is of great toxicological and hygienic importance. In the
white-lead trade it is, as might be expected, most frequently witnessed;
but also in all occupations which involve the daily use of lead in
almost any shape. The chief signs of chronic poisoning are those of
general ill-health ; the digestion is disturbed, the appetite lessened, the
bowels obstimately confined, the skin assumes a peculiar yellowish hue,
and sometimes the sufferer is jaundiced. The gums show a black streak
from two to three lines in breadth, which microscopical examination
and chemical tests alike show to be composed of sulphide of lead ;
occasionally the teeth turn black.” The pulse is slow, and all secretions
are diminished. Pregnant women have a tendency to abort. There
are also special symptoms, one of the most prominent of which is
often lead colic.
In 142 cases of lead-poisoning, treated between 1852 and 1862 at
the Jacob's Hospital, Leipzig, forty-four patients (or about 31 per cent.)
suffered from colic. Arthralgia—that is, pains in the joints—is also
very common; it seldom occurs alone, but in combination with other
symptoms. Thus, in seventy-five cases of lead-arthralgia treated at
Jacob's Hospital, in only seven were pain in the joints without other
complications, fifty-six being accompanied by colic, five by paralysis,
and seven by other affections of the nervous system. The total
percentage of cases of lead-poisoning, in which arthralgia occurs, varies
from 32 to 57 per cent.
Paralysis, in some form or other, Tanqueril f found in 5 to 8 per cent.
of the cases, and noticed that it occurred as early as the third day after
* The black line soon develops; Masazza has seen it in a dog, exposed to the
influence of lead, in so short a period as three days (Riforma med., 1889, Nos. 248–
257, 1).
t Tanqueril des Planches, Traité des Maladies de Plomb, Paris, 1839.
Tanqueril's monograph is a classical work full of information.
4Q
626 POISONS: THEIR EFFECTS AND DETECTION. [$ 783.
working in lead. The muscles affected are usually those of the upper
extremity, then the legs, and still more rarely the muscles of the trunk.
It is only exceptionally that the paralysis extends over an entire limb ;
it more usually affects a muscular group, or even a single muscle. Its
common seat is the extensors of the hand and fingers; hence the expres-
sion “dropped-wrist,” for the hands droop, and occasionally the triceps
and the deltoid are affected. The paralysis is usually symmetrical on
both sides. Although the extensors are affected most, the flexors nearly
always participate, and a careful investigation will show that they are
weakened. If the paralysis continues, there is a wasting and degenera-
tion of the muscle; but this is seen in paralysis from any cause. The
muscular affection may cause deformities in the hands, shoulders, etc.
Anaesthesia of portions of the skin is generally present in a greater or
less degree. A complete analgesia affecting the whole body has been
noticed to such an extent that there was absolute insensibility to burns
or punctures; but it is usually confined to the right half of the body,
and is especially intense in the right hand and wrist.
§ 783. The older writers recognised the toxic effect of lead on the
nervous system. Thus Dioscorides speaks of delirium produced by lead,
Aretaeus of epilepsy, and Paul of AEgina refers to it as a factor of
epilepsy and convulsions. But in 1830, Tanqueril first definitely de-
scribed the production of a mental disease, which he called “lead
encephalopathy.” This he divided into four forms — (1) a delirious
form ; (2) a comatose ; (3) a convulsive; and (4) a combined form, com-
prising the delirious, convulsive, and comatose. Dr. Henry Rayner,”
and a few other English alienists, have directed their attention to this
question ; and, according to Dr. Rayner's researches, the number of male
patients admitted into Hanwell Asylum, engaged in trades such as
plumbing, painting, and the like, is larger in proportion to the number
admitted from other trades than it should be, compared with the propor-
tion of the various trades in the county of Middlesex, as ascertained
from the census. Putting aside coarse lead-poisoning which may occa-
sionally produce acute mania, the insanity produced by prolonged minute
lead intoxications possesses some peculiar features. It develops slowly,
and in nearly all cases there are illusions of the senses, of hearing, taste,
or smell, and especially of sight. Thus, in one of Dr. Rayner's cases
the patient saw round him “wind-bags blown out to look like men,”
apparitions which made remarks to him and generally worried him.
Besides this form, there is also another which closely resembles general
paralysis, and, in the absence of the history, might be mistaken for it.
* See an important paper, “Insanity from Lead-Poisoning,” by Drs. H. Rayner,
Robertson, Savage, and Atkins, Journ. of Mental Science, vol. xxvi. p. 222; also a
paper by Dr. Barton, Allgemeine Zeitschrift für Psychiatrie, Bd. xxxvij. H. 4, p. 9.
§ 784.] LEAD. 627
§ 784. The degenerative influence on the organ of sight is shown in
six of Dr. Robertson's patients, whose insanity was ascribed to lead—
four of the six were either totally or partially blind.
The amaurosis has been known to come on suddenly, and after a
very brief exposure to lead—e.g. a man, thirty-four years of age, after
working for three days in a white-lead factory, was seized with intense
ciliary neuralgia, had pains in his limbs and symptoms of lead-poisoning,
and the right eye became amaurotic.” This form of impairment or loss
of vision is different from the Retinitis albuminurica, f which may also be
produced as a secondary effect of the poison; the kidneys in such cases
being profoundly affected. The kind of diseased kidney produced by
lead is the granular contracted kidney.
Eulenberg speaks of the sexual functions being weakened, leading
to more or less impotence.
Lewy, f in 1186 patients suffering from lead-poisoning, has found
caries or necrosis in twenty-two cases, or about 1.8 per cent. ; fifteen
were carious affections of the upper jaw, four of the fore-arm, two of the
thigh, and one of the rib and sternum. Epilepsy and epileptiform con-
vulsions occur in a few cases; it is very possible that the epilepsy may
be a result of the uraemic poisoning induced by diseased kidneys.
Five cases of fatal poisoning occurred between 1884–6 among the
employees of a certain white-lead factory in the east of London. The
cases presented the following common characters. They were all adult
women, aged from 18 to 33, and they had worked at the factory for
short periods, from three to twelve months. They all exhibited mild
symptoms of plumbism, such as a blue line round the gums, and more or
less ill-defined indisposition; paralyses were absent. They were all in
their usual state of health within a few hours or days preceding death.
Death was unexpected, mostly sudden. In four cases it was preceded
by epileptic fits and coma; but in the fifth case no convulsions were
noted, although they may have occurred in the night.
The senior author § had an opportunity of investigating by chemical
means the distribution of lead in the fourth and fifth cases in the liver,
kidney, and brain.
In the fourth case, from 402 grms. of liver 24-26 mgrms. of lead
sulphate were separated. The right kidney (weighing 81 grims.) yielded
5:42 mgrms. of lead sulphate. The brain was dehydrated with alcohol,
* Samelsohn, Momatsbl. f. Awdenheilk, vol. xi. p. 246, 1873. See also a case of
lead amaurosis, described by Mr. W. Holder, Pharm. Journ., Oct. 14, 1876.
t Ran, Arch. f. Ophthal., vol. i. (2), p. 205, 1858, and Schmidt's Jahrbuch,
Bd. cxxxiii. p. 116; Bd. cxliii. p. 67.
it Die Berufskrank d. Bleiarbeiter, Wien, 1873, S. 16.
§ “The Distribution of Lead in the Brains of two Lead Factory Operatives,”
Jowrm. of Mental Science, Jan. 1888.
628 POISONS : THEIR EFFECTS AND DETECTION. [$ 785.
and then treated with ether, hot alcohol, and chloroform until an
albuminoid residue remained ; lead was extracted from each of these
portions, viz., the alcohol used for dehydration, the ethereal and chloro-
form extracts, and the albuminoid residue, as follows:—
Mgrms. of Lead
Sulphate.
Soluble in cold alcohol, . © tº tº g te 1*11
Soluble in ether and chloroform and hot alcohol, . 25*47
Albuminoid residue, . & is e e e ſº 7.76
34°34
In the fifth case, the brain was examined more in detail, and the lead
present estimated in the following solutions and substances:—
1. Alcohol used for dehydration. This may be called “the watery
extract,” for, after the brain has remained in strong alcohol for some
weeks, the result is that the alcohol contains much water and substances
extracted with water.
2. White matter—(a) from cerebrum; (b) from cerebellum.
3. Kephalin—(a) from cerebrum; (b) from cerebellum.
4. Ether extract, kephalin-free—(a) from cerebrum; (b) from cere-
bellum. -
5. Substances soluble in cold alcohol—(a) from cerebrum; (b) from
cerebellum.
6. The albuminoid residue—(a) from cerebrum; (b) from cerebellum.
The general results were as follows:—
Cerebrum, Cerebellum,
460°8 grms. 156-2 grims.
Mgrms. of PbSO4. Mgrms. of PbSO4.
White matter freed from kephalin by ether, . . O'0 5-0
Kephalin, . g © ſº e * e . 1°5 6'0
Ether extract, kephalin-free, tº e g . O'() 0-0
Substances soluble in cold alcohol, tº * ... 0-0 0-0
Albuminoid residue, . e ſº tº ~ . 40°0 6-0
41°5 17:0
The aqueous extract contained 1.5 mgrm. of lead sulphate. In neither
of the cases did the pathologist ascertain the total weight of the brain,
but, presuming that the weight was an average weight, and that the lead
in the remainder of the brain was similarly distributed, the amount of
lead calculated as sulphate would amount to 117 mgrms. From these
results it appears to the authors probable that lead forms a substitution
compound with some of the organic brain matters. This view would
explain the absence of changes apparent to the eye found in so many of
the fatal cases of lead encephalopathy.
§ 785. Lead taken for a long time causes the blood to be impregnated
with uric acid. In 136 cases of undoubted gout, 18 per cent of the
§ 786,786A.] LEAD. 629
patients were found to follow lead occupations, aud presented signs of
lead impregnation.* -
Ellenberger and Hofmeister f found that, with chronic poisoning of
sheep with lead, excretion of hippuric acid ceased, and the output of
uric acid was diminished. This may be explained by the formation of
glycocol being arrested.
§ 786. There are some facts on record which would seem to counten-
ance the belief that disease, primarily caused by an inorganic body like
lead, may be transmitted. M. Paul (e.g.) has related the history of the
offspring (thirty-two in number) of seven men, who were suffering from
lead-poisoning—eleven were prematurely born and one still-born ; of the
remaining twenty, eight died in the first year, four in the second, and
five in the third year, so that of the whole thirty-two only three survived
three years.
The influence of the poison on pregnant women is, indeed, very
deleterious. M. Paul noted that in four women who were habitually
exposed to the influence of lead, and had fifteen pregnancies, ten termi-
nated by abortion, two by premature confinement, three went the full
term—but one of the three children was born dead, a second only lived
twenty-four hours; so that, out of the whole fifteen, one only lived fully.
In another observation of M. Paul, five women had two natural confine-
ments before being exposed to lead. After exposure, the history of the
thirty-six pregnancies of these women is as follows:—there were twenty-
six abortions (from two to five months), one premature confinement, two
infants born dead, and five born alive, four of whom died in the first year.
Chronic poisoning may be nearly always accounted for by the inhaling
of lead dust, or by the actual swallowing of some form of lead ; but, if we
are to accept the fact narrated by the late Dr. Taylor, viz., that he him-
self had an attack of lead colic from sitting in a room for a few hours
daily in which there was a large canvas covered with white lead and
drying oil, and one or two other similar cases, we must allow that there
is some subtle volatile organic compound of lead evolved. In the present
state of our knowledge, it seems more reasonable to account for such cases
by the suggestion that lead has entered the system by an unsuspected
channel.
§ 786A. Lead in Drinking Water.—Attention of recent years has
been directed to the contamination of certain moorland waters by lead,
* “On Lead Impregnation in Relation to Gout,” by Dyce Duckworth, M.D., St.
Barth. Hosp. Reports, vol. xvii., 1881.
t Arch, f, wiss, w. pract. Thierheilk., Bd. x., 1884.
# The gate-keeper of a graveyard at Bordeaux continually used the remnants of
crosses, covered with lead paint, to replenish his fire; the chimney smoked ; gradu-
ally paralysis of the extensors of the right wrist developed itself, and he suffered from
colic and other signs of lead-poisoning.—Marmisse, Gaz, des Hôpit., No. 25, 1866,
63o POISONS : THEIR EFFECTS AND DETECTION. [$ 786A.
and elaborate investigations have been made by the medical depart-
ment of the Local Government Board, the results of which are most
important and interesting.”
Dr. Houston, in his extended experiments, found that “action on lead”
by water could be conveniently divided into “erosive ability” and
“plumbo-solvent ability”; neutral distilled water, pure rain water, and
pure snow water all erode lead, but possess little power of dissolving
lead. In erosion the metal is detached in scales; it is a process
analogous to the rusting of iron—the product of the reaction is insoluble
in neutral liquids, and is only slightly dangerous to public health.
The plumbo-solvent waters are mostly moorland waters, acid in
reaction, the plumbo-solvent power as a rule being in direct relation to
the degree of acidity as determined by titration, using lacmoid as an
indicator. According to Houston, the acidity is produced in peat by
special forms of bacteria; in a few cases of plumbo-solvent waters,
the water has been found to be contaminated by a mineral acid
(sulphuric) derived from the oxidation of pyrites, over which the water
flowed or through which it percolated.
In 1882, a very interesting case occurred at Keighley, in which a
mechanic, aged 42, died from the supposed effects of lead-poisoning,
induced from drinking the town water, which was proved by Mr. Allen
to contain about ; of a grain of lead per gallon. For six months he had
been out of health, and a week before his death he suffered from colic,
vomiting, constipation, and a blue line round the gums, and occasional
epileptiform seizures. After death the kidneys were found granular,
and the heart somewhat enlarged. The viscera were submitted to
Mr. Allen for analysis; no lead was found in the heart or brain, a
slight, non-estimable trace in the kidneys, and about a grain was
separated from the liver and spleen. Dr. Tidy, who was called in as
an expert, gave a very, guarded opinion rather against the theory of
direct lead-poisoning; and the verdict returned by the jury was to the
effect that the deceased died from granular kidney, accelerated by lead-
poisoning. -
The usual test in the absence of iron for lead in drinking waters
is to add to 50 c.c. in a Nessler cylinder, ammonium sulphide;
a black colour or precipitate not discharged or dissolved by hydro-
chloric acid or by potassic cyanide, is an indication of the presence
of lead.
The lead may be estimated colorimetrically by imitating the dark
* “On the Causes of Lead-Poisoning,” by Mr. W. H. Power, F.R.S., Twenty-
third Annual Report of the Loc. Govt. Bd., 1893–94 (supplement). Report by Dr.
Houston on “Moorland Waters in regard of their Action on Lead,” Thirtieth Annual
Report of the Loc. Govt. Bd., 1900–1 (supplement).
§ 786B) LEAD. 63i
colour produced in a known solution of lead acetate by ammonium
sulphide. In important researches it may be advisable to estimate the
lead by weight; in this case a sufficient amount of the water is con-
centrated down, ammonium sulphide added, and the precipitate of
lead sulphide collected and washed ; after standing many hours, the
sulphide is either weighed as sulphide, or treated by the electrolytic
process to be described.
Berntrop” finds lead phosphate absolutely insoluble in water con-
taining free sodic phosphate. He therefore examines waters by adding,
if necessary, calcium chloride and excess of sodium phosphate. The
precipitate which forms during twenty-four hours is said to contain all
the lead as phosphate; it is collected and dissolved in dilute nitric acid,
and identified by the usual tests.
§ 786B. The Plumstead Murder Case.—Murder by the administra-
tion of doses of sugar of lead is rare, but such a case has occurred. At
the Central Criminal Court, in December 1882, Louisa Jane Taylor
was indicted for poisoning Mary Ann Tregillis at Plumstead, and con-
victed. From the evidence it appeared that the prisoner, who was
thirty-six years of age, came to reside with Mr. and Mrs. Tregillis, an
aged couple of eighty-five and eighty-one years respectively. The
prisoner was proved to have purchased at different times an ounce and
half an ounce of sugar of lead, and to have added a white powder to the
medicine of Mrs. Tregillis. The illness of the latter extended from
about August 23 to October 23—a period of two months. It is difficult
to say when the first dose could have been given, but it was probably
some time between August 13 and 23, while the administration, without
doubt, ceased on or before October 6, for on that date different nursing
arrangements were made. The symptoms observed were nausea, vomit-
ing, pain in the pit of the stomach, burning in the throat, very dark
teeth, a blue line round the gums, and slight jaundice. There was
great muscular weakness, with trembling of the hands, and a week
before death there was paralysis of the right side.
Lead was discovered in most of the viscera, which were in great
part normal; but the kidneys were wasted, and the mucous membrane
blackened. The actual quantity of lead recovered by analysis was small,
viz., 16.2 mgrms. (4 grain) from the liver; from 8 ounces of brain,
3.2 mgrms. (ºr grain); from half of the stomach, 16.2 mgrms. (# grain);
and from the spleen, the kidneys, and the lungs, small quantities. It is,
therefore, probable that, if the whole body had been operated upon, the
yield would have been more than 15 grm. (a little over 2 grains); but
then, it must be remembered that the deceased lived, at least, seventeen
days after the last dose.
* Chem. Zeit., 1896, 1020.
632 Poisons: THEIR EFFECTS AND DETECTION. [$ 787, 788.
§ 787. Post-mortem. Appearances.—In acute cases of poisoning by
the acetate, there may sometimes be found a slight inflammatory appear-
ance of the mucous membrane of the stomach and intestines. Orfila
considered that streaks of white points adherent to the mucous membrane
were pathognomonic ; but there have been several cases in which only
negative or doubtful signs of inflammatory or other action have presented
themselves. A general contraction of the intestines has often been
noticed, and is of considerable significance when present ; so also are
slaty patches on the intestinal mucous membrane; in the Plumstead
case Dr. Stevenson found such patches contained lead, hence they are
probably caused by the deposition of lead sulphide. Loen found in dogs
and guinea-pigs, poisoned by lead, local inflammation areas in the lungs,
liver, and kidneys, but in no case fatty degeneration of the epithelial
cells of the liver, kidneys, or intestines. As a rule, no unabsorbed
poison will be found in the stomach; the case related by Christison, in
which a person died on the third day after taking at a single dose some
large quantity of acetate of lead—and at the autopsy a fluid was
obtained from the stomach which had a sweet metallic taste, on
evaporation smelt of acetic acid, and from which metallic lead was
obtained—is so very extraordinary in every respect, that its entire
accuracy is to be questioned. In death from chronic lead-poisoning,
there is but little that can be called diagnostic ; a granular condition of
the kidneys, and all the pathological changes dependent on such a con-
dition, are most frequently seen. If the patient has suffered from colic,
a constriction of portions of the intestine has been noticed; also, in cases
in which there has been long-standing paralysis of groups of muscles,
these muscles are wasted, and possibly degenerated. In instances, again,
in which lead has induced gout, the pathological changes dependent upon
gout will be prominent. The blue line around the gums, and sometimes
a coloration by sulphide of lead of portions of the intestines, may help a
proper interpretation of the appearances seen after death ; but all who
have given any attention to the subject will agree that, simply from
pathological evidence, it is impossible to diagnose chronic lead-poisoning.
§ 788. Physiological Action of Lead.—The action of lead is still
obscure, but it is considered to have an effect mainly on the nervous
centres. The paralysed muscles respond to the direct current, but not
to the induced, leading to the suspicion that the intramuscular termina-
tions of the nerves are paralysed, but that the muscular substance itself
is unattacked. On the other hand, the restriction of the action to groups
of muscles supports the theory of central action.
The lead colic is due to a true spasmodic constriction of the bowel, the
exciting cause of which lies in the walls of the bowel itself; the relief
given by pressure is explained by the pressure causing an anaemia of the
§ 789, 790.] LEAD. 633
intestinal walls, and thus lessening their sensibility. The slowing of the
pulse produced by small doses is explained as due to a stimulation of the
inhibitory nerves; and, lastly, many nervous phenomena, such as epi-
lepsy, etc., are in part due to imperfect elimination of the urinary excreta,
causing similar conditions to those observed in uraemia.
§ 789. Elimination of Lead.—When a large dose of acetate or car-
bonate is taken, part is transformed into more or less insoluble compounds
—some organic, others inorganic ; so that a great portion is not absorbed
into the body at all, but passes into the intestines, where, meeting with
hydric sulphide, part is changed into sulphide, colouring the alvine evacu-
ations black. Some of the lead which is absorbed is excreted by the
kidneys, but the search often yields only traces. Thudichum * states
that in fourteen cases of lead-poisoning, in two only was obtained a
weighable quantity from a day's urine; in the remaining twelve lead was
detected, but only by the brownish colour produced in an acid solution
of the ash by hydric sulphide.
The elimination of lead by the kidneys is favoured by certain medi-
cines, such, for example, as potassic iodide. Annuschat found in dogs
poisoned by lead from 3-8 to 4:1 mgrms. in 100 c.c. of urine; but, after
doses of potassic iodide, the content of lead rose to 6-9 and even to 14
mgrms. Lead appears to be eliminated by the skin, being taken up by the
epithelial cells, and minute, insoluble particles coming away with these
cells. If a person who has taken small doses of lead for a time be placed
in a sulphur water-bath, or have his skin moistened with a 5 per cent.
solution of sodium sulphide, the upper layer of the epidermis is coloured
dark; but the perspiration excited by pilocarpin or other agency contains
no lead.
§ 790. Fatal Dose—(a) Sugar of Lead.—It may almost be said that
it is impossible to destroy human life with any single dose likely to be
taken or administered. In three cases an ounce (28°3 grns.) has been
taken without fatal result. Although it must be allowed that repeated
moderate doses, extending over some time, are more dangerous to health
and life than a single large dose, yet there seems to be in some indi-
viduals a great tolerance of lead. Christison has given 18 grm. in
divided doses daily for a long time without any bad effect, save the pro-
duction of a slight colic. Swieten has also given daily 39 grns. (60
grains) in ten days without observing toxic effects. That, in other cases,
less than a grain per gallon of some lead compound dissolved in drinking-
water, or in some way introduced into the economy, causes serious illness,
is most inexplicable.
(b) The Basic Acetate in solution is more poisonous apparently than
the acetate—60 c.c. (1% drms.) have caused serious symptoms.
* Pathology of the Urime, p. 550.
634 POISONS: THEIR EFFECTS AND DETECTION. [$ 791, 792.
(c) The Carbonate of Lead.—Doses of anything like 28 grims. (an
ounce) would probably be very dangerous to an adult ; the only case of
death on record is that of a child who took some unknown quantity
—probably, from the description of the size of the lump, about 10 grns.
(2% drms.).
§ 791. Antidotes and Treatment.—Soluble sulphates (especially
magnesic sulphate) have been given largely in both acute and chronic
cases; in the acute, it stands to reason that it is well to ensure the
presence of plenty of sulphates in the stomach and intestines, in order
to form the sparingly soluble lead sulphate, should any residue remain,
but to expect this double decomposition to go on in the blood and tissues
is not based upon sound observation. The chronic lead-poisoning is best
treated by removal from the source of mischief, the administration of
large quantities of distilled water, and medicinal doses of potassic iodide.
§ 792. Localisation of Lead.—In a dog, which was killed by chronic
lead-poisoning, Heubel found in the bones 0.18 to 0:27 per 1000 of
lead; in the kidneys, 0-17 to 0-20; liver, 0.10 to 0:33; spinal cord,
0-06 to 0-11 ; brain, 0.04 to 0-05; muscles, 0:02 to 0.04; in the intes-
tines, traces, 0:01 to 0-02; in the spleen, the blood, and the bile he also
only found traces. Ellenberger and Hofmeister found in the kidneys of
the sheep, 0:44 to 0-47; liver, 0.36 to 0-65; pancreas, 0:54; salivary
glands, 0.42; bile, 0.11 to 0.40; bones, 0.32; faces, 0.22; spleen, 0.14;
central nervous system, 0.07 to 0-18; blood, 0.05 to 0-12; flesh, 0.05
to 0-08; urine, 0.06 to 0-08; and in the unstriped muscles and the lungs,
0.03 per 1000 of lead.
Without going so far as to say that lead is a natural constituent of
the body, it is certain that it may be frequently met with in persons
who have been apparently perfectly healthy, and quite free from all
symptoms of lead-poisoning. Legrip found in the liver and spleen of a
healthy person, 5.4 mgrims, of lead oxide in every kilogramme ; Oidtmann,
in the liver of a man fifty-six years of age, 1 mgrm. of lead oxide per
kilogramme, and in the spleen 3 mgrms. per kilogramme. G. Meillere *
has also found traces of lead in a majority of subjects examined. Hence
the analyst, in searching for poison, must be very careful in his con-
clusions. Grave and serious errors may also arise from complications;
suppose, e.g., that a deceased person previous to death had partaken of
game, and inadvertently swallowed a shot--if the analyst had not care-
fully searched the contents of the stomach for solid bodies, but merely
treated them at once with acid solvents, he would naturally get very
decided lead reactions, and would possibly conclude, and give evidence
to the effect, that a poisonous soluble salt of lead had been administered
shortly before death.
* Compt. Revd. Soc. Biol., 1903.
$793, 793A) LEAD. 635
§ 793. Detection and Estimation of Lead.—A great number of
fluids (such as beer, wines, vinegar, water, etc.), if they contain
anything like the amount of one-tenth of a milligramme in 100 c.c.,
will give a very marked dark colour with SH3. It is, however, safest
to destroy all organic matter by evaporating to dryness and incinera-
tion at a very low red heat in a muffle ; the incineration should be
fairly complete, for it has been shown that carbon retains lead with
considerable tenacity.
If (in the usual course of routine research) a hydrochloric acid
solution is obtained from the treatment or destruction of organic sub-
stances by that agent, and lead sulphide (mixed possibly with other
sulphides) is filtered off, any arsenical sulphide may first be extracted
from the filter by ammonia, and any antimonious sulphide by sodic
sulphide; then the sulphide may be extracted by warm hydrochloric
acid, which will leave undissolved such sulphides as those of copper and
mercury. On diluting the liquid, and filtering at a boiling temperature,
crystals of lead chloride will be deposited on cooling.
In the case of sulphate of lead, which may be always produced in
an ash from organic substances by previous treatment with sufficient
sulphuric acid, a very excellent method of identification is to convert it
into sugar of lead. To do this, it is merely necessary to boil it with
carbonate of ammonia, which changes it into carbonate of lead ; treat-
ment with acetic acid will now give the acetate; the solution may (if
the lead is in very small quantity) be concentrated in a watch-glass, a
drop evaporated to dryness on a circle of thin microscopic glass, and the
crystals examined by the microscope; the same film next exposed to the
fumes of SH2, which will blacken it; and lastly, the solution (which
should be sweet) tasted. A crystalline substance possessing a sweet
taste, and blackening when exposed to SH2, can, under the circum
stances, be no other substance than acetate of lead.
Lead in solution can be converted into sulphide ; in this case it is
however, absolutely necessary that there should be no great excess of
acid, since as little as 2.5 per cent. of free hydrochloric acid will pre-
vent all the lead going down. On obtaining the sulphide, the latter, as
already described, can be converted into chloride by hydrochloric acid,
and the crystalline chloride is extremely characteristic.
§ 793A. Tetra-methyl-diamino-phenyl-methane as a Test for Lead
Peroxide.—The salt is the leuco-derivative of malachite green. It may be
made by the reduction of malachite green and by various processes; but
the most convenient method of preparation is to boil 30 grims. of dimethyl-
aniline with 25 c.c. of a 40 per cent. solution of formaldehyde, the
solution being made up to 200 c.c. with water. The excess of dimethyl-
aniline is got rid of by blowing steam through. On cooling, the tetra-
636 POISONS: THEIR EFFECTS AND DETECTION. [$ 793B, 794.
methyl compound crystallises out, and should be dissolved in hot alcohol
and recrystallised from that solvent.
The test solution is made by dissolving 5 grns. of the crystals
in 100 c.c. of water, with the addition of 10 c.c. of acetic acid.
The solution is very sensitive to light and air. Paper dipped in the
solution and dried in the dark will readily “print” if exposed behind a
negative, the unshaded parts of the paper becoming green.
A fragment of lead binoxide or manganese binoxide strikes with the
reagent a deep blue or blue-green colour—chloriue, chromic acid, and
oxidising substances generally also reproduce, in more or less purity,
malachite green (which, by the way, is not a true green, but a blue
green). Hence if utilised as a test for lead binoxide or peroxide, the
test must be used in such a way as to exclude possibility of confusion
with other oxidising substances. This is fairly easy when the test is
applied to the results of an electrolytic operation ; under such circum-
stances the test is of great delicacy, a just visible speck of lead binoxide,
or a just visible stain of the same substance deposited by the galvanic
current on a platinum wire, giving at once a blue colour.
§ 793B. Electrolytic Method of Separating Lead as Dioxide.—Lead
can be separated, estimated, and identified in the most minute quantity
by an electrolytic method under exact conditions of acidity, strength of
current, and temperature.
The lead should be converted into nitrate; the proportions of lead,
acid, and water in 100 c.c. should be not more than 0-2 lead, 13–14 c.c.
nitric acid (14 specific gravity), and the solution made up to 100 with
water. The temperature should be from 60°–70°, the current from
37–40 volts and 11–13 ampères, and it is best to use a rotating
cathode; * under these conditions the lead is thrown down mainly
as dioxide within twenty minutes. The film is washed with water
without interrupting the current, and then with alcohol and ether.
The pole with deposit should be dried for half an hour at a tempera-
ture of 200°–230°, and then weighed. It is usual to multiply the
weight found by 0-8643; but, according to Hollard (Bull. Soc.
Chim., 1904), if a platinum anode roughened by the sand-blast be
used, the ratio of Pb : PbO takes a constant value represented by the
factor 0.855. -
After weighing the lead dioxide, the identity of the substance may
be confirmed by the tetra-methyl-phenyl test. *
§ 794. Estimation of Lead.—By far the greater number of estima-
tions of lead is made by weighing as lead sulphate, first precipitating as
sulphide; careful oxidation with nitric acid of the latter converts it
rapidly into sulphate. Recently, ammonium persulphate has been
* Ralph A. Smith, Journ. Amer. Chem. Soc., 1905.
§ 795–797.] COPPER. 637
recommended * as a precipitant with a view to estimation. Ammonium
persulphate added to an acid solution of a lead salt, precipitates the lead
quantitatively. -
The best precipitant is a 2 per cent. ammonium persulphate solution
containing a trace of silver nitrate ; this is heated to 80°, and
the lead solution added to it drop by drop. The solution should be
kept at 80° for three hours, then filtered and washed with a 3 per cent.
solution of ammonium sulphate ; finally, the precipitate, consisting of
lead oxide, lead peroxide, and lead sulphate, is converted into lead
sulphate by igniting with a drop of sulphuric acid. Every 100 parts of
lead sulphate equal 73-6 PbO.
Estimation as binoxide and the colorimetric method have already
been described.
Lead is also estimated as chloride, as chromate, and as sulphide, but
the processes detailed are sufficient for the toxicologist.
2. COPPER.
§ 795. Copper, Cu + 63-5; specific gravity, from 8:921 to 8:952;
fusing-point, 1091” (1996 F.). Copper in analysis occurs either as a
film or coating on such metals as platinum, iron, etc., or in a state of
fine division, or, finally, as a bead. In thin films, copper has a
yellowish or a yellowish-red colour; it dissolves readily in nitric,
slowly in hydrochloric acid. If air be excluded, hydrochloric acid fails
to dissolve copper, and the same remark applies to ammonia; but, if
there be free access of air, ammonia also acts as a slow solvent.
Metallic copper in a fine state of division can be fused at a white heat
to a bright bluish-green globule, which, on cooling, is covered with
black oxide.
§ 796. Cupric Oxide, CuO=79.5—specific gravity, 6:5; composition
in 100 parts, Cu 7990, O 20-10—is a brownish-black powder, which
remains in the absence of reducing gases unaltered at a red heat. It
is nearly insoluble in water, but soluble in Clh, NOAH, etc.; it is
hygroscopic, and, as everyone who has made a combustion knows, is
readily reduced by ignition with charcoal in the presence of reducing
gases.
§ 797. Cupric Sulphide, CuS = 95.66, produced in the wet way, is
a brownish powder so insoluble in water that, according to Fresenius,
950,000 parts of water are required to dissolve one part. It is not
quite insoluble in ClFI, and dissolves readily in nitric acid with separa-
tion of sulphur. By ignition in a stream of H it may be converted
into the subsulphide of copper. It must always be washed by SH,
* Max Dittrich and A. Reise, Ber. d, deutsch. chem. Ges., 1905.
638 POISONS : THEIR EFFECTS AND DETECTION. [$ 798.
water. It is slightly soluble in the alkaline polysulphides, especially
in the presence of sulphides of arsenic, antimony, and tin.
§ 798. Solubility of Copper in Water and Various Fluids. The
solubility of copper in water and saline solutions has been very care-
fully studied by Carnelley.* Distilled water exerts some solvent action,
the amount varying, as might be expected, according to the time of
exposure, the amount of surface exposed, the quantity of water acting
upon the copper, etc. It would appear that, under favourable circum-
stances, 100 c.c. of distilled water may dissolve 3 mgrm. of copper
(2 grain per gallon).
With regard to salts, those of ammonium exert a solvent action on
copper more decided than that of any others known. With the others,
however, the nature of the base exerts little influence, the action of the
salt depending chiefly on the nature of its acid radical. Thus, beginning
with the least effective, the following is the order of dissolving strength
—nitrates, sulphates, carbonates, and chlorides. It will then at once
be evident that a water contaminated by sewage, and, therefore, con-
taining plenty of ammonia and chlorides, might exert a very considerable
solvent action on copper.
Almost all the oils and fats, as well as syrups, dissolve small
quantities of copper; hence its frequent presence in articles of food
cooked or prepared in copper vessels. In the very elaborate and careful
experiments of Mr. W. Thompson,t the only oils which took up no
copper, when digested on copper foil, were English meats'-foot oil,
tallow oil, one sample of olive oil, palm-mut oil, common tallow oil, and
white oil, which was protected from the air by a thick coating of oxidised
oil on its surface.
The formation of copper compounds with the fatty acids takes place
so readily that Jeannel i has proposed the green colouring of fats by
copper as a test for the presence of copper; and Bottger § recommends
a brandy holding copper to be shaken up with olive oil to free it
from copper.
Lehmann has made some useful researches on the amount of copper
taken up by fats under different conditions. 100 c.c. of strongly rancid
fat dissolved in fourteen days 8-7 mgrms. of copper; but when heated to
160° for one hour, and then allowed to stand, a similar amount was
found. Some rancid butter was rubbed into a brass bowl of 90 c.c.
capacity, and then allowed to stand for twenty-four hours; the butter
became of a blue-green colour. Into this dish, thus partially attacked
* Journ. Chem. Soc., 1876, vol. ii. p. 4. •"
+ “Action of Fatty Oils on Metallic Copper,” Chem. News, vol. xxxiv. pp. 176,
200, 313.
# L'Union pharmac., xvii. 81. § Arch. de Pharm., 1853, cxxvi. 67.
§ 798.] COPPER. 639
by fatty acids, 50 c.c. of rancid butter was poured in a melted con-
dition, and allowed to stand for twenty-four hours. The amount taken
up was found to be equal to 10 mgrms. of copper for every 100 c.c. of
fluid butter.
Hilger found a fatty soup, which had stood twelve hours in a clean
copper vessel, to contain 0.163 per cent. copper. According to Tschirch,
the easiest fatty salt to form is the oleate, hydrated copper oxide dissolv-
ing in oleic acid with great ease, and even copper oxide dissolving to
some extent; the palmitate and the stearate are not so readily produced
-—hence the amount of copper dissolved is greater in the case of olive oil
and butter (both rich in oleic acids) than in the case of the firmer
animal fats. Copper oleate, according to H. Baum and R. Seeliger
(Zeit. Öffentl. Chem., iv. 181—210), is more poisonous than either the
acetate or sulphate. Acid solutions, such as clarets, acetic acid,
vinegars, and so forth, as might be expected, dissolve more or less
copper. The amount likely to be dissolved in practice has been
investigated by Lehmann. He steeped 600 square metres of copper
sheeting or brass sheeting in vessels holding 2 litres each of acid claret ;
the sheets were in some of the experiments wholly immersed, in others
partly so. More copper was dissolved by the wine when the copper
was partly immersed than when it was wholly immersed; and more
copper was dissolved from brass sheeting than from pure copper sheeting.
With a sheet of copper, partly immersed, claret may contain as much
as 56 mgrms. per litre. Lehmann also investigated the amount of
copper, as acetate, which could be dissolved in wine before the taste
betrayed its presence: with 50 mgrms. per litre no copper taste ; with
100 mgrms, there was a weak after-taste ; with 150 mgrms. it was
scarcely drinkable, and there was a strong after-taste; with 200 mgrms.
per litre it was quite undrinkable, and the colour was changed to bluish-
green. Winegar, acting under the most favourable circumstances on
sheet brass or copper, dissolved, in seven days, 195 mgrms. of copper
per litre from the copper sheet, 195 from the brass sheet.
Lehmann discusses the amount of copper which may be taken at a
meal under the circumstance that everything eaten or drank has been
artificially coppered, but none “coppered” to the extent by which the
presence of the metal could be betrayed by the taste; and the following
is, he thinks, possible:—
300 c.c. of soup boiled in a copper vessel, . e 20 mgrms. Cu.
1 litre of wine which has been standing in a copper vessel, 50 , ,
50 c.c. vinegar which has been kept in a copper vessel, . 10 , ,
50 grims, of fat which has been used for frying in a copper
vessel, e e e e e º - e - 5 , ,
200 grms. of strongly coppered peas, & - * º 50 , ,
500 grims. of strongly coppered bread. & -> e te 60
64o POISONS : THEIR EFFECTS AND DETECTION. [$ 799.
The total amounts to 195 mgrims, of copper, which only slightly exceeds
a high medicinal dose. The metal is tasted more easily in liquids, such
as wine, than in bread; bread may be coppered so that at a meal a
person might eat 200 mgrms. of a copper compound without tasting it.
It is pretty well accepted that cooking in clean bright copper vessels
will not contaminate any ordinary food sufficiently to be injurious to
health.
§ 799. Copper in the Vegetable and Animal Kingdom and in
Foods.-Copper is widely distributed in the vegetable kingdom, and is a
constant constituent of the chief foods we consume ; the following quan-
tities, for example, have been separated from the chief cereals:—
Wheat, . e º & º tº 5'2 to 10.8 mgrims. per kilo.
Rye, e o º º * & 5 mgrms. 5 §
Oats, . te e o g e 8'5 ,, 5 3
Barley, . & º & g . 11°8 , , 5 §
Rice, & g g § º tº 1°6 , , 3 5
Bread, . º e e de ſº 1°5 to 4'4 mgrms. 3 J
It has also been found in vermicelli (2–10 mgrms. per kilo.), groats
(1.6–3 mgrms. per kilo.), potatoes (1.8 mgrm. per kilo.), beans (2–11
mgrms. per kilo.). In similar small quantities it has also been found in
carrots, chicory, spinach, hazel-nuts, blackberries, peaches, pears, figs,
plums, tamarinds, black pepper, and many other fruits and spices. The
most common food which has a high copper content is cocoa, which con-
tains from 12 mgrms. to 29 mgrms. per kilo., the highest amount of
copper being in the outer husk; copper has also been found in many
supplies of drinking water, in aerated waters, in brandies, wines, and
many drugs.
It has been calculated that the ordinary daily food of an average man
contains the following:—
Copper.
900 grms, bread, . fe e tº t st * 0°45 mgrm.
260 grims, meat, . tº * g g e e 0.25 ,,
200 grms. fruit and vegetables, . g {º tº 0-25 ,,
0.95 mgrm.
That is to say, that, neglecting altogether foods artificially contaminated
with copper, each of us eats daily about 1 mgrm. of copper (0.015 grain).
In the animal kingdom it is a constant and natural constituent of
the blood of the cephalopods, crustacea, and gasteropods, and is nearly
always present in the liver and kidneys of domestic animals, as well
as in men. Dr. Dupré” found 035 to 029 grain (1.8 to 2 mgrims.)
in human livers, or about 1 part in 500,000. Bergeron and L. L.
Hote's researches on fourteen bodies, specially examined for copper, fully
* Analyst, No. 13, 1877.
§ 800.] COPPER. 64I
substantiate those of Dr. Dupré : in twelve the copper was found in
quantities of from 7 to 1.5 mgrm. ; in the remaining two the amount of
copper was very minute, and was not estimated.* Copper is also found
normally in the kidneys, and Dupré f detected in human kidneys about
1. in 100,000 parts; it is also found in the bile, and in minute traces in
the blood. I
In the kidneys and livers of the ruminants copper may always
be found, a sheep's liver containing about 1 part in 20,000.S Church
found copper in the feather of the wings of the turaco; melopsitt in
the feathers of a parroquet (Melopsittacus undulatus).|| In these cases
the copper enters into the composition of the colouring matter to which
the name of “turacin” has been given. Turacin contains 7 per cent. of
copper, and gives to analysis numbers which agree with the formula
of Cs2HsiCugno'O39.
Copper has been discovered in aerated waters, its presence being due
to the use of copper cylinders, the tin lining of which had been rendered
defective by corrosion."
Accidents may also occur from the use of copper boilers. Mr. W.
Thompson found in one case ** no less than 3:575 grains in a gallon (51
mgrms. per litre) in water drawn from a kitchen boiler.
At Roubaix, in France, sulphide of copper had been deposited on the
roof, as a consequence of the use of copper flues; the sulphide was
changed into sulphate by the action of the air, and washed by the rain
into the water-tank.it
That preserved vegetables are made of a bright and attractive green
colour by impregnation with copper, from the deliberate use of copper
vessels for this purpose, is a fact long known. Green peas especially
have been coloured in this way, and a number of convictions for this
offence have taken place in England.
$ 800. The “Coppering” of Vegetables.—The fact that green
vegetables, such as peas, beans, cucumbers, and so forth, preserve their
green colour, if boiled in copper vessels, has long been known. In this
“coppering” the French have been more active than the English
traders; the French operate in two different ways. One method is, to
dip from 60 to 70 litres of the green vegetables in 100 litres of 0-3 to
0.7 per cent, of copper sulphate, to leave them there for from five
to fifteen minutes, then to remove them, wash and sterilise in an
autoclave. A second method is to put the vegetables into a copper
* Compt. Rend., vol. lxxx. p. 268. f Op. cit.
† Hoppe-Seyler, Handbuch der physiologisch. Analyse, p. 415.
§ Dupré, op. cit. | Chem. News, xxviij. 212.
"I “On the Presence of Lead and Copper in Aerated Waters,” by Dr. James
Milne, Chem. News, xxxi. p. 77.
** Chem. News, xxxi. No. 801. tº Blyth, Dictionary of Hygiene, p. 167.
4 I
642 POISONS : THEIR EFFECTS AND DETECTION. [$800.
vessel, the wall of which is connected with the negative pole of an
electric current ; the positive pole dips in a solution of salt in the
same vessel, the current is allowed to pass for three minutes, and
the vegetables are afterwards sterilised. Fruits are simply allowed to
stand with water in copper vessels, the natural acidity of the juice
dissolving sufficient copper.
The amount of copper taken up in this way is appreciable, but yet
not so much as might be expected. The prosecutions for selling
“coppered" peas in England have been based upon quantities varying
from 1 to 3 grains per lb. ; the highest published amount of copper
found in peas artificially coloured is 0:27 per kilo., or 18.9 grains
per lb.
The reason why vegetables preserve their green colour longer when
treated with a copper salt has been proved by Tschirch * to be owing to
the formation of a phyllocyanate of copper.
Phyllocyanic acid is a derivative of chlorophyll, and allied to it in
composition ; the formula of C23Has N2O4 has been ascribed to it. Under
the action of acids generally, mineral or organic, chlorophyll splits
up into this acid and other compounds. Copper phyllocyanate,
(C23H31N3O4)3Cu, contains 8:55 per cent, of copper; it forms black
lamellae, dissolving easily in strong alcohol and chloroform, but in-
soluble in water; it is a little soluble in ether, insoluble in petroleum
ether, and dissolved neither by dilute acetic acid nor by dilute nor
concentrated hydrochloric acid. The compound dissolves in caustic
alkali on warming. In alcohol it forms a beautiful non-fluorescent
solution. A solution of 1 : 100,000 is still coloured strongly green.
This solution, in a stratum 25 mm. thick, gives four absorption
bands when submitted to spectroscopic observation, and Tschirch has
worked out a process of estimation of the amount of copper phyllo-
cyanate based upon the disappearance of these bands on dilution.
Green substances, so carefully treated that they only contain
phyllocyanate of copper, would yield but small quantities of copper,
and probably they would not be injurious to health ; but the coppering
is usually more extensive, and copper leguminate and other compounds
are formed—for the vegetables, when exhausted by alcohol, give a
residue which, successively exhausted by water, by soda-lye, and lastly
by hydrochloric acid, parts with copper into the three solvents
mentioned.
It might be argued that, from the insoluble character of the phyllo-
cyanate of copper, and especially seeing that it does not dissolve in
strong hydrochloric acid, that it would be perfectly innocuous; but
Tschirch has proved that, whether the tartrate of copper (dissolving
* Das Kupfer, Stuttgart, 1893.
§ 8on.] COPPER, 643
easily in water), or copper oxide (not dissolving at all in water, but
soluble in hydrochloric acid), or phyllocyanate of copper (insoluble both
in water and in hydrochloric acid) be used, the physiological effect is
the same. :
Copper may be found in spirits owing to the use of copper con-
densers, a remark which applies also to the essential oils, such as oleum
cajepute, menthae, etc.” In France, it has been added fraudulently to
absinthe, to improve its colour.f Green sweetmeats, green toys, green
papers, have all been found to contain definite compounds of copper to
a dangerous extent.
§ 801. Preparations of Copper used in Medicine and the Arts.
(1) Medicinal Preparations:—
Sulphate of Copper, Cupri Sulphas, CuSO,5H,0.—This well-known
Salt is soluble in water at ordinary temperature, 3 parts of water
dissolving 1 of the sulphate ; but boiling water dissolves double its
weight. One part of copper sulphate dissolves in 2% of glycerin; it
reddens litmus, and is slightly efflorescent ; its solution responds to all
the usual tests for copper and sulphuric acid. A watery solution of the
Salt to which twice its volume of a solution of chlorine has been added,
gives, when treated with ammonia in excess, a clear sapphire-blue solu-
tion, leaving nothing undissolved, and thus showing the absence of
iron. Besides iron, sulphate of copper has been found to contain zincic
sulphate.
Nitrate of Copper, Cu(NO3)33H2O, is officinal; it is very soluble.
Cuprum Aluminatum.–A preparation, called cuprum aluminatum
(Pierre divine), is in use in France and Germany, chiefly as an
external wash. It is composed of 16 parts cupric sulphate, 16
potassic nitrate, 16 alum, fused in a crucible, a little camphor being
afterwards added.
Regular and irregular medical practitioners, veterinary surgeons,
farriers, and grooms, all use sulphate of copper (bluestone) as an appli-
cation to wounds. Copper as an internal remedy is not in favour
either with quacks or vendors of patent medicines.
(2) Copper in the Arts.-Copper is used very extensively in the
arts; it enters into the composition of a number of alloys, is one of the
chief constituents of the common bronzing powders, is contained in
many of the lilac and purple fires of the pyrotechnist, and in a great
variety of pigments. The last-mentioned, being of special importance,
will be briefly described:—
* According to Eulenberg (Gewerbe Hygiene, p. 716), Oleum cajepute, Menth.
pip., Melissae, Tanaceti, etc., are almost always contaminated with copper.
t Tardieu, Étude Méd.-Lég. sur l'Empoisonnement.
644 POISONS: THEIR EFFECTS AND DETECTION. [$802, 803.
Pigments:—
Schweinfurt and Scheele's Green * are respectively the aceto-arsenite
and the arsenite of copper (see art. “Arsenic”).
Brighton Green is a mixture of impure acetate of copper and chalk.
Brunswick Green, originally a crude chloride of copper, is now
generally a mixture of carbonate of copper and chalk or alumina.
Mountain Green, or Mineral Green, is the native green carbonate of
copper, either with or without a little orpiment.
Neuwieder Green is either the same as mountain green, or Schwein-
furt green mixed with gypsum or sulphate of baryta.
Green Verditer is a mixture of oxide and carbonate of copper with
chalk.
Verdigris is an acetate of copper, or a mixture of acetates. Its
formula is usually represented as (C, H,02)CuO. It is much used in the
arts, and to some extent as an external application in medicine. Its
most frequent impurities or adulterations are chalk and sulphate of
copper.
§ 802. Dose—Medicinal Dose of Copper.—Since sulphate of copper
is practically the only salt administered internally, the dose is generally
expressed as so many grains of sulphate. This salt is given in quantities
of from 016 to 129 grm. (3 to 2 grains) as an astringent or tonic ; as
an emetic, from 324 to 648 grrm. (5 to 10 grains).
The sulphate of copper is given to horses and cattle in such large
doses as from 30 up to 120 grains (1-9 to 7-7 grms.); to sheep, from
1.3 to 2-6 grms. (20 to 40 grains); rabbits, 0648 to 1296 grm.
(1 to 2 grains).
§ 803. Effects of Soluble Copper Salts on Animals.-Harnack has
made some experiments on animals with an alkaline tartrate of copper,
which has no local action, nor does it precipitate albumin. ; to #
mgrm. of copper oxide in this form, administered subcutaneously, was
fatal to frogs, '05 grm. to rabbits, 4 grn. to dogs. The direct excita-
bility of the voluntary muscles was gradually extinguished, and death
took place from heart paralysis. Vomiting was only noticed when the
poison was administered by the stomach.f The temperature of animals
poisoned by copper, sinks, according to the researches of F. A. Falck,
many degrees. These observations are in agreement with the effects
of copper salts on man, and with the experiments of Orfila, Blake,
C. Ph. Falck, and others. -
* The synonyms for Schweinfurt green are extremely numerous:–Mitic green,
Viennic green, imperial green, emerald green, are the principal terms in actual use.
+ On the other hand, Brunton and West have observed vomiting produced in
animals after injection of copper peptone into the jugular vein.—Barth. Hosp, Rep.,
1877, xii.
§ 8o3.] COPPER. 645
Roger * experimented on the effect of copper leguminate which was
administered subcutaneously; he found gradual increasing paralysis of
the motor spinal tracts, which finally destroyed life by paralysis of the
breathing centre. The heart beat after the breathing had stopped. . The
irritability and contractility of the muscles of frogs were lost, while
sensibility remained. He also found that, if the copper was injected into
the intestinal vessels, the dose had to be doubled in order to destroy life ;
that is, doubtless, because the liver, as it were, strained the copper off
and excreted it through the bile. Roger was unable to destroy life by
large doses of copper given by the mouth, for then vomiting supervened
and the poison in great part was removed.
Bernatzic f considers that the poisonous properties of copper are
similar to those of zinc and silver. He says: “Silver, copper, and zinc
are, in their medicinal application, so much allied that, with regard to
their action, they graduate one into the other and show only minor
differences; copper, which is a little the more poisonous of the three so
far as its remote action is concerned, stands between the other two. If
taken, in not too small a quantity, for a long time, the functional activity
of the muscular and nervous systems is influenced injuriously, the
development of the animal cells is inhibited, the number of the red
blood corpuscles decreased, and therefore the oxidising process and
metabolism are likewise diminished, leading ultimately to a condition
of marked cachexia. . . . From a toxic point of view, the three
metals named also stand near each other, and their compounds differ
from other metals injurious to the organism in this, that they do not
produce notable changes of the tissues or coarse functional disturbances
leading to death as other poisonous metals, and therefore are not to be
considered poisons in the same sense as lead, mercury, arsenic, antimony,
phosphorus are considered poisons; for, on stopping the entry of the
poison, any injurious effect is completely recovered from and the
functions again become normal.” -
Lehmann also has experimented on the effects of copper; his
experiments were made on both animals and men. He found that
small quantities were more thoroughly absorbed than medium or large
doses; the method of separation appeared to be different in different
animals—thus, the chief copper-excreting organ in dogs is the liver, in
rabbits the intestine, and in man the kidneys. Of 3 mgrms. of copper
taken by a man in three days, 1 mgrm., or a third, was recovered from
the urine. Lehmann experimented on 6 rabbits, 4 cats, and 1 dog.
During the first few days the animals were given 10 to 30 mgrms. of
* Revue de Médecime, 1877, xii.
i Encycloped. d. ges. Heilkwºnde, xi. S. 429.
† Munch, med. Wochemschrift, 1891, Nr. 35 u. 36.
646 POISONS : THEIR EFFECTS AND DETECTION. [$804.
copper, in the form of a salt, in their food; then the dose was raised to
50 mgrms. or even to 100 mgrms., and the experiment continued for
from two to four months; in one case, six months. The sulphate,
acetate, chloride, oleate, butyrate, and lactate were all tried, but no
essential difference in action was discovered ; apart from slight vomiting,
and in a few cases, as shown by post-mortem, a slight catarrh of the
stomach, the animals remained well. A few increased in weight.
Nervous symptoms, cramps, convulsions, diarrhoea, or the reverse, were
not observed. The analysis of the organs showed considerable copper
absorption ; the liver of the cats gave a mean amount of 12 mgrms, of
copper, and in the other organs there was more copper than is found in
cases of acute poisoming.
Lehmann has also made experiments upon himself and his pupils on
the effect of the sulphate and the acetate when taken for a long time :-
One of the experimenters took for 50 days 10 mgrims. daily Cu as
- sulphate.
33 } } ,, . then for 30 , 20 } } 33
Another took for 3 days e e tº 5 mgrms, as acetate.
3 y then for 10 days * & . 10 } % 2 3
} % } } 1 day t tº . 15 } % 5 y
35 } } 19 days º tº . 20 3 J. 35
} } } } 18 days tº e . 30 5 5 } }
None of these daily doses had the least effect.
Five further experiments showed that 75 to 127 mgrrms. of copper
in peas and beans, divided in two meals, could be taken daily without
effect ; but if 127 mgrms, were taken at one meal in 200 grims. of peas,
then, after a few hours, there might be vomiting ; and Lehmann con-
cludes that doses of copper in food of about 100 mgrms. may produce
some transient derangement in health, such as sickness, a masty taste in
the mouth, and a general feeling of discomfort, but nothing more. Some
slight colicky pains and one or two loose motions are also possible, but
were not observed in Lehmann's experiments.
§ 804. Toxic Dose of Copper Salts.--This is a difficult question,
because copper salts generally act as an emetic, and therefore very large
doses have been taken without any great injury. In fact, it may be laid
down that a medium dose taken daily for a considerable time is far more
likely to injure health, or to destroy life, than a big dose taken at once.
In Tschirch’s” careful experiments on animals, he found 10 mgrm. doses
of CuO given daily to rabbits, the weight of which varied from 1200
to 1650 grns., caused injury to health—that is, about 3.5 mgrms. per
kilo. If man is susceptible in the same proportion, then daily doses of
* Das Kupfer, Stuttgart, 1893.
§ 805.] COPPER. 647
227-5 mgrms. (or about 3% grains) would cause serious poisonous
symptoms; although double or treble that quantity might in a single
dose be swallowed and, if thrown up speedily, no great harm result.
120 grns. of sulphate of copper have been swallowed, and yet the
patient recovered after an illness of two weeks.” Lewin f mentions
the case of an adult who recovered after ten days' illness, although the
dose was 15 grms. ; there is also on record the case of a child, four and
a half years old, who recovered after a dose of 16.5 grms. (a little over
half an ounce). On the other hand, 77 grims, have been with difficulty
recovered from.f A woman died in seventy-two hours after taking 27
grims. (7 drms.) of copper sulphate mixed with 11-6 grims. (3 drms.) of
iron sulphide ; 56-6 grns. (2 ozs.) of copper acetate have caused death
in three days, 14.2 grims. (0-5 oz.) in sixty hours.S
$ 805. Cases of Acute Poisoning.—Acute poisoning by salts of
copper is rare: in the ten years ending 1903, there were registered in
England 5 deaths from this cause—3 suicidal (2 males, 1 female)
and 2 accidental (males). The symptoms produced by the sulphate
of copper are those of a powerful irritant poison : there is immediate
and violent vomiting; the vomited matters are of a greenish colour—
a green distinguished from bile by the colour changing to blue on the
addition of ammonia. There is pain in the stomach, and in a little
time affections of the nervous system, as shown by spasms, cramps,
paralysis, and even tetanus. Jaundice is a frequent symptom, if life is
prolonged sufficiently to admit of its occurrence.
One of the best examples of acute poisoning by copper sulphate is
recorded by Maschka.|| A youth, sixteen years old, took an unknown
large dose of powdered copper sulphate, mixed with water. Half an
hour afterwards there was violent vomiting, and he was taken to the
hospital. There was thirst, retching, constriction in the throat, a cop-
pery taste in the mouth, and pain in the epigastrium, which was painful
on pressure. The vomit was of a blue colour, and small undissolved
crystals of copper sulphate were obtained from it. The patient was pale,
the edges of the lips and the angles of the mouth were coloured blue,
the surface of the tongue had also a blue tint, the temperature was
depressed, the extremities cold, mails cyanotic, and the pulse small and
quick. Several loose greenish-yellow evacuations were passed ; there
was no blood. The urine was scanty, but contained neither blood nor
albumen. During the night the patient was very restless ; the next
morning he had violent headache, pain in the epigastrium, burning in
* Referred to by Bernatzic, on the authority of Ketli, in Encycl. d, ges.
Heilkunde, xi. S. 433
+ Toacicologie, S. 133. # Taylor, op. cit. § Sonnenschein, op. cit.
| Wiener med, Wochenschr., 1871, Nro. 26, p. 628.
648 POISONs: THEIR EFFECTS AND DETECTION. [$ 806-808.
the mouth and gullet, but no vomiting. The urine was scanty, con-
tained blood, albumen, and colouring matter from the bile. On the
fourth day there was marked jaundice. The mucous membrane was
very pale, the temperature low, pulse frequent ; and great weakness,
cardiac oppression, and restlessness were experienced. There were
diarrhoea and tenesmus, the motions being streaked with blood; the
urine also contained much blood. The liver was enlarged. The patient
died in a state of collapse on the seventh day.
In 1836 a girl, sixteen months old, was given bluestone to play with,
and ate an unknown quantity; a quarter of an hour afterwards the
child was violently sick, vomiting a bluish-green liquid containing some
pieces of sulphate of copper. Death took place in four hours, without
convulsions, and without diarrhoea. r
§ 806. Subacetate of Copper, Subchloride, and Carbonate, all act
very similarly to the sulphate when given in large doses.
$ 807. Post-mortem. Appearances.—In Maschka's case, the chief
changes noted were in the liver, kidneys, and stomach. The substance
of the liver was friable and fatty; in the gall-bladder there was but a
few drops of dark tenacious bile. The kidneys were swollen, the
cortical substance coloured yellow, the pyramids compressed and pale
brown. In the mucous membrane of the stomach there was an excori-
ation the size of a shilling, in which the epithelium was changed into a
dirty brown mass, easily detached, laying bare the muscular substance
beneath, but otherwise normal.
In a case of poisoning by verdigris (subacetate of copper) recorded
by Orfila,” the stomach was so much inflamed and thickened that
towards the pyloric end the opening into the intestine was almost
obliterated. The small intestines throughout were inflamed, and per-
foration had taken place, so that part of the green liquid had escaped
into the abdomen. The large intestines were distended in some parts,
contracted in others, and there was ulceration of the rectum. In other
cases a striking discoloration of the mucous membrane, being changed
by the contact of the salt to a dirty bluish-green, has been noticed, and,
when present, will afford valuable indications.
§ 808. Chronic Poisoning by Copper.—Symptoms have arisen among
workers in copper or its salts, and also from the use of food accidentally
contaminated by copper, which lend support to the existence of chronic
poisoning. In the symptoms there is a very great resemblance to those
produced by lead. There is a green line on the margin of the gums
Dr. Clapton f found the line very distinct in a sailor and two working
coppersmiths, and the two men were also seen by Dr. Taylor. Cases of
* Toacicologie, vol. i. p. 787 (5th ed.).
i Med. Times and Gazette, June 1868, p. 658.
§ 808.] COPPER. 649
chronic poisoning among coppersmiths have also been treated by Dr.
Cameron,” but this symptom was not noticed. Corrigan speaks of the
line round the gums, but describes it as purple-red. Among workers in
copper, Lancereaux f has seen a black coloration of the mucous mem-
brane of the digestive canal; its chemical characters appear to agree
with those of carbon. *
Metallic copper itself is not poisonous. A Mr. Charles Reed has
published a letter in the Chemical News of Jan. 12, 1894, stating that
he was, when a boy, wounded in the shin by a copper percussion-cap,
and the cap remained in the tissues; it was removed from the shin
after a sojourn there of some twelve years; about the year 1873 he
noticed that whenever a piece of clean iron or steel came in contact with
his perspiration it was at once covered with a bright coating of copper,
and this continued until the percussion-cap was removed. Presuming
the truth of this, it shows conclusively that metallic copper deposited in
the tissues is in itself not poisonous, and further, that one method of
elimination is by the skin. The experiments already cited throw doubt
as to whether repeated small doses of copper taken for a long time
produce, in a scientific sense, chronic poisoning; those which apparently
support the view that there is such a thing as chronic poisoning by
copper have been produced by copper mixed with other metals, and
there is the possibility that these cases are really due to lead or arsenic
and not to copper. The great use of late years of solutions of copper
sulphate as a dressing to plants, for the purpose of preventing the
ravages of various parasites, has provided, so far as animals are concerned,
much material for the judgment of this question. Sheep have been fed
with vines which have been treated with copper sulphate, oxen and pigs
have consumed for a long time grass treated with a 3 per cent. of copper
sulphate, without the least health disturbance. Mach f has fed cows
with green food coppered up to 200 mgrms. of copper sulphate, without
observing the slightest bad effect, for long periods of time; and Tschirch Š
summarises the evidence as to chronic poisoning as follows:—“So it
appears the contention that there is no chronic poisoning in men or
animals is at present uncontradicted; it is further to be considered
proved that the small amounts of copper naturally in food, or carefully
introduced into food, are not injurious to the health of those that take
such food, because the liver, kidneys, and other organs excrete the
copper through the urine and bile, and prevent a pernicious accumu-
lation.” At the same time, Tschirch does not consider the question is
* Med. Times and Gazette, 1870, vol. i. p. 581.
+ Atlas of Pathological Anatomy.
† Mach, Bericht iber die Ergebnisse der im Jahre 1886 ausgeführten Versuche zwr
Bekämpfwng der Peronospora, St. Michele, Tyrol. § Op. cit.
65o POISONS : THEIR EFFECTS AND DETECTION. [$809.
definitely settled ; the experiments should, he thinks, have been con-
tinued not for months, but for years, to obtain a trustworthy judgment.
It may also be remarked that, if we are to rely upon the separation
of copper by the kidneys and the liver, those organs are presumed to be
in a healthy state, which is not the case with a percentage of the popu-
lation ; to persons whose liver or kidneys are unsound, even the small
amounts of copper found in “coppered ” peas may act as a poison, and
the experiments previously detailed throw no light upon the action of
copper under such circumstances.
§ 809. Detection and Estimation of Copper.—In routine analysis,
a solution of inorganic salts, acidified only moderately with hydrochloric
acid, will have been saturated with hydric sulphide, and any precipitate
treated with ammonium sulphide to dissolve out the sulphides of arsenic,
antimony, and tin; the sulphides remaining insoluble may be silver,
mercury, bismuth, lead, copper, cadmium, zinc, and there may be, if
platinum vessels have been used, a trace of platinum sulphide. These
mixed insoluble sulphides are attacked by mitric acid, diluted with its
own volume of water, and the mixture boiled. Soluble nitrates are
formed of most of the metals, but sulphide of mercury will not be dis-
Solved, nor platinum sulphide—the lead sulphide, if present, will also
in great part have been converted into sulphate, so that these, with
free sulphur, can be filtered off. In the nitric acid solution, any silver
may be detected and separated by hydrochloric acid, lead by dilute
sulphuric acid, and bismuth by adding an excess of ammonia and
filtering off any white precipitate. Should copper be present, the
ammoniacal liquid will be of a blue colour. To separate the copper the
liquid may be evaporated to dryness, and the nitrate decomposed by
heating with a little sulphuric acid; the resulting sulphate is dissolved
in water, boiled, and to the boiling liquid hyposulphite of sodium
solution added, which produces a precipitate of cuprous sulphide,
Cu°S, mixed with sulphur. This sulphide may be readily converted
into a soluble copper salt and further identified by tests.
Electrolysis of Copper Salts.-Both as a means of detection and
estimation of copper, electrolysis is much used. Copper is readily
deposited from an acidified solution on either bright iron or bright
zinc. An old method of estimating copper was to treat a solution with
zinc-foil and dilute sulphuric acid, but this somewhat crude process is
now but little used. The ordinary process of electrolytic deposition of
copper is to dissolve up to 1-5 grm. of the substance containing copper
in dilute sulphuric acid, to add a small quantity of nitric acid, and to
dilute up to 130 c.c. with water, using platinum poles; the anode may
conveniently be a platinum dish. The solution is heated to about
60°–65°, and the current should be 2.5–3 ampères and 2 volts. The
§ 810.] COPPER. 651
deposit is washed (without interrupting the current) first with water,
then with alcohol, and finally with ether, and is then carefully dried and
weighed. Should iron, nickel, or cobalt be present, Kufferath * adds
2 grims. of formaldehyde, which prevents their deposition.
Special Tests for Salts of Copper.—Hydrazine Sulphate.—A 3 per
cent. solution of hydrazine sulphate added to a solution of a copper
salt, in presence of an excess of sodium hydroxide, precipitates the
copper as metallic copper; the metal may be filtered off, dried, ignited,
and weighed as cupric oxide.i.
Diphenyl-Carbazide Test.—A cold saturated solution of the carbazide
in benzene, agitated with an aqueous solution of a copper salt, produces
a violet compound which dissolves in the benzene.: Carbazide gives
colours similarly with a number of metals, but the hue of the copper
compound differs from all others.
Formaldozime.—Formaldoxime is made by adding hydroxylamine
hydrochloride to formaldehyde in solution in the proportion 1 : 5. This
solution is mixed with the solution to be tested for copper and a slight
excess of potash solution; should copper be present, a violet colour
results. It is stated that one part per million of copper in aqueous
solution may be detected by this reagent.S
The Bromine Test.—On evaporating a solution containing a copper
Salt to dryness, and then adding bromine water and again evaporating
to dryness, a black residue of copper bromide is formed ; this will,
according to Vitali, detect one part of copper sulphate in a million of
water.|
Micro-Chemical Tests for Copper.—A dilute solution of a copper
salt, to which ammonia has been added, gives a precipitate with
potassic ferrocyanide of ammonium ferrocyanide of copper (Fe(CN). Cus,
4NHs, H2O) in pale yellow characteristic crystals; the crystals, without
changing their form, gradually lose ammonia, and then the colour
becomes a red-brown or brick-red.
A copper salt dissolved in a concentrated solution of potassium
nitrite, to which acetic acid in excess has been added and then a small
fragment of lead acetate, is converted into a triple nitrite of potassium,
copper, and lead 2NO.K., (NO”), Pb, (NO),Cu 6H,0; this salt is in
highly refractive cubes, and is very characteristic.
$ 810. Volumetric Processes for the Estimation of Copper.—A
number of volumetric processes have been devised for the estimation of
* Zeit, angew. Chem., 1904.
+ Paul Jannasch and K. Biedermann, Ber., 1900.
† Paul Cazeneuve, Compt. Rend., 1900.
§ Dunstan and Rossi, Journ. Chem. Soc., Trans., 1898. A. Bach, Compt.
Rend., 1899.
| D. Vitali, Boll. Chim. Farm., xxxviii.
652 POISONs: THEIR EFFECTS AND DETECTION. [$ 811–814.
copper, but for the purposes of this work it is unnecessary to detail
them. When copper is in too small a quantity to be weighed, it may
then be estimated by a colorimetric process.
One of the best of these is based upon the brown colour which ferro-
cyanide of potash produces in very dilute solutions of copper. A
standard copper solution is obtained by dissolving sulphate of copper in
a litre of water, so that each c.c. contains 0.1 mgrm. Cu, and a solution
of ferrocyanide of potash in water is prepared, strength 4 per cent. It
is also convenient to have a solution of nitrate of ammonia, which is
found to render the reaction much more delicate.
The further details are on the well-known lines of colorimetric
estimations.
3. BISMUTH.
§ 811. Bismuth, Bi = 210; specific gravity, 9:799; fusing-point, 264”
(507-2” F.).-Bismuth, as obtained in the course of analysis, is either a
black metallic powder or an extremely brittle bead of a reddish-white
colour. The compounds which it will be necessary to briefly notice are
the peroxide and tersulphide.
$812. The peroxide of bismuth, Bi,0s = 468—specific gravity, 8:211;
Bi, 89-64 per cent. ; 0, 10:36 per cent.—as prepared by igniting the car-
bonate or nitrate, is a pale lemon-coloured powder, which can be fused
without loss of weight, but is reduced on charcoal, or in a stream of
carbon dioxide, to the metallic state. It is also reduced by fusion with
potassic cyanide or by ignition with ammonium chloride.
§ 813. The Sulphide of Bismuth, Bi, Sa-516–Bi, 81.25 per cent. ;
S, 18.75 per cent.—occurs, in the course of analysis, as a brownish-
black or quite black precipitate, insoluble in water, dilute acids, alkalies,
alkaline sulphides, sulphate of soda, and cyanide of potassium, but
dissolving in moderately concentrated nitric acid with separation of
sulphur. It continually increases in weight when dried in the ordinary
way, and is completely reduced when fused with cyanide of potassium.
§ 814. Preparations of Bismuth used in Medicine and the Arts.
(1) Pharmaceutical Preparations:—
Bismuthi Submitras, BiONO3.H2O. —A heavy white powder, insol-
uble in water, and responding to the usual tests for bismuth and nitric
acid. The formula should yield 77 per cent. of bismuth oxide.
Commercial preparations, however, vary from 79 to 82 per cent.
Bismuth Lozenges (Trochisci bismuthi) are composed of submitrate
of bismuth, magnesia carbonate, precipitated lime carbonate, sugar, and
gum, mixed with rose water. Each lozenge should contain 0.13 grm.
(2 grains) of submitrate of bismuth.
§ 815, 816.] - BISMUTH. 653
Solution of Citrate of Bismuth and Ammonia (Liquor Bismuthi et
Ammoniae citratis), a colourless neutral or slightly alkaline fluid,
specific gravity 1-07, responding to the tests for bismuth and ammonia.
As an impurity lead may be present, citric acid being so frequently
contaminated with lead. Carbonate of bismuth (Bismuthi carbonas),
(Bi,0,00), H.O, is a fine white powder answering to the tests for
carbon dioxide and bismuth ; it should yield 89°l per cent. of bismuth
oxide.
A Nitrate of Bismuth, Bi(NO3)3, an oleate of bismuth, an oxide of
bismuth, a subgallate of bismuth (dermatol), and a Subiodide of bismuth
are also used in medicine.
(2) Bismuth in the Arts.”
The chief use of bismuth is in alloys and solders. The chromate is
employed in calico-printing, and the subnitrate as a paint under the
name of pearl-white.
The salts of bismuth also occur in washes for the hair, and
pearl-white is used as a cosmetic, but only to a small extent.
§ 815. Medicinal Doses of Bismuth. –The submitrate and carbon-
ate are prescribed in doses from 0648 to 1296 grim. (1 to 20 grains);
the valerianate, from 1296 to 648 grn. (2 to 10 grains); and the
solution, from 1:7 c.c. to 5-2 c.c. ($ drachm to 1% drachm).
§ 816. Toxic Effects of Bismuth.-From the researches of Meyer
and Steinfeld f on animals, it appears that if birds or mammals are
poisoned with bismuth salts introduced subcutaneously, or by direct
injection, into the veins, death follows in from twenty-four to forty-
eight hours, the fatal issue being preceded by convulsions; after death
the colon is intensely blackened, and it may be ulcerated, while the
small intestimes and the stomach are healthy. If, however, sulphur
preparations are given by the mouth, there is then blackening of the
stomach, and there may also be ulcers. Meyer is of the opinion that
SH2 precipitates bismuth in the parenchyma, and the particles occluding
the capillaries thus cause small local necroses; that which escapes pre-
cipitation is mainly excreted by the kidneys. Poisonous symptoms in
man have been known to occur from the treatment of wounds with
bismuth preparations; I the symptoms have been somewhat similar to
mercurial poisoning ; there have been noticed stomatitis with salivation,
loosening of the teeth, a black colour of the mucous membrane of the
mouth, and ulceration—also catarrh of the intestines, and the inflamma-
* Bismuth is contained in all copper coinage—from the Bactrian coins to our
own ; in all cupreous ores, except the carbonates, and in nearly all specimens of
commercial copper.—Field, Chem. News, xxxvi., 261.
t L. Feyder-Meyer, Rossbach’s pharmak. Unters., iii., 1882, No. 23; Steinfeld,
Wirkwng des Wismut. Inaug. Diss., Dorpat, 1884; Arch, ea:p. P., Bd. xx. 1886.
† B. Med. Jowrmal, 1887, i. 749.
654 POISONS: THEIR EFFECTS AND DETECTION. [$ 817.
tory condition of the kidneys usual when that organ has to excrete
metallic substances not natural to the body, the “metallniere,” or metal
kidney, of the German writers. One case is recorded of death in nine
days of an adult after taking 7-7 grims. (2 drms.) of bismuth submitrate.
The recorded symptoms were a metallic taste in the mouth, pain in the
throat, vomiting, purging, coldness of the surface, and spasms of the
arms and legs. A post-mortem examination showed inflammatory changes
in the gullet, windpipe, and throughout the intestinal canal. Recovery
has, however, taken place from a single dose three times the amount
mentioned. It is possible that the fatal case was due to impure
bismuth.
§ 817. Extraction and Detection of Bismuth in Animal Matters.
—Bismuth appears to be excreted principally by the bowels as sulphide
of bismuth ; but it has also been detected in the urine, spleen, and
liver, and Lubinsky has found it in the saliva and in the epithelium of
the mouth of persons taking one of its preparations. Without denying
the possibility of its existing in a soluble state in the saliva, its presence
in the mouth may, under such circumstances, be ascribed to the
lodgment of particles of submitrate or subcarbonate of bismuth in the
interstices of the teeth, etc. It will then be evident that, if a person is
supposed to have been poisoned by a large dose of bismuth, and the
analyst fail to find it in the stomach, the contents of the bowels should
be next examined.
The extraction of bismuth must be undertaken by nitric acid, and
boiling for at least two hours may be necessary to dissolve it out from
the tissues. Such organs as the liver and spleen are boiled in a finely
divided state with a litre of dilute nitric acid (strength, 5 per cent.), for
the time mentioned, filtered, and the filtrate evaporated to dryness ; the
remainder is then carbonised by strong nitric acid ; and, finally, the
charcoal is boiled with equal parts of mitric acid and water, and
the whole evaporated to dryness. By this method every trace of
bismuth is extracted. The dry residue may now be brought into
solution and tested for bismuth. The best solvent for the nitrate of
bismuth is dilute nitric acid 50 per cent. ; the dry residue is therefore
dissolved in 100 or 200 c.c. of the acid, and fractional parts taken for
examination —
(1) The solution, poured into a large volume of warm distilled water,
gives a crystalline precipitate of submitrate of bismuth. The only metal
giving a similar reaction is antimony, and this is excluded by the
method employed.
(2) The filtered fluid gives on addition of sodic chloride a precipitate
of oxychloride. This again is distinguished from oxychloride of antimony
by its insolubility in tartaric acid.
§ 818.] BISMUTH. 655
(3) Any bismuth precipitate, fused with soda on charcoal, gives a
brittle bead of bismuth. The charcoal is coated, whilst warm, a dark
orange-yellow ; on cooling, citron-yellow. -
(4) The bead may be identified by powdering it, placing it in a short
subliming tube, and passing over it dry chlorine. The powder first turns
black, then melts to an amber-yellow fluid, and finally, by prolonged
heating, sublimes as terchloride of bismuth. ..
(5) A very delicate test proposed by Abel and Field, in 1862,”
specially for the detection of bismuth in copper (but by no means con-
fined to mineral analysis), utilises the fact that, if iodide of lead be
precipitated from a fluid containing the least trace of bismuth, instead of
the yellow iodide the scales assume a dark orange to a crimson tint. A
solution of nitrate of lead is used ; to the nitric acid solution ammonia
and carbonate of ammonia are added; the precipitate is washed, and
dissolved in acetic acid ; and, finally, excess of iodide of potassium is
added. It is said that thus so small a quantity as ‘00025 grm. may be
detected in copper with the greatest ease, the iodide of lead becoming
dark orange; 001 grain imparts a reddish-brown tinge, and 01 grain
a crimson.
(6) A solution of bismuth salt, which must contain no free HCl, when
treated with ten parts of water, 2 of potassium iodide, and 1 part of
cinchonine, gives a red orange precipitate of cinchonine iod.-bismuth.f
(7) Wan Kobell's test, as modified by Hutchings, and proposed more
especially for the detection of bismuth in minerals, is capable of being
applied to any solid compound suspected of containing the metal:—A
mixture of precipitated and purified cuprous iodide, with an equal
volume of flowers of sulphur, is prepared, and 2 parts of this mixture
are made into a paste with 1 part of the substance, and heated on a slip
of charcoal on an aluminium support by the blowpipe flame. If bismuth
be present, the red bismuth iodide will sublime, and on clean aluminium
is easily distinguishable.
Micro-Chemical Test.—Either caesium or rubidium chloride, added
to a hydrochloric acid solution of bismuth salts, gives a double chloride
crystallising in hexagonal tables.
$ 818. Estimation of Bismuth. –The estimation of bismuth, when in
any quantity easily weighed, is, perhaps, best accomplished by fusing the
sulphide, oxide, or other compound of bismuth, in a porcelain crucible
with cyanide of potassium ; the bismuth is reduced to the metallic state,
the cyanide can be dissolved out, and the metallic powder washed (first
with water, lastly with spirit), dried, and weighed.
* Journ. Chem. Soc., 1862, vol. xiv. p. 290; Chem. News, vol. xxxvi. p. 261.
t E. Légar, Bull. de la Soc. Chim., vol. iv., 1888, 91.
# Chem. News, vol. xxxvi. p. 249.
656 POISONS : THEIR EFFECTS AND DETECTION. [$ 818.
Mr. Pattison Muir has shown ‘ that bismuth may be separated from
iron, aluminium, chromium, and manganese, by adding ammonia to the
acid solutions of these metals.
This observation admits of many applications, and may be usefully
taken advantage of in the separation of bismuth from the nitric acid solu-
tion of such animal matters as liver, etc. The acid liquid is partially
neutralised by ammonia, and, on diluting with warm water containing a
little sodium or ammonium chloride, the whole of the bismuth is precipi-
tated as oxychloride, which may be collected, and fused with cyanide of
potassium, as above.
If the bismuth precipitate is in small quantity, or if a number of
estimations of bismuth are to be made, it is most convenient to use a
volumetric process. In the case first mentioned, the oxychloride could
be dissolved in nitric acid, sodium acetate added in excess, and sufficient
acetic acid to dissolve any precipitate which has been produced, and then
titrated by the following method, which we also owe to Mr. Pattison
Muir –
Estimation of Bismuth by Potassium Dichromate.f-A solution
of recrystallised potassium dichromate (strength, 1 per cent.) is
prepared. A known weight of pure bismuthous oxide (BigOs) is
dissolved in excess of nitric acid, and a solution of sodium acetate is
added to this liquid until a copious white precipitate is thrown
down; acetic acid is then added in quantity sufficient to dissolve the
precipitate completely, and to insure that, when the liquid is made
up with water to a fixed volume, no precipitate shall be formed. A
certain volume of this liquid is withdrawn by means of a pipette,
placed in a beaker, and heated to boiling; the potassium dichromate is
then gradually run in from a burette, the liquid being boiled between
each addition of the solution, until a drop of the supernatant liquid
gives a faint reddish-brown coloration when spotted with silver nitrate
on a white slab.
Another very generally applicable volumetric method for bismuth has
been proposed by Mr. Muir, f This depends on the fact (observed by
Sonchay and Leussen),S that normal bismuth oxalate splits up on boiling
into a basic oxalate of the composition Bi,032C2O3 + OH, but slightly
soluble in nitric acid. The process is performed by precipitating the
bismuth by excess of Oxalic acid, dissolving the precipitate (first purified
from free oxalic acid) in dilute hydrochloric acid, and lastly, titrating by
* Pattison Muir on “Certain Bismuth Compounds,” Journ. Chem. Soc., p.
7, 1876.
t Pattison Muir on “Certain Bismuth Compounds,” Journ. Chem. Soc., p. 659,
1879.
£ Ibid., 1877. § Ann. Chem. Pharm., vol. cv. p. 245.
§ 819–821.] SILVER. 657
permanganate. The absence of free hydrochloric acid before precipitating
must be insured.
Electrolytic Estimation. — An adherent deposit of bismuth
from the sulphate or nitrate, suitable for quantitative estimation,
may be obtained by dissolving up to 0-6 grim. with 3–4 grms. of
carbamide or formaldehyde or acetaldehyde in 5–6 c.c. nitric acid
and diluting to 150 c.c. with water; the solution may be warmed
to from 80°-90° ; the current density should be from 0.04–0.08
ampère, and the E.M.F. from 15–19 volts. The precipitated metal
is washed without stopping the current, and ultimately dried at
100° C.#
Karl Wummenauer fuses 1–2 c.c. of glycerol, and lays stress on the
importance of agitating the solution constantly (which is easiest
effected by using a rotating cathode). He recommends a current of
0-1 ampère; this, should indications of peroxide be detected, is
reduced to 0:05 ampère. The temperature of the solution is to be
raised to 50° and maintained at that temperature.
4. SILVER.
$ 819. Silver – 108; specific gravity, 10-5 ; fusing-point, 1023°
(1873 F.).-Silver, as separated in analysis, is either a very white,
glittering, metallic bead, or a dull grey powder. It does not lose weight
on ignition, and is soluble in dilute nitric acid.
$ 820. Chloride of Silver, AgCl = 143-5–specific gravity, 5-552;
Ag, 75.27 per cent. ; Cl, 24*73 per cent.—is a dense, white, curdy
precipitate when produced in the wet way. It is very insoluble in
water, dilute nitric acid, and dilute sulphuric acid ; in many warm
solutions (especially aqueous solutions of the chlorides generally, the
alkaline and alkaline-earthy mitrates, and tartaric acid solutions) the
silver is dissolved to an appreciable extent, but deposited again on
diluting and cooling. The complete solvents of chloride of silver are—
ammonia, cyanide of potassium, and hyposulphite of soda. Chloride
of silver cannot be fused at a high heat without some slight loss by
volatilisation ; on charcoal in the R.F., it fuses very easily to a globule.
It can with soda be reduced to metal, and can also readily be reduced
by ignition in a current of hydrogen, carbon oxide, or carburetted
hydrogen gas.
$821. Sulphide of Silver, Ag,S = 24.8—specific gravity, 7-2; Ag, 87°l
per cent. ; S, 12.9 per cent.—when prepared in the wet way, is a black
precipitate, insoluble in water, dilute acids, and alkaline sulphides. If
* Dmitry Balachowsky, Compt. Rend., czzxi. 1900.
† Zeit, amorgan, Chemie, xxvii. 1901.
658 POISONS : THEIR EFFECTS AND DETECTION. [$ 822.
q-
ignited in hydrogen it may be reduced to the metallic state ; it is soluble
in nitric acid, with separation of sulphur.
$ 822. Preparations of Silver used in Medicine and the Arts.
(1) Medicinal Preparations:– *
Nitrate of Silver, AgNO, ; Ag, 63’51 per cent. ; N,0s, 36.49 per
cent.—This salt is either sold crystallised in colourless rhombic prisms,
or in the form of small white pencils or sticks. It gives the reactions for
silver and nitric acid, and stains the skin black. 100 parts, dissolved in
distilled water, should give, with hydrochloric acid, a precipitate which,
when washed and dried, weighs 83°4 parts. The silver is, however, far
more quickly estimated by the blowpipe than in the wet way. One grm.
fused in a cavity on charcoal should give a little globule of metallic
silver, weighing about 6351 grm. The chief adulterations of this
substance are copper, lead, and nitrate of potash. If all the silver is
precipitated by hydrochloric acid, carefully filtered off, and the filtrate
evaporated to dryness, any residue will denote adulteration or impurity.
Argenti Oxidum, Oxide of Silver, Ag,0=232; Ag, 93-19 per cent.
—A dark olive-brown powder, soluble in ammonia and nitric acid. By
ignition it readily yields metallic silver. The P.B. directs that 29 grains
of the oxide should yield 27 of metallic silver.
Nitrate of Silver and Potash (Argentum nitricum cum kali
nitrico), AgNO3 + KNOs–This preparation is in most of the pharma-
copoeias, Austrian, German, Danish, Swedish, Russian, Swiss, and the
British ; it is directed by the B.P. to be composed of 1 part of silver
nitrate and 1 part of potassic nitrate fused together. A “toughened
silver nitrate * is made by fusing together potassic nitrate 5, silver
nitrate 95. Mild caustic points are used by oculists by fusing 1 of
silver nitrate with 2, 3, 3}, and 4 parts of potassic nitrate.
(2) Silver in the Arts.-The uses of the metal in coinage, articles for
domestic purposes, for ornament, etc., are too well known to require
enumeration. The only forms in which silver is likely to give rise to
accident are the salts used in medicine, photography, in the dyeing of
hair, and in the manufacture of marking inks.
Hair-Dyes.—About one-half of the hair-dyes in use are made with
nitrate of silver. The following are only a few of the recipes:—
Aqua Orientalis.—Grain silver 2 drms., nitric acid 1 oz., steel filings
4 drms, distilled water 13 oz. –the whole finally made up to 3% fluid
OzS., and filtered.
Argentan Tincture.—Nitrate of silver 1 drachm, rose water 1 fluid
oz., sufficient nitrate of copper to impart a greenish tint.
Eau d'Afrique.—Two solutions—one of nitrate of silver, the other
of potash, containing ammonium sulphide.
$ 823, 824.] SILVER. 659
The photographer uses various salts of silver, the chief of which are
—the nitrate, iodide, bromide, cyanide, and chloride of silver.
Marking-Inks.--Some of the more important recipes for marking-
ink are as follows:—
Nitrate of silver, 1.0 part ; hot distilled water, 3-6 parts; mucilage,
previously rubbed with sap-green, 1-0 part. With this is sold a “pounce,”
or preparation consisting of a coloured solution of sodic carbonate.
Another preparation is very similar, but with the addition of ammonia
and some colouring matter, such as indigo, syrup of buckthorn, or sap-
green. A third is made with tartaric acid and nitrate of silver, dis-
solved in ammonia solution, and coloured.
Redwood's Ink consists of equal parts of nitrate of silver and potas-
sic bitartrate, dissolved in ammonia, with the addition of archil green
and sugar; according to the formula, 100 parts should equal 16-6 of
silver nitrate.
Soubeiran's Ink is composed of cupric nitrate 3, argentic nitrate 8,
sodic carbonate 4, and the whole made up to 100 parts, in solution of
ammonia. In one of Mr. Reade's inks, besides silver, an ammoniacal
solution of a salt of gold is used.
§ 823. Medicinal Dose of Silver Compounds.-The nitrate and the
oxide of silver are given in doses from 0162 to 1296 grim. (+ grain to 2
grains). Anything like “1944 to 2592 grm. (3 or 4 grains) would be
considered a large, if not a dangerous dose ; but nothing definite is
known as to what would be a poisomous dose.
§ 824. Effects of Nitrate of Silver on Animals.-Nitrate of silver
is changed into chloride by the animal fluids, and also forms a com-
pound with albumen. Silver chloride and silver albuminate are both
somewhat soluble in solutions containing chlorides of the alkalies, which
explains how a metallic salt, so very insoluble in water, can be absorbed
by the blood.
The action of soluble salts of silver on animals has been several times
investigated. There appears to be some difference between its effects on
warm- and cold-blooded animals. In frogs there is quickly an exaltation
of the functions of the spinal cord; tetanic convulsions appear, similar to
those induced by strychnine; later, there is disturbance of the respiration
and cessation of voluntary motion.
The first symptoms with dogs and cats are vomiting and diarrhoea;
muscular weakness, paralysis, disturbance of the respiration, and weak
clonic convulsions follow. Rouget, as well as Curci, considers that the
action of silver is directed to the central nervous system; there is first
excitement, and then follows paralysis of the centres of respiration and
movement. Death occurs through central asphyxia. According to the
researches of F. A. Falck, subcutaneous injections of silver nitrate into
66O POISONs: THEIR EFFECTS AND DETECTION. [$ 825, 826.
rabbits cause a fall of temperature of 67° to 17.6°, the last being the
greatest fall which, in his numerous researches on the effect of poisons on
temperature, he has seen. -
Chronic poisoning, according to the experiments of Bogoslowsky on
animals, produces emaciation, fatty degeneration of the liver, kidneys, and
also of the muscles—a statement confirmed by others.
$ 825. Toxic Effects of Silver Nitrate in Man—(1) Acute Poison-
ing.—This is very rare. Orfila relates an attempt at suicide; but most
of the cases have been accidental, and of these, in recent times, about
five are recorded, mostly children. The accident is usually due to the
application of the solid nitrate to the throat, as an escharotic, the
stick breaking or becoming detached, and being immediately swallowed ;
such an accident is related by Scattergood.* A piece of silver nitrate
# inch long, slipped down the throat of a child, aged fifteen months—
vomiting immediately occurred, followed by convulsions and diarrhoea;
chloride of sodium was administered, but the child died in six hours. In
other cases paralysis and an unconscious state has been observed.
(2) Chronic Poisoning.—Salts of silver taken for a long period cause
a peculiar and indelible colour of the skin. The body becomes of a greyish-
blue to black colour; it begins first around the nails and fingers, then
patches of a similar hue appear in different parts of the body, and
gradually coalesce, being most marked in those parts exposed to the light.
The colour is not confined to the outer skin, but is also seen in the
mucous membranes. There is also a slight inflammation of the gums,
and a violet line around their edge. Gimpon observed this line after two
months' treatment of a patient by silver nitrate; the whole quantity taken
being 39 grims. (about 60 grains). The peculiar colour of the skin is
only seen after large doses; after 8 grms, taken in divided doses Chaillon
could not observe any change, but after 15 grms. had been taken it was
evident. So also Riemer has recorded a case, in which, after a year's use
of silver nitrate (total quantity 17:4 grms.), a greyish-black colour of the
face was produced, and, when nearly double the quantity had been taken,
the colour had invaded the whole body.
$ 826. Post-mortem. Appearances.—In the acute case recorded by
Scattergood, the mucous membranes of the gullet, of the great curva-
ture of the stomach, and parts of the duodenum and jejunum were
eroded, and particles of curd-like silver chloride adhered to the mucous
membrane.
In the case recorded by Riemer of the long-continued use of silver
mitrate, the serous and mucous membranes were coloured dark ; the
choroid plexus was of a blue-black; the endocardium, the valves of the
heart, and the aorta pale to dark grey, as well as the rest of the vessels;
* Brit. Med. Journ., May 1871.
§ 827.] SILVER. 661
the colouring was confined to the intima. The liver and kidney also
showed similar pigmentation. The pigment (probably metallic silver)
was in the form of very fine grains, and, as regards the skin, was situate
under the rete Malpighia in the upper layer of the corium, and also in
the deeper connective tissue and in the sweat glands. Liouville has
also found the kidneys of a woman similarly pigmented, who took silver
nitrate daily for 270 days, in all about 7 grns., five years before her
death. e
§ 827. Detection and Estimation of Silver.—The examination of
the solid salts of silver usually met with (viz., the nitrate, bromide,
iodide, cyanide, and chloride) is most speedy by the dry method on
charcoal; in this way in less than 120 seconds any practical chemist
could identify each compound. The nitrate, bromide, iodide, and
cyanide, all, if ignited on charcoal, yield buttons of metallic silver—
deflagration, bromine vapours, iodine vapours, and cyanogen vapours
being the respective phenomena observed. Chloride of silver fuses to a
pearl-grey, brown, or black globule on charcoal, according to its purity;
but is only in the R.F. gradually reduced to metal. With soda, or fused
in hydrogen or coal gas, the reduction is rapid enough.
Nitrate of Silver in solution might be identified by a very large
number of tests, since it forms so many insoluble salts. In practice one
is, however, satisfied with three tests, viz.: (1) A curdy precipitate of
chloride, on the addition of hydrochloric acid or alkaline chlorides, soluble
only in ammonia, cyanide of potassium, or hyposulphite of soda ; (2) a
yellow precipitate, but little soluble in ammonia, on the addition of
iodide of potassium ; and (3) a blood-red precipitate on the addition of
chromate of potash.
The separation of silver from the contents of the stomach is best
ensured by treating it with cyanide of potassium ; for, unless a very
large quantity of silver nitrate has been taken, it is tolerably certain
that the whole of it has passed into chloride, and will, therefore, not be
attacked easily by acids. The contents of the stomach, then, or the
tissues themselves, are placed in a flask and warmed for some time with
cyanide of potassium, first, if necessary, adding ammonia. The fluid is
separated from the solid matters by subsidence (for an alkaline fluid of
this kind will scarcely filter), and them decomposed by hydrochloric acid
in excess. The flask containing this fluid is put on one side in a warm
place, and the clear fluid decanted from the insoluble chloride. The
latter is now collected on a filter, well washed with hot water, and then
dried and reduced on charcoal ; or it may be put in a little porcelain
crucible with a rod of zinc and a few drops of hydrochloric acid. The
silver is soon deposited, and must be washed with water, then with
sulphuric acid. By the aid of a wash-bottle the particles of silver are
662 POISONs: THEIR EFFECTS AND DETECTION. [$ 828–830.
now collected on a small filter, again washed, and on the moist mass a
crystal of mitrate of potash and a little carbonate of soda laid. The
whole is then dried, and all the filter cut away, save the small portion
containing the silver. This small portion is now heated on charcoal
until a little button of pure silver is obtained, which may first be
weighed, then dissolved in nitric acid, and tested by the methods
detailed.
In a similar way hair, suspected of being dyed with silver, can be
treated with chlorine gas, and the chloride dissolved in potassic cyanide.
Spots on linen, and, generally, very small quantities of silver, may
be detected by a simple galvanic process:–The substance is treated
with solution of cyanide of potassium, and submitted to a weak galvanic
current, using for the negative plate a slip of copper, for the positive,
platinum ; the silver is deposited on the former.
5. MERCURY.
§ 828. Mercury, Hg = 200; specific gravity, 13:596; boiling-point,
350° (662°F.); it becomes solid at — 39-4 (-39 F.). This well-known
and familiar fluid metal evaporates and sublimes to a minute extent at
all temperatures above 5”.
When precipitated or deposited in a finely divided state, the metal
can be united into a single globule only if it is fairly pure ; very slight
fatty impurities especially will prevent the union. It is insoluble in
hydrochloric acid, soluble to a slight extent in dilute cold sulphuric
acid, and completely soluble in concentrated sulphuric and in nitric
acids. It combines directly with chlorine, bromine, and iodine, which
in presence of free alkali, readily dissolve it. It is unalterable at 100",
and, when exposed to a high temperature, sublimes unchanged.
Mercurous Chloride (Calomel, HgCl = 235-5; specific gravity,
7.178; subliming temperature, 111'6"; Hg, 84.94 per cent., Cl, 15-06
per cent.), when prepared in the wet way is a heavy white powder,
absolutely insoluble in cold, but decomposed by boiling water. It may
be converted into the mercuric chloride by chlorine water and aqua
regia. Chloride of ammonium, potassium, and sodium, all decompose
calomel into metallic mercury and mercuric chloride. It is easily
reduced to metal in a tube with soda, potash, or burnt magnesia.
§ 829. Sulphide of Mercury (HgS, Hg, 86°21 per cent, S, 1379 per
cent.) is a black powder, dissolving in nitromuriatic acid, but very in-
soluble in other acids or in water. It is insoluble in alkaline sulphides,
with the exception of potassic sulphide.
§ 830. Medicinal Preparations of Mercury.—Mercury in the liquid
state has been occasionally administered in constipation; its internal
§ 830.] MERCURY. 663
use is now (or ought to be) obsolete. Gmelin has found samples con-
taminated with metallic bismuth—a metal which only slightly diminishes
the fluidity of mercury; the impurity may be detected by shaking the
mercury in air, and thus oxidising the bismuth. Mercury may also
contain various mechanical impurities, which are detected by forcing
the metal by means of a vacuum pump through any dense filtering
substance. Tin and zinc may be dissolved out by hydrochloric acid, and
all fixed impurities (such as lead and bismuth) are at once discovered
on subliming the metal.
Mercury and Chalk (Hydrargyrum cum creta).-Mercury, 33-33
per cent. ; chalk, 66-67.
Blue Pill (Pilula hydrargyri).—Mercury in a finely divided state,
mixed with confection of roses and liquorice root ; the mercury should
be in the proportion of 33.33 per cent.*
Mercury Plaster (Emplastrum hydrargyri). —Made with mercury,
olive oil, sulphur, and lead plaster; it should contain Hg 33 per cent.,
sulphur 18 per cent.
Ammoniac and Mercury Plaster (Emplastrum ammoniaci cum
hydrargyro).-Gum, ammonia, mercury, olive oil, and sulphur; it
should contain 20 per cent. of Hg, and 1 per cent. of sulphur.
Mercurial Ointment (Unguentum hydrargyri).-Mercury mixed
with lard and suet; the strength should be nearly 50 per cent. mercury
—commercial samples often contain as little as 38 per cent.
Compound Mercury Ointment (Unguentum hydrargyri composi-
tum).-Made with ointment of mercury, yellow wax, olive oil, and
camphor; it should contain 22*2 per cent. Hg.
Liniment of Mercury (Linimentum hydrargyri) is made of
mercurial ointment, solution of ammonia, and liniment of camphor; it
contains about 16% per cent. of mercury. -
Mercurial Suppositories (Suppositoria hydrargyri).-Composed of
* The chemical composition of blue pill varies according to its age. Harold
Senier has made a careful series of analysis, with the following result (Pharm.
Journ., Feb. 5, 1876):— -

Metallic Mercuri Mer orani
Age. Nº | * | *|An ºf
l 18 hours, ſº º 32°49 In OII e. a trace. I 20 66°31
2 3 weeks, . te 32°26 •09 •25 1 20 66 °20
3 3 months, . º 31'60 *24 "62 1*18 66°36
4 3 , , g ſº 31 "I5 '44 I "60 1 - 12 65°69
5 6 , , & to 32'44 ‘50 •80 1-70 64 °56
6 14 , , g tº 29 '86 '98 2' 60 1 °20 65°36
7 19 , , tº e 31°59 •50 2'50 I •00 64°41
8 2 years, & ę 28°40 1 - 80 4 °22 2*10 63 "48
9 (?) e e 30 °23 . 1 °06 3°24 1*03 64' 44
664 POISONS : THEIR EFFECTS AND DETECTION. [$ 830.
ointment of mercury and oil of theobroma. Each suppository should
weigh 15 grains and contain } of its weight of mercurial ointment.
Acetate of Mercury (Mercurous acetate) is not contained in the
B.P., but is officinal on the Continent. It is a salt occurring in white
micaceous scales, soluble in 133 parts of cold water, giving the reactions
of acetic acid and mercury, and very readily decomposed.
Mercuric Ethyl Chloride (Hydrargyrum aethylo-chloratum) is used
as a medicine on the Continent. It occurs in white, glittering, crystal-
line scales, which take on pressure a metallic appearance, and possess a
peculiar ethereal odour; it is but little soluble in water and ether, with
difficulty in cold alcohol, but copiously soluble on boiling, and depositing
crystals on cooling. It sublimes at about 40° without residue ; on
quick heating it burns with a weak flame, developing a vapour of
metallic taste and unpleasant odour. It gives no precipitate with silver
nitrate nor with albumen.
Corrosive Sublimate (Mercuric chloride), HgCl, = 271; Hg, 73-8
per cent. ; Cl, 26.2 per cent.—In commerce this salt occurs in trans-
parent, heavy, colourless masses, which have a crystalline fracture; if
placed in the subliming cell described at p. 260, it sublimes at about
82.2° (180° F.), and melts at higher temperatures. The sublimate is
generally in groups of plates drawn to a point at both ends, in crystalline
needles, or in octahedra with a rectangular base. It dissolves in 16
parts of cold water and about 3 of boiling, and is very soluble in
solutions of the alkaline chlorides; 100 parts of carbon disulphide
dissolve '031 at 8° ; 055 at 25°. One part of sublimate dissolves in
14 parts of glycerin. Acetic ether, methylal, and benzene all dissolve
to some extent corrosive sublimate ; it dissolves also in ether, and can
be, to a great extent, withdrawn from aqueous solutions by this agent.
Alcohol dissolves nearly one-third its weight of the salt, and its own
weight when boiling. It combines with albumen; gives, in solution, a
precipitate of mercuric oxide when tested with solution of potash, a
white precipitate with ammonia, a scarlet with iodide of potassium,
and a black precipitate of finely divided mercury with protochloride of
tin. If a crystal (when placed in the subliming cell) gives a crystalline
sublimate at about the temperature mentioned, and this sublimate
becomes of a red colour when treated with a droplet of iodide of
potassium, it can be no other substance than corrosive sublimate.
Solution of Perchloride of Mercury (Liquor hydrargyri per-
chloridi) is simply 10 grains of perchloride of mercury and chloride of
ammonium in a pint of water ; 100 c.c. therefore should contain 144
mgrms corrosive sublimate.
Yellow Mercurial Lotion (Lotio hydrargyri flava).-Perchloride
of mercury, 18 grains, mixed with 10 ounces of solution of lime.
§ 830.] MERCURY. 665
Calomel” (Hydrargyri subchloridum).-The properties of calomel
have been already described. It sometimes contains as an impurity
corrosive sublimate, which may be dissolved out by ether. Carbonate
of lead, sulphate, and carbonate of baryta, gum, and starch, are the
usual adulterants mentioned. If on the application of heat calomel
entirely sublimes, it must be free from the substances enumerated.
Oleate of Mercury (Hydrargyri oleatum) is composed of 1 part of
yellow oxide and 9 parts of oleic acid.
Black Mercurial Lotion (Lotio hydrargyri nigra).-Calomel, 30
grains, mixed with 10 fluid ounces of lime-water.
Compound Pill of Subchloride of Mercury.—Calomel and sulphur-
ated antimony, each 1 ounce, guaiac resin 2 ounces, castor-oil 1 fluid ounce.
One grain (0648 grnm.) of calomel, and the same quantity of antimony
sulphide, are contained in every 5 grains (324 mgrms.) of the pill mass,
*.e. calomel 20 per cent.
Ointment of Subchloride of Mercury (Unguentum hydrargyri
subchloridi).-Calomel mixed with benzoated lard ; strength about
1 : 6%.
White Precipitate (Hydrargyrum ammoniatum, NH, HgCl).-A
white, heavy powder, subliming by heat without residue, and insoluble
in water, alcohol, and ether. With soda, it yields a metallic sublimate.
When boiled with potash, ammonia is evolved, the yellow oxide of
mercury formed, and chloride of potassium passes into solution. It
should contain 79.5 per cent. of mercury.
The fusible white precipitate of the pharmacopoeia of the Nether-
lands does not appear to be of constant composition, varying between
69:4 to 65.6 per cent. of mercury.i. It melts on heating, and leaves as
a residue chloride of sodium.
Commercial white precipitate is frequently adulterated; Barnes has
found carbonates of lead and lime, the latter to the extent of nearly 2 per
cent. Calomel, according to Nickles,S has been substituted for white
precipitate, but this was several years ago. The methods for detection
are obvious.
Ointment of Ammoniated Mercury (Unguentum hydrargyri am-
moniati).-1 part of ammoniated mercury mixed with 9 parts of simple
ointment.
Red Iodide of Mercury (Hydrargyrum iodidum rubrum, HgI2).—
A crystalline powder of a scarlet colour, becoming yellow on gentle
* It would appear that in America a cosmetic is in use, consisting of calomel
mixed into a paste with water.—Wide “A Dangerous Cosmetic,” by C. H. Piesse,
Analyst (25), 1878, p. 241.
t Hirsch, Die Prüfung der Arzenečmittel.
† Proceed. Brit. Pharm. Conf., 1867, p. 10.
§ Jowrm. Pharm. et Chimo., le Série, 1858, vol. viij. p. 399.
666 POISONS : THEIR EFFECTS AND DETECTION, [$ 830.
heating. It is sparingly soluble in water, one part requiring from 6000
to 7000 parts; soluble in 130 parts of cold, 150 of hot alcohol; and
dissolving freely in ether, or in aqueous solution of iodide of potassium.
Ointment of Red Iodide of Mercury (Unguentum hydrargyri iodidi
rubri)—16 grains of the substance mixed with an ounce of simple
ointment.
Green Iodide of Mercury (Hydrargyri iodidum viride, HgI).—A
dingy, greenish-yellow powder, darkening on exposure to light, and
easily transformed by heat into the red iodide.
Red Oxide of Mercury (Hydrargyri oxidum rubrum), Hg,0= 216;
Hg, 92.12 per cent. ; specific gravity, 11 to 11:3; small, red, shining,
crystalline scales, slightly soluble in water, requiring about 20,000 parts;
entirely soluble in hydrochloric acid. By a heat below redness it may
be volatilised, and at the same time decomposed into mercury and
oxygen. Its principal impurity is nitric acid, readily detected by the
usual tests, or by heating in a test-tube, when, if nitric acid is present,
orange vapours will be evolved. Fixed red powders (such as brick-dust
and minium) are detected by being left as a residue, after the application
of heat sufficient to volatilise the mercury. An ointment (strength 1:8)
is officinal.
Sulphate of Mercury.—A white crystalline powder, converted by
water into the very slightly soluble basic salt of mercury, known as
Turbith mineral, HgSO2Hg0
Turbith, or Turpeth, Mineral is contained in the French pharma-
copoeia, HgSO,2HgO; Hg, 82.4 per cent. ; specific gravity, 8:319. It
requires for solution 2000 parts of cold and 600 of boiling water, but
dissolves with tolerable ease in hydrochloric acid.
The Sulphide of Mercury, known in commerce under the name of
Ethiops mineral, is officinal in France, the Netherlands, and Germany.
Its properties have been already described. The German and Dutch
pharmacopoeias require in it 50, the French only 33% per cent. of
metallic mercury.
Hahneman's Soluble Mercury (Hydrargyrum solubile Hahnemanni)
is officinal in the Dutch pharmacopoeia. As found in commerce it con-
tains metallic mercury, mitric acid, and ammonia. The mercury should
be in the proportion of 86.33 per cent., the ammonia 2:44 per cent.
Crystallised Nitrate of Mercury (Hydrargyrum nitricum oxidu-
latum) is officinal in the pharmacopoeias of Germany, Switzerland, and
France. The salt is in white crystals, giving the reactions of nitric acid
and mercury, decomposed by the addition of water, but fully soluble in
water, if first moistened with nitric acid. The formula of the neutral
salt is Hg2NOAHgC2H2O, which requires 69.4 per cent. of mercury.
An acid solution of mercuric nitrate is officinal.
§ 831.] MERCURY. 667
An Ointment of Nitrate of Mercury (Unguentum hydrargyri
nitratis)—often called citrine ointment—is contained in the B.P. ; it is
made with 4 parts of mercury, nitric acid 12, lard 15, olive oil, 32; the
strength is about 1 in 15%.
A Chloride of Mercury and Quinine exists in commerce, prepared
by mixing 1 part of corrosive sublimate in solution with three parts of
quinine chloride, evaporating, and crystallising.
Cyanide of Mercury, HgCy, is contained in the French pharma-
copoeia. It occurs in small, colourless, prismatic crystals, easily soluble
in water. If to the solution chloride of tin be added, a black precipitate
of reduced metal and stannous oxide is thrown down, and the odour of
prussic acid is developed.
Mercuric Sulphide (Sulphide of Mercury, Cinnabar, Vermilion) is
officinal in Germany, the Netherlands, and France ; HgS = 232; specific
gravity, solid, 82; Hg, 86°21 per cent., O, 13.79 per cent. For medicinal
purposes it is made artificially. It is a beautiful red powder insoluble in
all alkaline and all acid liquids, with the exception of aqua regia. The
solution gives the reactions of a sulphide and mercury. On heating, it
must burn away entirely without residue ; adulterations or impurities
are—minium, lead, copper, and other metals. The detection of minium
is conveniently executed in the dry way. Pure cinnabar, when heated
in a matrass, gives a black sublimate, which becomes red on friction.
If minium is present, sulphide of lead remains as a residue, and may be
recognised on coal; the same remark applies to sulphide of antimony.
If it be desired to take the percentage of mercury in cinnabar, equal
parts of oxalate and cyanide of potassium should be well mixed with
the cinnabar, and heated in the bent tube described at p. 685 ; by this
means the whole of the metallic mercury is readily obtained.*
§ 831. Mercury in the Arts.—The use of mercury in the arts is so
extensive, that any one in analytical practice is almost certain occasion-
ally to meet with cases of accidental poisoning, either from the vapouri
or some of its combinations.
Quicksilver is used in the extraction of gold, the silvering of mirrors,
the construction of barometers and various scientific instruments and
* Dr. Sutro has published a case (quoted by Taylor), in which the vapour of
vermilion, applied externally, produced poisonous symptoms; yet, according to
Polak, the Persians inhale it medicinally, smoking it with tobacco, catechu, muci-
lage, etc., the only bad effect being an occasional stomatitis. –Eulenberg, Gewerbe
Hygiene, p. 741. &
t A singular case is cited by Tardieu (Etude méd.-légal sur l'Empoisonnement),
in which a man, supposing he had some minerals containing gold, attempted the
extraction by amalgamation with mercury. He used a portable furnace (for the
purpose of volatilising the mercury) in a small room, and his wife, who assisted him,
suffered from a very well-marked stomatitis and mercurial eruption.
668 POISONS : THEIR EFFECTS AND DETECTION. [$ 832.
appliances; also for the preservation of insects, and occasionally for their
destruction.” An alloy with zinc and cadmium is employed by dentists
for stopping teeth ; but there is no evidence that it has been at all
injurious, the mercury, probably, being in too powerful a state of com-
bination to be attacked by the fluids in the mouth, f Cinnabar has
also been employed to give a red colour to confections, and it may be
found in tapers, cigarette papers, and other coloured articles. The
nitrate of mercury in solution finds application in the colouring of horn,
in the etching of metals, in the colouring of the finer sorts of wool, and
in the hat manufacture.
The sulphocyanide of mercury gives, when burnt, a most abundant
ash, a fact utilised in the toy known as Pharaoh's serpent ; the products
of combustion are mercurial vapours and sulphurous anhydride. That
the substance itself is poisonous is evident from the following experi-
ment:—‘5 grn. was given to a pigeon without immediate result ; but
ten hours afterwards it was indisposed, refused its food, and in forty
hours died without convulsions.j.
§ 832. The more Common Patent and Quack Medicines
containing Mercury.
Mordant's Norton’s Drops. –This patent medicine is a mixture of the tincture
of gentian and ginger, holding in solution a little bichloride of mercury, and coloured
with cochineal.
Solomon's Anti-impetigines is a solution of bichloride of mercury, flavoured
and coloured.
Poor Man's Friend.—An ointment of nitrate of mercury.
Brown's Lozenges.—Each lozenge contains 4 grain of calomel, and 3% grains of
resinous extract of jalap; the rest is white sugar and tragacanth.
Ching's Worm Lozenges.—Each lozenge contains 1 grain of calomel ; the rest
white sugar and tragacanth, with Saffron as a colouring matter.
Storey's Worm Cakes.—Each cake contains 2 grains of calomel, 2 grains of
cinnabar, 6 grains of jalap, 5 grains of ginger, and the remainder sugar and water.
Wright's Pearl Ointment is said to be made up of 8 ozs. of white precipitate
rubbed to a cream in 1 pint of Goulard's extract, and to the mixture is added 7 lbs.
of white wax and 10 lbs. of olive oil.
Keyser's Pills.-The receipt for these pills is—red oxide of mercury 1% oz., dis-
tilled vinegar (dilute acetic acid) 1 pint ; dissolve, add to the resulting solution
manma 2 lbs., and triturate for a long time before the fire until a proper consistence
is attained ; lastly, divide the mass into pills of 1% grain each.
Mitchell’s Pills. -Each pill contains aloes 8 grain, rhubarb 1:6 grain, calomel
‘16 grain, tartar emetic “05 grain.
Many Antibilious Pills will be found to contain calomel, a few mercury in a
finely divided state.
* Forty-three persons were salivated from fumigating rooms with mercury for the
purpose of destroying bugs (Sonnenschein's Handbuch, p. 96).
| More danger is to be apprehended from the vulcanised rubber for artificial
teeth ; and, according to Dr. Taylor, accidents have occurred from the use of such
supports or plates. # Eulenberg, op. cit., p. 472.
§ 833–835.] MERCURY. - 669
§ 833. Mercury in Veterinary Medicine.—Farmers and farriers
use the ointment (blue ointment) to a dangerous extent, as a dressing
for the fly, and wholesale poisoning of sheep has been in several
instances the consequence.* Ethiops mineral and Turpeth mineral are
given to dogs when affected by the distemper, worms, or the
mange. Mercury, however, is not very frequently given to cattle by
veterinary surgeons, ruminants generally appearing rather susceptible
to its poisonous effects.
§ 834. Medicinal and Fatal Dose—Horses.—Cinnabar 14.2 grims.
(; oz.), calomel 14.2 grims. (3 oz.) or more, corrosive sublimate 13 to
38 grn. (2 to 6 grains), and as much as 13 grm. (20 grains) have been
given in farcy.
Cattle.—Mercury with chalk 3-8 to 11:6 grms. (1 to 3 drms.),
calomel 3-8 to 7-7 grms. (1 to 2 drnms.) for worms; '65 to 13 grim. (10
to 20 grains) as an alterative; Ethiops mineral, 7-7 to 15:5 grms. (2 to
4 drms.).
Dogs.-Ethiops or Turpeth mineral 13 to 13 grn. (2 to 20 grains),
according to the size.
Fowls.—Mercury and chalk are given in fractions of a grain.
Hogs are also treated with mercury and chalk; the dose usually
given does not exceed 32 grim. (5 grains).
It may be remarked that many of the doses quoted appear very
large; the writers cannot but consider that 20 grains of corrosive sub-
limate administered to a horse would be more likely to kill the animal
than to cure the disease.
Man.—Corrosive sublimate has been fatal in a dose so small
as '19 grm. (3 grains); white precipitate has caused dangerous
symptoms in doses of from 19 to 2-6 grm. (30 to 40 grains); the
cyanide of mercury has killed a person in a dose of 64 grim. (10
grains)—Christison ; and Turpeth mineral has proved fatal in doses
of 2-6 grms. (40 grains).
- Other preparations of mercury have also been fatal, but a doubt has
existed as to the precise quantity. Sometimes, also, there is probably a
chemical change in the substance, so that it is impossible to state the
fatal dose. For example, it is well known that calomel, under the in-
fluence of alkaline chlorides, can be converted into the bichloride—a
fact which probably explaims the extensive corrosive lesions that have
been found after death from large doses of calomel.
$835. Poisoning by Mercury— Statistics.—In the Registrar-
General's death returns for the ten years ending 1903, it appears that
* Twenty-five tons of blue ointment are said to have been sold to farmers by a
druggist in Boston, Lincolnshire, in the course of a single year.—Taylor's Medical
Jurisprudence, vol. i. p. 279.
670 POISONS : THEIR EFFECTS AND DETECTION. [$ 836.
in England the deaths from mercurial poisoning * were 62 males,
35 females; of these, 48 males and 18 females were cases of suicide,
the remainder were referred to accident.
§ 836. (1) Effects of Mercurial Vapour, and of the Non-Corrosive
Compounds of Mercury.
The effects of the different compounds of mercury may be divided
into two groups, viz.: (1) Those caused by the finely divided metal and
the non-corrosive compounds; (2) the effects caused by the corrosive
compounds.
(a) Vegetable Life.—Priestley and Boussingault have shown that
plants under a glass shade in which mercury is exposed in a saucer,
first exhibit black spots on the leaves; ultimately, the latter blacken
entirely, and the plants die.
(b) Animal Life.—Mercury in the form of vapour is fatal to animal
life, but it is only so by repeated and intense application. Eulenberg f
placed a rabbit under a large glass shade, and for four days exposed it
daily for two hours to the volatilisation of 2 grns. of mercury on warm
sand ; on the sixth and seventh day 1.5 grn. was volatilised. On the
fifteenth day there was no apparent change in the aspect of the animal;
5 grms. of mercury were then heated in a retort, and the vapour blown
in at intervals of ten minutes. Fourteen days afterwards the gums
were reddened and swollen, and the appetite lost; the conjunctivae
were also somewhat inflamed. The following day these symptoms
disappeared, and the animal remained well.
In another experiment 20 grms. of mercury were volatilised, and a
rabbit exposed to the vapour under a small glass shade. The following
day the conjunctivae were moist and reddened; two days afterwards 10
grms. of mercury were volatilised in the same way; and in two days'
interval other 10 grims. were volatilised in three-quarters of an hour.
There was no striking change noticeable in the condition of the animal,
but within forty-eight hours it was found dead. The cause of death
proved to be an extravasation of blood at the base of the brain. The
bronchia were reddened throughout and the lungs congested. Mercury,
as with man, is also readily absorbed by the broken or unbroken skin;
hence thousands of sheep have been poisoned by the excessive and
ignorant external application of mercurial ointment as a remedy against
the attacks of parasites. The sheep become emaciated, refuse food, and
seem to be in pain, breathing with short quick gasps.
In experiments on rabbits, dogs, and warm-blooded animals generally,
* The deaths are registered under the term “Mercury,” but the majority are
poisonings by “Corrosive Sublimate.”
t Op. cit., p. 728.
§ 837.] MERCURY. 671
salivation and stomatitis are found to occur as regularly as in man ; So
also in animals and man, paralytic and other nervous affections have
been recorded.
§ 837. (c) Effects on Man.—In 1810 * an extraordinary accident
produced, perhaps, the largest wholesale poisoning by mercurial vapour
on record. The account of this is as follows:—H.M.S. Triumph, of
seventy-four guns, arrived in the harbour of Cadiz in the month of
February 1810; and in the following March, a Spanish vessel, laden
with mercury for the South American mines, having been driven on
shore in a gale, was wrecked. The Triumph saved by her boats 130
tons of the mercury, and this was stowed on board. The mercury
was first confined in bladders, the bladders again were enclosed in small
barrels, and the barrels in boxes. The heat of the weather, however,
was at this time considerable; and the bladders, having been wetted
in the removal from the wreck, soon rotted, and mercury, to the
amount of several tons, was speedily diffused as vapour through the
ship, mixing more or less with the bread and the other provisions. In
three weeks 200 men were affected with ptyalism, ulceration of the
mouth, partial paralysis, and, in many instances, with diarrhoea. The
Triumph was now ordered to Gibraltar, the provisions were removed,
and efforts were made to cleanse the vessel. On restowing the hold,
every man so employed was salivated. The effects noted were not
confined to the officers and ship's company, for almost all the stock died
from the fumes—mice, cats, a dog, and even a canary bird shared the
same fate, though the food of the latter was kept in a bottle closely
corked up. The vapour was very deleterious to those having any
tendency to pulmonic affections. Three men, who had never complained
before they were saturated with mercury, died of phthisis; one, who
had not had any pulmonic complaint, was left behind at Gibraltar,
where his illness developed into a confirmed phthisis. Two died from
gangrene of the cheeks and tongue. A woman, confined to bed with a
fractured limb, lost two of her teeth; and many exfoliations of the
jaw took place.
Accidents from the vapour of mercury, quite independently of its
applications in the arts, have also occurred, some of them under curious
circumstances; such, for example, is the case mentioned in the footnote
to p. 667. Witness, again, a case mentioned by Seidel, f in which a
female, on the advice of an old woman, inhaled for some affection or
other 2.5 grms. of mercury poured on red-hot coals, and died in ten
days with all the symptoms of mercurial poisoning.
* “An Account of the Effect of Mercurial Vapours on the Crew of His Majesty's
Ship Triumph, in the year 1810.”—Phil. Trans., 113, 1823.
t Maschka's Handbuch, Bd. ii. 295.
672 POISONS: THEIR EFFECTS AND DETECTION. [$838,839.
The metal taken in bulk into the stomach has been considered non-
poisonous, and, probably, when perfectly pure, it is so; we have,
however, the case of a girl who swallowed 4% ozs. by weight of the
liquid metal, for the purpose of procuring abortion—this it did not
effect; but, in a few days, she suffered from a trembling and shaking
of the body and loss of muscular power. These symptoms continued
for two months, but there was no salivation and no blue marks on the
gums. This case is a rare one, and a pound or more has been taken
without injury.
§ 838. Absorption of Mercury by the Skin.—Mercury in a finely
divided form, rubbed into the skin, is absorbed, and all the effects of
mercurialism result. This method of administering mercury for medi-
cinal purposes has long been in use, but, when the inunction is excessive,
death may occur. Thus, Leiblinger records a case in which three persons
were found dead in bed; the day before they had rubbed into the body,
for the purpose of curing the itch, a salve containing 270 grims. of
mercury finely divided. -
It is difficult to say in what proportion workers in mercury, such as
water-gilders, etc., suffer. According to Hirt, not only do 15 to
2.1 per cent. of the workmen employed in smelting mercury ores
suffer acutely, but as high a proportion as 87 per cent, are slightly
affected.
§ 839. Symptoms of Poisoning by Mercury Vapour.—The symp-
toms of poisoning by mercury vapour, or by the finely divided metal, are
the same as those which arise from the corrosive salts, with the exception
of the local action. In mild cases there is pallor, languor, and sore mouth
(from slightly inflamed gums), footid breath, and disorder of the diges-
tive organs. If the action is more intense, there is an inflammation of
the gums and, indeed, of the whole mouth, and salivation, which is
sometimes so profuse that as much as two gallons of saliva have been
secreted daily. The saliva is alkaline, has a bad odour, and its specific
gravity in the early stages is increased, but ultimately becomes normal ;
the gums are raised into slight swellings, which gradually enlarge and
coalesce. The teeth that are already carious, decay more rapidly; they
become loose, and some may be shed; the inflammatory action may
extend to the jaw, and necrosis of portions of the bone is no unusual
occurrence. On recovery the cheeks sometimes form adhesions with the
gums, and cicatrices always mark the loss of substance which such an
affection entails. With the stomatitis there are disturbances of the
gastro-intestinal tract—nausea and vomiting, pain in the stomach, and
diarrhoea alternating with constipation. Conjunctivitis is very common,
both in man and animals, from exposure to mercury vapours. The
further action of the metal is shown in its profound effects on the
§ 840.] MERCURY. 673
nervous system. The patient is changed in his disposition, he is excit-
able, nervous, or torpid; there are sleeplessness and bad dreams, at the
same time headache, noises in the ears, giddiness, faintings, etc.
§ 840. Mercurial Tremor—Mercurial tremor * may follow, or ac-
company the above state, or it may be the chief and most prominent
effect. It specially affects the arms, partly withdrawing the muscles
from the control of the will, so that a person affected with mercurial
tremor is incapacitated for following any occupation, especially those
requiring a delicate and steady touch. In cases seriously affected, the
tremor spreads gradually to the feet and legs, and finally the whole
body may be invaded. The patient is no longer master of his muscles
—the muscular system is in anarchy, each muscle aimlessly contracting
and relaxing independently of the rest—the movement of the legs
becomes uncertain, the speech stuttering, the facial expressions are
even distorted into grimaces, and the sufferer sinks into a piteous state
of helplessness. The convulsive movements generally cease during
sleep. The tremors are accompanied by interference with the functions
of other organs: the respiration is weakened and difficult ; dyspnoea, or
an asthmatic condition, results; the pulse is small and slow ; paresis,
deepening into paralysis of the extremities, or of a group of muscles,
follows; and, lastly, if the condition is not alleviated, the patient
becomes much emaciated and sinks from exhaustion. Pregnant women
are liable to abortion, and the living infants of women suffering from
tremor have also exhibited tremor of the limbs.
In the case of the “mass poisoning” on board the Triumph, it
has been mentioned that several of the sailors became consumptive, and
the same effect has been noticed among all workers in the metal ; it is
now, indeed, an accepted fact that the cachexia induced by mercurial-
ismus produces a weak habit of body specially liable to the tuberculous
infection.
The course of the poisoning is generally more rapid when it has
resulted from the taking of mercury internally as a medicine than when
inhaled by workers in the metal, e.g. a patient suffering from mercurial
tremor shown to the Medical Society by Mr. Spencer Watson in 1872,
had resisted for seven years the influence of the fumes of mercury ; and
then succumbed, exhibiting the usual symptoms. Idiosyncrasy plays a
* A case of mercurial tremor (in Bericht. des K. K. allgem. Krankenhauses ºw
Wien im Jahre 1872, Wien, 1873) is interesting, as showing the influence of preg-
nancy. A woman, twenty years of age, employed in making barometers, had, in
1869, mercurial tremor and salivation. During a three months’ pregnancy the
tremor ceased, but again appeared after she had aborted. She again became preg-
nant, and the tremor ceased until after her confinement in November 1871. The
tremor was so violent that the patient could not walk ; she also had stomatitis ; but
ultimately, by treatment with galvanism and other remedies, she recovered.
43
674 POISONS : THEIR EFFECTS AND DETECTION. [$ 841.
considerable rôle ; some persons (and especially those whose kidneys are
diseased) bear small doses of mercury ill, and are readily salivated or
affected ; this is evidently due to imperfect elimination.
§ 841. Mercuric Methide, Hg(CH3)2. This compound is obtained
by the action of methyl iodide on sodium amalgam in the presence of
acetic ether. It is a dense, stable liquid, of highly poisonous properties.
In 1865, mercuric methide, in course of preparation in a London
laboratory, caused two cases of very serious slow poisoning.” One was
that of a German, aged 30, who was engaged in preparing this com-
pound for three months, and during this time his sight and hearing
became impaired ; he was very weak, his gums were sore, and he was
ultimately admitted into St. Bartholomew's Hospital, February 3rd,
1865. His urine was found to be albuminous, and his mental faculties
very torpid. On the 9th he became noisy, and had to be put under
mechanical restraint. On the 10th he was semi-comatose, but there
was no paralysis; his breath was very offensive, his pupils dilated ; at
intervals he raised himself and uttered incoherent howls. There was
neither sensation nor motion in the left leg, which was extended rigidly ;
the knee and the foot were turned slightly inward. On the 14th he
died insensible.
The only appearance of note seen at the autopsy was a congestion of
the grey matter in the brain ; the kidneys and liver were also congested,
and there were ecchymoses in the kidneys. -
The second case—a young man, aged 23, working in the same
laboratory—was admitted into the hospital, March 28th, 1865. In the
previous January he had been exposed to the vapour of mercuric
methide for about a fortnight ; during the illness of the other assistant
he felt ill and weak, and complained of Soreness of the gums and loose-
ness of the teeth. He had also dimness of vision, pain and redness of
the eyes, giddiness, nausea and vomiting, the ejected matters being
greenish and watery. At the beginning of March his sight and taste
became imperfect—all things tasted alike ; his tongue was numb and
his gums sore, he was also salivated slightly. A week before admission
he lost his hearing, and first his hands and then his feet became numb ;
on admission his breath was very offensive, his pupils dilated ; the sight
impaired ; he was very deaf, and his powers of speech, taste, and smell
were deficient. There was anaesthesia of the body, and the movement of
the limbs was sluggish and difficult. He continued in the hospital for
nearly a month, with but little change. On April 24th, it was noticed
that he was getting thinner and slightly jaundiced ; he moved his arms
aimlessly in an idiotic manner, and passed his urine involuntarily. On
April 27th he was more restless, and even violent, shrieking out, and
* St. Barth. Hosp. Reports, vol. i., 1866, p. 141.
§ 842.] MERCURY. 675
making a loud, incoherent moise, or laughing foolishly ; he passed his
motions and urine beneath him. On July 7th he was in a similar state
—perfectly idiotic. He died on April 7th, 1866, about a year and three
months from his first exposure to the vapour; the immediate cause of
death was pneumonia. The post-mortem appearances of the brain and
membranes differed little from the normal state ; the grey matter was
pink, but otherwise healthy; there was a considerable amount of
cerebro-spinal fluid ; the arachnoid along the longitudinal fissure was
thickened; the total weight of the brain with medulla was 41 ozs. The
stomach was of enormous size ; the pyramids of the kidneys were con-
jested, as was also the small intestine; the lungs showed the usual signs
of pneumonia.”
§ 842. Effects of the Corrosive Salts of Mercury.—The type of the
corrosive salts is mercuric chloride, or corrosive sublimate—a compound
which acts violently when administered, either externally or internally,
in large doses. If the poison has been swallowed, the symptoms come
on almost immediately, and always within the first half hour; the whole
duration also is rapid. In 36 cases collected by F. A. Falck, 11 died on
the first or second day, and 11 on the fifth day; so that 61 per cent. died
in five days—the remainder lived from six to twenty-six days. The
shortest fatal case on record is one communicated to Dr. Taylor by
Mr. Welch ; in this instance the man died from an unknown quantity
within half an hour.
In the very act of swallowing, a strong metallic taste and a painful
sensation of constriction in the throat are experienced. There is a burn-
ing heat in the throat extending downwards to the stomach. All the
mucous membranes with which the solution comes in contact are attacked,
shrivelled, and whitened; so that, on looking into the mouth, the appear-
ance has been described as similar to that produced by the recent appli-
cation of silver nitrate. The local changes may be so intense as to cause
Oedema of the glottis, and death through asphyxia. In a few minutes
violent pain is felt in the stomach; so much so, that the sufferer is
drawn together, and is in a fainting condition ; but there are rare cases
in which pain has been absent. There are nausea and vomiting, the
ejected matters being often streaked with blood; after the vomiting there
is purging; here also the motions are frequently bloody. ; The tempera-
* St. Barth. Hosp. Reports, vol. ii. p. 211.
t The effects on animals are similar to those on man. Richard Mead gave a dog
with bread 3-8 grms. (60 grains) of corrosive sublimate :-‘‘Within a quarter of an
hour he fell into terrible convulsions, casting up frequently a viscid frothy mucus,
every time more and more bloody, till, tired and spent with this hard service, he lay
down quietly, as it were, to sleep, but died the next morning.”
f The mixture of blood with the evacuations is more constantly observed, in
poisoning by corrosive sublimate than in poisoning by arsenic, coppel; or lead. ' ' , , ;
*
*
*
676 POISONS: THEIR EFFECTS AND DETECTION. [$ 843–845.
ture of the body sinks, the respiration is difficult, and the pulse small,
frequent, and irregular. The urine is generally scanty, and sometimes
completely suppressed.* Sometimes there is profuse haemorrhage from
the bowel, stomach, or other mucous membrane, and such cases are
accompanied by a considerable diminution of temperature. In a case
recorded by Loewy, f after a loss of blood by vomiting and diarrhoea, the
temperature sank to 33.4°. The patient dies in a state of collapse, or
insensibility, and death is often preceded by convulsions.
§ 843. Two remarkable cases of death from the external use of corro-
sive sublimate are recorded by Anderseck. An ointment, containing
corrosive sublimate, was rubbed into the skin of two girls, servants, in
order to cure the itch. The one, during the inunction, complained of a
burning of the skin; the other also, a little while after, suffered in the
same way. During the night the skin of each swelled, reddened, and
became acutely painful. There were thirst and vomiting, but no diarrhoea.
On the following day there was an eruption of blebs or little blisters.
On the third day they had diarrhoea, tenesmus, fever, and diminution of
the renal secretion; on the fourth day, foºtid breath, stomatitis, hyper-
aesthesia of the body, and a feeling of “pins and needles” in the hands
and feet were noted. The first girl died in the middle of the fifth day,
fully conscious ; the other died on the sixth. So also Taylor f gives the
case of a girl, aged 9, who died from the effects of an alcoholic solution
of corrosive sublimate (strength, 80 grains to the oz.) applied to the
scalp as a remedy for ringworm. The same author $ further quotes the
case of two brothers who died—the one on the fifth, the other on the
eleventh day—from the effects of absorbing corrosive sublimate through
the unbroken skin.
§ 844. The Nitrates of Mercury are poisons, but little (if at all)
inferior in corrosive action to mercuric chloride. Death has resulted
from both the external and internal use. Application of the nitrate as
an escharotic to the OS uteri, in one case, produced all the symptoms of
mercurial poisoning, but the woman recovered; in another case," its use
as a limiment caused death.
§ 845. When taken internally, the symptoms are scarcely different
from those produced by corrosive sublimate. It seems an unlikely
vehicle for criminal poisoning, yet, in the case of Reg. v. E. Smith
(Leicester Summer Assizes, 1857), a girl was proved to have put a solu-
* In a case recorded by Dr. Wegeler (Casper's Wochenschrift, January 10, 1846,
p. 30), a youth, aged 17, swallowed 11-6 grms. (3 drachms) of the poison. No pain
was experienced on pressure of the abdomen; he died on the sixth day, and during
the last three days of life no urine was secreted.
+ Vierteljahrsschr, für ger. Med., 1864, vol. i. p. 187.
... + Cº. cil. . § Poisons, 1848, p. 394.
;: ||..}º. Hazette, vol. xlv. p. 1025. T I'dim. Monthly Journal, 1864, p. 167.
$846–849.] MERCURY. 677
tion of nitrate of mercury in some chamomile tea, which had been pre-
scribed for the prosecutrix. The nauseous taste prevented a fatal dose
being taken ; but the symptoms were serious.
$846. Mercuric Cyanide acts in a manner very similar to that of
corrosive sublimate, 13 grim. (about 20 grains) in one case,” and in
another f half the quantity, having destroyed life.
§ 847. White Precipitate (ammoniated mercury), as a poison, is weak.
Out of fourteen cases collected by Taylor, two only proved fatal; one of
these formed the subject of a trial for murder, Reg. v. Moore (Lewes
Lent Assizes, 1860). The effects produced are vomiting, purging, etc.,
as in corrosive sublimate. { Other preparations of mercury, such as the
red iodide, the persulphide, and even calomel, Š have all a more or less
intense poisonous action, and have caused serious symptoms and death.
§ 848. Treatment of Acute and Chronic Poisoning.—In acute
poisoning, vomiting usually throws off some of the poison, if it has been
swallowed ; and the best treatment seems to be, to give copious albu-
minous drinks, such, for example, as the whites of eggs in water, milk,
and the like. The vomiting may be encouraged by subcutaneous
injections of apomorphine. The after-treatment should be directed to
eliminating the poison, which is most safely effected by very copious
drinks of distilled water (see “Appendix").
The treatment of slow poisoning is mainly symptomatic ; medicinal
doses of zinc phosphide seem to have done good in mercurial tremors.
Potassic iodide is also supposed to assist the elimination of mercury.
§ 849. Post-mortem Appearances.—The pathological effects seen
after chronic poisoning are too various to be distinctive. In the museum
of the Royal College of Surgeons there is (No. 2559) the portion of a
colon derived from a lady aged 74. || This lady had been accustomed
for forty-three years to take a grain of calomel every night; for many
years she did not suffer in health, but ultimately she became emaciated
and cachectic, with anasarca and albuminuria. The kidneys were found
to be granular, and the mucous membrane of a great part of the
intestine of a remarkable black colour, mottled with patches of a lighter
hue, presenting somewhat the appearance of a toad's back. From the
portion of colon preserved, mercury was readily obtained by means of
Reinsch's test. The black deposit is in the submucosa, and it is,
without doubt, mercurial, and probably mercury sulphide. In acute
poisoning (especially by the corrosive salts) the changes are great and
* Orfila, i. p. 735. f Christison, p. 427.
# See Dr. Th. Stevenson, “Poisoning by White Precipitate,” Guy's Hospital
Reports, vol. xix. p. 415.
§ Seidel quotes a case from Hasselt, in which a father, for the purpose of
obtaining insurance money, killed his child by calomel.
| Path. Soc. Trams., xviii. 111.
678 POISONS : THEIR EFFECTS AND DETECTION. [$850.
striking. After rapid death from corrosive sublimate, the escharotic
whitening of the mouth, throat, and gullet, already described, will be
seen. The mucous membrane right throughout, from mouth to anus,
is more or less affected and destroyed, according to the dose and con-
centration of the poison. The usual appearances in the stomach are
those of intense congestion, with ecchymoses, and portions of it may be
destroyed. Sometimes the coats are very much blackened ; this is
probably due to a coating of sulphide of mercury.
In St. George's Hospital Museum (Ser. ix.43, y. 337) there is a stomach, rather
large, with thickened mucous coats, and having on the mucous surface a series of
parallel black, or black-brown lines of deposit ; it was derived from a patient who
died from taking corrosive sublimate. With the severe changes mentioned, per-
foration is rare.” In the intestines there are found hyperamia, extravasations,
loosening of the mucous membrane, and other changes. The action is particularly
intense about the caecum and sigmoid flexure ; in one case, indeed, there was little
inflammatory redness of the stomach or of the greater portion of the intestine, but
the whole surface of the caecum was of a deep black-red colour, and there were
patches of sloughing in the coats. The kidneys are often swollen, congested, or
inflamed ; changes in the respiratory organs are not constantly seen, but in a majority
of the cases there have been redness and swelling of the larynx, trachea, and bronchi,
and sometimes hepatisation of Smaller or larger portions of the lung.
In St. George's Hospital Museum there are (from a patient dying in the hospital)
preparations which well illustrate what pathological changes may be expected in
any case surviving for a few days. The patient was Francis L , aged 45, admitted
to the hospital, February 27, 1842. He took a quantity of corrosive sublimate spread
on bread and butter, was immediately sick, and was unable to take as much as he
had intended. The stomach-pump and other remedies were used. On the follow-
ing day his mouth was sore, and on March 1st his vision was dim ; his mouth was
drawn over to the right side, and he lost power over the left eyelid, but he had
no pain ; he passed some blood from the bowel. On the 2nd he passed much
blood, and was salivated ; still no pain. On March 4, on the evening of the
sixth day, he expired ; he was drowsy during the last day, and passed watery
evacuations.
Prep. 14a, Ser. ix., shows the pharynx, oesophagus, and tongue ; there is ulcera-
tion of the tonsils, and fibrinous exudation on the gullet. The stomach (43b, 199)
shows a large dark slough, three inches from the cardiac extremity; the margin sur-
rounding the slough is thickened, ulcerated, and irregular in shape, the submucous
tissue, to some extent, being also thickened ; there is fibrine in the ileum, pharynx,
and part of the larynx. The action extended to the whole intestine ; the rectum in
prep. 145a, 36, is seen to be thickened, and has numerous patches of effused fibrine.
It is a curious fact that the external application of corrosive sublimate
causes inflammatory changes in the alimentary canal of nearly the same
intensity as if the poison had been swallowed. Thus, in the case of the
two girls mentioned ante (§ 843), there was found an intense inflamma-
tion of the stomach and intestines, the mucous tissues being scarlet-
red, swollen, and with numerous extravasations.
$ 850. The effects of the nitrate of mercury are similar to the pre-
* There is only one case of perforation on record.
:: : . . . . . ; f Lancet, 1845, p. 700.
*
ve * * ſº * &
$ 851.] w- MERCURY. 679
ceding; in the few cases which have been recorded, there has been
intense redness, and inflammation of the stomach and intestines, with
patches of ecchymosis. White precipitate, cyanide of mercury, mercuric
iodide, and mercurous sulphide (turpeth mineral) have all caused inflam-
mation, more or less intense, of the intestinal tract.
$ 851. Elimination of Mercury.—The question of the channels by
which mercury is eliminated is of the first importance. It would
appear certain that it can exist in the body for some time in an inactive
state, and then, from some change, be carried into the circulation and
show its effects.” Woit considers that mercury combines with the
albuminous bodies, separating upon their oxidation, and then becoming
free and active.f
Ullmann f found mercury as follows:—Kidneys, liver, spleen, a
small quantity in the stomach, no mercury in the small intestine, but
some in the large intestine ; small weighable quantities in the heart and
skeletal muscles, also in the lungs; but no mercury, when the dose
was small, in brain, the salivary glands, abdominal glands, thyroid
glands, the bile, or the bones.
The main channel by which absorbed mercury passes out of the
body is the kidneys, whilst mercurial compounds of small solubility are
in great part excreted by the bowel. A. Bynssen,' after experimenting
with mercuric chloride (giving 015 to 15 grin, with a little morphine
hydrochlorate), came to the conclusion that it could be detected in the
urine about two hours, and in the saliva about four hours, after its
administration ; he considered that the elimination was finished in
twenty-four hours.
From the body of a hound that, in the course of thirty-one days,
took 2:789 grims. of calomel (2°368 Hg) in eighty-seven doses, about 94
per cent. of the substance was recovered on analysis:–
Mercurous Sulphide,
Grms.
In the faeces, º * e e tº * e º 2-1175
,, urine, e g tº * § & & 0.0550
,, brain, heart, lungs, spleen, pancreas, kidneys,
scrotum, and penis, * & g g e 0 °0090
,, liver, & g tº e e * º e 0 0140
,, muscles, . * ſe g g e & t 0.0114
2 °2069
* Tuson gave a mare, first, 4 grains, and afterwards 5 grains of corrosive sub-
limate twice a day; at the end of fourteen days, in a pint of urine no mercury was
detected, but at the end of three weeks it was found.
t Woit, Physiol, chem. Unters., Augsburg, 1857.
# Chem. Centr., 1892, ii. 941.
§ Journal de l’Amat. et de Physiol., 1872, No. 5, p. 500. On the separation of
mercury by the urine, see also Salkowsky in Virchow's Archiv, 1866.
68O Poisons: THEIR EFFECTS AND DETECTION. [$ 852.
This equals 1-9 of metallic mercury.* Thus, of the whole 2.2 grns.
of mercuric sulphide separated, over 95 per cent. was obtained from the
faeces. 4.
This case is of considerable interest, for there are recorded in toxico-
logical treatises a few cases of undoubted mercurial poisoning in which
no poison had been detected, although there was ample evidence that it
had been administered by the mouth. In such cases, it is probable
that the whole length of the intestimal canal had not been examined,
and the analysis failed from this cause. When (as not unfrequently
happens) the mercurial poison has entered by the skin, it is evident
that the most likely localities are the urine, the liver, and the kidneys.i
In a case related by Vidal, the Liquor Bellostii (or solution of
mercuric nitrate) was ordered by mistake instead of a liniment. Al-
though externally applied, it caused salivation, profuse diarrhoea, and
death in nine days. The whole of the intestimal tract was found
inflamed with extravasations, and mercury detected in the liver.
In any case of external application, if death ensues directly from the
poison, evidence of its presence will probably be found; but too much
stress must not be laid upon the detection of mercury, for, as Dr. Taylor
says, “Nothing is more common than to discover traces of mercury in
the stomach, bowels, liver, kidneys, or other organs of a dead body.”$
$ 852. Tests for Mercury.—-Mercury, in combination and in the
solid form, is most readily detected by mixing the substance intimately
with dry anhydrous sodic carbonate, transferring the mixture to a glass
tube, sealed at one end, and applying heat. If mercury be present, a
ring of minute globules condenses in the cool part of the tube. If the
quantity of mercury is likely to be very minute, it is best to modify the
process by using a subliming cell (p. 260), and thus obtain the sublimate
on a circle of thin glass in a convenient form for microscopical examina-
tion. If there is any doubt whether the globules are those of mercury
or not, this may be resolved by putting a fragment of iodine on the
lower disc of the subliming cell, and then completing it by the disc
which contains the sublimate (of course, the supposed mercurial surface
must be undermost); on placing the cell in a warm, light place, after a
time the scarlet iodide is formed, and the identification is complete.
Similarly, a glass tube containing an ill-defined metallic ring of mercury
can be sealed or corked up with a crystal of iodine, and, after a few
* Riederer, in Buchner's Neues Repert. f. Pharm., Bd. xvii. 3, 257, 1868.
t A woman died from the effects of a corrosive sublimate lotion applied by a
quack to a wound in her leg. The senior author found no poison in the stomach, but
separated a milligramme of metallic mercury from the liver; the urine and intestines
were not sent.
† Gaz, des Hôp., Juillet 1864.
§ Taylor, Medical Jurisprudence, i. p. 288.
$ 853.] MERCURY. 68 I
hours, the yellow iodide, changing to scarlet, will become apparent.
There are few (if any) tests of greater delicacy than this.
Mercury in solution can be withdrawn by acidulating the liquid, and
then inserting either simply a piece of gold foil, gold wire, or bright
copper foil; or else, by a galvanic arrangement, such as iron wire wound
round a gold coin, or gold foil attached to a rod of zinc ; or, lastly, by
the aid of gold or copper electrodes in connection with a battery. By
any of these methods mercury is obtained in the metallic state, and the
metal with its film can be placed in a subliming cell, and globules
deposited and identified, as before described.
The Precipitating Reagents for mercury are numerous: a solution
of stannous chloride, heated with a solution of mercury, or any com-
bination, whether soluble or insoluble, reduces it to the metallic state.
Mercurous Salts in solution yield, with potash, soda, or lime, a
black precipitate of mercurous oxide; Mercuric Salts, a bright yellow
precipitate of mercuric oxide.
Mercurous Salts yield black precipitates, with sulphides of
ammonium and hydrogen. Mercuric Salts give a similar reaction, but,
with sulphuretted hydrogen, first a whitish precipitate, passing slowly
through red to black.
Mercurous Salts, with solutions of the chlorides, give a white
precipitate of calomel; the Mercuric Salts yield no precipitate under
similar circumstances. Mercurous Salts, treated with iodide of
potassium, give a green mercurous iodide ; Mercuric, a scarlet.
$ 853. The Detection of Mercury in Organic Substances and
Fluids.-Simple treatment of the organs or tissues with hydrochloric
acid may give qualitative evidence of mercury, for distinct evidence of
mercury in the liver has been obtained on a piece of copper gauze in a
case where a child had been given 2 grains of calomel before death.
“Four ounces of the liver were treated with hydrochloric acid and
water, and a small piece of pure copper placed in the acid liquid while
warm, and kept there for about forty-eight hours. It acquired a slight
silvery lustre, and globules of mercury were obtained from it by
sublimation.”
To detect the cyanide of mercury may require special treatment,
and Vitali” recommends the following process:–The fluid is acidified
with tartaric acid and neutralised by freshly precipitated CaCOs; a
slight excess of hydric sulphide is added, and the flask allowed to rest
for twenty-four hours in the cold. Then a further quantity of SH, is
added, and a current of hydrogen passed through the liquid ; the
effluent gas is first made to bubble through a solution of bismuth
nitrate in dilute nitric acid (for the purpose of absorbing SH3), and
* L’Orosi, xii. 181–196.
682 POISONS : THEIR EFFECTS AND DETECTION. [$ 853.
then through aqueous potash (to absorb HCl); in the first flask the
analyst will separate and identify mercury sulphide, while in the last
flask there will be potassic cyanide, which will respond to the usual
tests.
In those cases where no special search is made for mercury, but an
acid (hydrochloric) solution is treated with sulphuretted hydrogen,
mercury is indicated by the presence of a black precipitate, which does
not dissolve in warm nitric acid.
The further treatment of the black sulphide may be undertaken in
two ways:—
(1) It is collected on a porcelain dish, with the addition of a little
nitric acid, and evaporated to dryness in order to destroy organic
matter. Hydrochloric and a few drops of nitric acid are next added ;
the action is aided by a gentle heat, the solution finally evaporated to
dryness on the water-bath, and the residue taken up by warm distilled
water. The solution is that of a persalt of mercury, and the mercury
can be separated by electrolysis, or indicated by the tests already
detailed.
(2) The other method, and the most satisfactory, is to mix the sul-
phide while moist with dry carbonate of soda, make it into a pellet
which will easily enter a reducing or subliming tube, dry it carefully,
and obtain a sublimate of metallic mercury.
A meat method of recognising mercury when deposited as a film on
copper has been proposed by E. Brugmatelli : * the copper, after being
washed, is transferred to a glass vessel, and a porcelain lid, on which a
drop of gold chloride solution has been placed, adjusted over the dish.
The whole is heated by a water-bath. The mercury vapour reduces the
gold chloride, and gold is deposited as a bluish-violet stain ; #5 mgrm.
mercury may by this test be identified.
Of special methods for the separation and detection of mercury,
Ludwig's f (or some modifications thereof) is the best when organic
matters have to be dealt with : the finely divided solid substances are
boiled for some hours with hydrochloric acid, strength 20 per cent. ;
then the liquid is cooled to 60°, and potassic chlorate added in half-
gramme quantities until the dark liquid becomes clear; the liquid is
cooled and filtered, and the substances on the filter washed with water.
To the filtrate 5 grims. of zinc dust are added, and the liquid is violently
shaken from time to time; a second portion is afterwards added, and
also vigorously shaken. After some hours the clear liquid is separated
from the zinc and the zinc washed, first with water, then with a little
soda solution, and finally, again with water. The zinc is now collected
* Gazzetta, xix. 418–422.
+ Zeit. f. physiolog. Chemie, 1882, i. 495; Chem. Centrblt., 1892, ii. 941.
$ 853A, 853B.] MERCURY. 683
on a glass-wool filter, treated with absolute alcohol to remove water,
and dried by suction in a stream of air. The zinc is put into a combus-
tion-tube, the tube being drawn out into a thin capillary extremity,
and a combustion made, the mercury collecting at the capillary part.
It is a necessary refinement, should the zinc be contaminated with a
trace of organic matter, to pack the combustion-tube as follows:—First,
the zinc dust on which any mercury present has been deposited, then a
plug of asbestos; next, some cupric oxide; and lastly, some pure zinc
dust. Bondzynski “ prefers to use copper rather than zinc ; for he says
that zinc so frequently contains cadmium, which latter metal also gives
a mirror, so that, unless the mercury is afterwards identified by turning
it into an iodide, error may be caused.
O. Schumm (Zeit, anal. Chem., 1905) has made a number of
experiments showing that it is not necessary to entirely destroy the
organic matter of the organs in searching for mercury. The organs
and tissues, finely divided, are treated with hydrochloric acid and potassic
chlorate in a capacious flask attached to an inverted (reflux) con-
denser, and then the filtered fluid submitted to electrolysis—the anode
being platinum foil, the cathode a piece of gold foil 10 mm. broad and
30 mm. long; the tension should be 4 volts, and the electrolysis be
continued for twenty-four hours. In a case of mercury-poisoning Schumm
found in the kidney 1-89 mgrm., liver 1 mgrm., pancreas 44 mgrm.,
and lung 4 mgrm.—total separated, 3.73 mgrms.f
$ 853A. Separation of Mercury by Hydroxylamine.—Paul Jannasch
(Ber., 1898) has shown that mercury may be separated quantitatively
from copper, bismuth, lead, nickel, cadmium, arsenic, antimony, and tin,
by an ammoniacal solution of hydroxylamine. The mercury should
be converted into chloride, and, to the hydrochloric acid solution,
tartaric acid, ammonia, and hydroxylamine hydrochloride are added in
excess, and the solution heated until the precipitation is complete ; the
mercury is collected, redissolved in fuming nitric acid, the solution
evaporated to dryness, the residue taken up with hydrochloric acid, and
the mercury precipitated as sulphide. Mercury may be similarly
separated from aluminium, chromium, or manganese in the presence of
oxalic acid; mercury and cobalt may also be separated by the addition
of ammoniacal hydroxylamine to a slightly acid solution of their salts.
$ 853B. Detection of Mercury in the Urine.—One of the best
methods is to acidify with concentrated hydrochloric acid, and add
* Zeit. f. anal. Chem..., xxxii. 302–305.
t Schumm also shows that a fluid capable of filtration can be obtained by
digesting or incubating at 37° with an equal bulk of water to which, as an antiseptic,
chloroform is added. Under these circumstances in about a week auto-digestion, to a
great extent, will have taken place. For the same purpose he also uses pepsin and
hydrochloric acid; but such time-consuming processes are hardly practical.
684 POISONS : THEIR EFFECTS AND DETECTION. [$ 853B.
potassic chlorate in the proportion of about 1 grm. for every 100 c.c.;
the urine is heated until it no longer smells of chlorine, and then mixed
with a dilute solution of stanmous chloride ; in this mixture a piece of
gilt platinum foil is placed for fifteen minutes, the foil heated with nitric
acid, and the solution evaporated to a small bulk and then tested with
hydrogen sulphide. This method will detect 0.07 mgrm. of mercury.*
Schumacher and W. Junyi use a similar process, but add sodium
chloride, and after boiling with the hydrochloric acid and potassic
chlorate, cool to 80° and add rasped zinc ; in about two hours the
undissolved zinc is collected, washed, heated with dilute potassium
hydroxide, and again washed. It is then dissolved in 50 c.c. of dilute
hydrochloric acid with the addition of potassic chlorate ; after boiling
out most of the chlorine, the last traces are removed by the addition
of alcohol. Hydrogen sulphide is added, the mixture made up to 100
c.c., and the yellowish-brown colour compared colorometrically with
standard solutions of mercuric chloride.
Ernst Jānecke (Zeit. f. anal. Chem., 1904) separates mercury from
urine on the foregoing principles, obtaining the metal first on a spiral
of copper wire. The wire is washed with hot water and air-dried. It
is then put in a dry reagent tube, which is drawn out just beyond the
wire to a capillary tube; by means of strong heat the mercury is then
distilled into the capillary portion. The capillary tube is then cut off,
and crushed in a reagent glass containing 5 c.c. of dilute nitric and
sulphuric acids. The mixture is warmed for an hour on the water-bath,
and then transferred to a watch-glass—bringing the whole up to 10 c.c.
by a 5 per cent. solution of potassic sulphate. This solution is submitted
to the electrolysis of a platinum-gold couple, made of gold and platinum
wire. The gold wire weighs about 25 mgrms., and has a length of 18–20
cm., with a diameter of 0.1 mm. The gold wire is weighed carefully in
a Nernst balance both before and after the electrolysis; in each case it
is carefully dried.
According to Bruno Bardach (Chem. Centr., 1901), mercury in the
urine may be separated and estimated as follows:—250–1000 c.c. of the
urine are mixed with 0.8 grim. of finely-divided egg albumim ; 5–7 c.c.
of 30 per cent. acetic acid are added, and the albumin precipitated on
the water-bath. The precipitate contains all the mercury; it is filtered
off and dissolved in 10 c.c. of hydrochloric acid of specific gravity 1:19.
This solution is heated for forty-five minutes with a clean copper spiral in
* Adolf Jolles, Zeit. amal. Chem., 1900. † Ibid., 1902.
# The Nernst balance (Ber. xxxvi., 1903) is a micro-balance with torsional
control, having a sensitiveness of '038 mgrm. per scale division, and capable of being
read to gº division. It can scarcely be in English commerce at present, but can be
obtained from Spindler & Hoyer, Gottingen ; it is an instrument likely to be of use
in toxicological investigation.
$ 854, 855.] MERCURY. 685
the water-bath. The spiral is washed with water, alcohol, and ether,
carefully dried between filter-paper, and then heated in a long glass
tube with a particle of iodine. The yellowish-red iodide of mercury, if
present, will condense in the colder part of the tube.
$ 854. Estimation of Mercury. — All pharmaceutical substances
containing mercury, as well as the sulphide prepared in the wet way,
and minerals, are best dealt with by obtaining and weighing the metal
in the solid state. The assay is very simple and easy when carried out
on the method that was first, perhaps, proposed by Domeyko. A glass
tube (which should not be too thin), closed at one end, is bent, as shown
in the figure; the diameter should be about three lines, the length from
7 to 8 inches, the shorter arm not exceeding 2 inches. The powdered
substance is mixed with two or three times its weight of litharge, and
introduced into the tube at a. The portion of the tube containing the
mercury is at first heated gently, but finally brought to a temperature
sufficient to fuse the substance and soften the glass. The mercury
collects in an annular film at b in the cooler limb, and may now, with a
little management of the lamp, be concentrated in a well-defined ring ;
the portion of the tube containing this ring is cut off, weighed, then
cleansed from mercury, and reweighed. Many of the pharmaceutical
preparations do not require litharge, which is specially adapted for ores,
and heating with sodic carbonate (in great excess) will suffice. Mercury
mixed with organic matter must be first separated as described, by copper
or gold, the silvered foil rolled up, dried, introduced into the bent tube,
and simply heated without admixture with any substance; the weight
may be obtained either by weighing the foil before and after the opera-
tion, or as above.
$ 855. Volumetric Processes for the Estimation of Mercury.—
When a great number of mercurial preparations are to be examined, a
volumetric process is extremely convenient. There are several of these
processes, some adapted more particularly for mercuric, and others for
mercurous compounds. For mercuric, the method of Personne * is the
best. The conversion of the various forms of mercury into corrosive
sublimate may be effected by evaporation with aqua regia, care being
taken that the bath shall not be at a boiling temperature, or there will
be a slight loss.
Personne prefers to heat with caustic soda or potash, and then pass
* Compt. Rend., lvi. 68 ; Sutton’s Vol. Amal., 177.

686 POISONS : THEIR EFFECTS AND DETECTION. [$856.
chlorine gas into the mixture; the excess of chlorine is expelled by
boiling, mercuric chloride in presence of an alkaline chloride not being
volatilised at 100°. The standard solutions required for this process
al’6 —
(1) 33-2 grms. of potassic iodide in 1 litre of water, 1 c.c. = 0.01 grn.
Hg, or 0:01355 grim. HgCl,
(2) A solution of mercuric chloride containing 13:55 grms. to the
litre, 1 c.c. = 0°l grm. Hg.
The process is founded on the fact that, if a solution of mercuric
chloride be added to one of potassic iodide, in the proportion of one of the
former to four of the latter, mercuric iodide is formed, and immediately
dissolved, until the balance is overstepped, when the red colour is
developed ; the final reaction is very sharp, and with solutions properly
made is very accurate. The mercuric solution must always be added to
the alkaline iodide ; a reversal of the process does not answer. It there-
fore follows that the solution to be tested must be made up to a definite
bulk, and added to a known quantity of the potassic iodide until the
red colour appears.
Mercurous Salts may be titrated with great accuracy by a decinormal
solution of sodic chloride. This is added to the cold solution in very
slight excess, the calomel filtered off, the filtrate neutralised by pure
carbonate of soda, and the amount of sodic chloride still unused found
by titration with nitrate of silver, the end reaction being indicated
by chromate of potash. Several other volumetric processes are fully
described in works treating upon this branch of analysis.
III. PRECIPITATED BY HYDRIC SULPHIDE FROM
A NEUTRAL SOLUTION.
Zinc—Nickel—Cobalt.
1. ZINC.
$ 856. Zinc–at. wt., 65; specific gravity, 6-8 to 7:1; fusing-point,
412° C (773°F)—is a hard, bluish-white, brittle metal, with a crystalline
fracture. Between 100° and 150° it becomes ductile, and may be easily
wrought ; but at a little higher temperature it again becomes brittle, and
at a bright red heat it fuses, and then volatilises, the fumes taking fire
when exposed to the air. In analysis, zinc occurs either as a metallic
deposit on a platinum foil or dish, or as a brittle bead, obtained by
reducing a zinc compound with soda on charcoal.
The salts of zinc to be briefly described here are the carbonate, the
$ 857–860.] ZINC. 687
oxide, and the sulphide—all of which are likely to occur in the separa-
tion and estimation of zinc, and the sulphate and chloride—salts more
especially found in commerce, and causing accidents from time to
time.
$ 857. Carbonate of Zinc, in the native form of calamine, contains, as
is well known, 64.8 per cent. of oxide of zinc ; but the carbonate obtained
in the course of an analysis by precipitating the neutral hot solution of
a soluble salt of zinc by carbonate of potash or soda, is carbonate of zinc
plus a variable quantity of hydrated oxide of zinc. Unless the precipi-
tation takes place at a boiling temperature, the carbonic anhydride retains
a portion of the oxide of zinc in solution. By ignition of the carbonate,
oxide of zinc results.
§ 858. Oxide of Zinc (ZnO = 81; specific gravity, 5-612; Zn,
80-24, O, 1976) is a white powder when cool, yellow when hot. If
mixed with sufficient powdered sulphur, and ignited in a stream of
hydrogen, the sulphide is produced ; if ignited in the pure state in
a rapid stream of hydrogen gas, metallic zinc is obtained; but, if it
is only a feeble current, the oxide of zinc becomes crystalline, a portion
only being reduced.
$ 859. Sulphide of Zinc (ZnS =97; specific gravity, 4:1; Zn, 67.01,
S, 32.99).-The sulphide obtained by treating a neutral solution of a
soluble salt of zinc by hydric sulphide is hydrated sulphide, insoluble in
water, caustic alkalies, and alkaline sulphides, but dissolving completely
in nitric or in hydrochloric acid. When dry, it is a white powder, and
if ignited contains some oxide of zinc. The anhydrous sulphide is pro-
duced by mixing the precipitated sulphide with sulphur, and igniting in
a crucible in a stream of hydrogen gas. -
Pharmaceutical Preparations.—The officinal compounds of zinc used
in medicine are the acetate, carbonate, chloride, oacide, sulphate, sulpho-
carbolate, and valerianate.
Sulphate of Zinc (ZnSO,7H,0=161 + 126; specific gravity, crystals,
1931).-This salt is officinal in all the pharmacopoeias, is used in
calico-printing, and is commonly known as white vitriol. By varying
the temperature at which the crystals are allowed to be formed,
it may be obtained with 6, 5, 2, or 1 atoms of water. The com-
mercial sulphate is in crystals exactly similar to those of Epsom
salts; it is slightly efflorescent, and gives the reactions of zinc and
sulphuric acid.
$ 860. Chloride of Zinc is obtained by dissolving zinc in hydro-
chloric acid, or by direct union of zinc and chlorine. Chloride of zinc
is the only constituent in the well-known “Burnett's disinfectant fluid.”
A solution of chloride of zinc may be heated until it becomes water-
free; when this takes place it still remains fluid, and makes a convenient
688 POISONS: THEIR EFFECTS AND DETECTION. [$ 861.
bath, for warmth may be applied to it above 370° without it emitting
fumes to inconvenience ; at a red heat it distils. A concentrated
solution of zinco-ammonic chloride (2H, NCIZnCl2) is used for the
purpose of removing the film of oxide from various metals preparatory
to soldering.
$ 861. Zinc in the Arts.-The use of zinc as a metal in sheeting
cisterns, articles for domestic use, alloys, etc., is well known ; oxide of
zinc enters largely into the composition of india-rubber. Sulphide of
zinc has been employed as a substitute for white lead, and may possibly
supersede it, Zinc white is further employed as a pigment, and, mixed
with albumen, is an agent in calico-printing; it is also used in the
decoloration of glass, in the polishing of optical glasses, and in the
manufacture of artificial meerschaum pipes.*
Chromate of Zinc (ZnCrO.) is used in calico-printing, and there is
also in commerce a basic chromate known as zinc yellow. Zinc green,
or Rinman's green, is a beautiful innocuous colour, formed by igniting
a mixture of dry zincic and cobaltous carbonates.
The use of zinc vessels in the preparation of foods may occasionally
bring the metal under the notice of the analyst. When exposed to
a moist atmosphere, zinc becomes covered with a thin film of oxide,
perfectly insoluble in ordinary water; but, if the water should be
charged with common salt, a considerable quantity may be dissolved.
It may generally be laid down as a rule that the solvent power of water
on zinc has a direct relation to the chlorides present, whilst carbonate of
lime greatly diminishes this solubility.f
Milk may become contaminated by zinc ; for, it is a matter of
common knowledge that milk contained in zinc vessels does not readily
turn sour. This may be explained by the zinc oxide combining with
the lactic acid, and forming the sparingly soluble lactate of zinc
2(CH3O3)Zn + 311,0, thus withdrawing the lactic acid as fast as it is
formed, preventing the coagulation of the casein. With regard to this
important practical subject, MM. Payne and Chevallier made several
experiments on the action of brandy, wine, vinegar, olive oil, soup,
milk, etc., and proved that zinc is acted on by all these, and
especially by alcoholic, acetic, and saline liquids. M. Schaufféle
has repeated these experiments, and determined the amount of zinc
dissolved in fifteen days by different liquids from a galvanised iron
as well as a zinc vessel.
* Artificial meerschaum pipes are composed of zinc white, magnesia usta, and
casein ammonium.
| Ziurek, indeed, found in a litre of water contained in a zinc cistern no less than
1 0104 grim. of zinc, and the same water showed only 0.074 grim. of common salt to
the litre, — Vierteljahrsschr, für gericht. Medicin, 1867, Bd. vi. p. 356.
§ 862, 863.] ZINC. 689
The amount found was as follows:—
ſº The liquid from
The liquid from the galvanised
the zinc vessel— iron vessel—
grms. per litre. grms. per litre.
Brandy, & t © * { } tº 0 '95 0-70
Wine, wº e º & e g 3'95 4°10
Orange-flower water, . º nº & 0 °50 0.75
Winegar, . ſe e ſº i. e 31-75 60-75
Fatty soup, . e ſº g & e 0'46 1-00
Weak soup, . e tº º re * 0 '86 1.76
Milk, te iº tº ſe * e 5*13 7:00
Salt water, . te e e tº * 1.75 0 °40
Seltzer water, tº ſº & º e 0-35 0 °30
Distilled water, . • • © º traces. traces.
Ordinary water, . ſº sº g & traces. traces.
Olive oil, . e tº e * sº Il OIle, IlOI) e.
$ 862. Effects of Zinc, as shown by Experiments on Animals.-
Harnack, in experiments with sodium-zinc oxide pyrophosphate, has
shown that the essential action of zinc salts is to paralyse the muscles
of the body and the heart, and, by thus affecting the circulation and
respiration, to cause death; these main results have been fully confirmed
by Blake, Letheby, and C. Ph. Falck. For rabbits the lethal dose is
'08 to '09 grn. of zinc oxide, or about :04 per kilogrim. The tempera-
ture during acute poisoning sinks notably—according to F. A. Falck’s
researches on rabbits, from about 7:3° to 130°. Zinc is eliminated
mainly by the urine, and has been recognised in that fluid four to five
days after the last dose. It has also been separated in small quantity
from the milk and the bile.
§ 863. Effects of Zinc Compounds on Man—(a) Zinc Oxide.—The
poisonous action of zinc oxide is so weak that it is almost doubtful
whether it should be considered a poison. Dr. Marcett has given a
pound (453:6 grms.) during a month in divided doses without injury to
a patient afflicted with epilepsy; and the workmen in zinc manufactories
cover themselves from head to foot with the dust without very apparent
bad effects. It is not, however, always innocuous, for Popoff has re-
corded it as the cause of headache, pain in the head, cramps in the
calves of the legs, nausea, vomiting, and diarrhoea ; and he also obtained
zinc from the urine of those suffering in this manner.” Again, a phar-
macy student t filled a laboratory with oxide of zinc vapour, and
suffered from well-marked and even serious poisonous symptoms, con-
sisting of pain in the head, vomiting, and a short fever. It must be
remembered that, as the ordinary zinc of commerce is seldom free from
* The so-called “zinc fever * has only been noticed in the founding of brass; it
is always preceded by well-marked shivering, the other symptoms being similar to
those described.
+ Rust’s Magazim, Bd. xxi. § 563.
44
690 POISONS: THEIR EFFECTS AND DETECTION. [$ 864, 865.
arsenic, and some samples contain gallium, the presence of these metals
may possibly have a part in the production of the symptoms described.
$ 864. (b) Sulphate of Zinc.—Sulphate of zinc has been very fre-
quently taken by accident or design, but death from it is rare. The
infrequency of fatal result is due, not to any inactivity of the salt, but
rather to its being almost always expelled by vomiting, which is so
constant and regular an effect, that in doses of 13 grm. (20 grains)
sulphate of zinc is often relied upon in poisoning from other substances
to quickly expel the contents of the stomach. In a case reported by
Dr. Gibb, an adult female swallowed 4.33 grms. (67 grains), but no
vomiting occurred, and it had to be induced by other emetics; this case
is unique. It is difficult to say what would be a fatal dose of zinc
sulphate, but the serious symptoms caused by 28 grms. (1 oz.) in the
case of a groom in the service of Dr. Mackenzie, leads to the view that,
although not fatal in that particular instance, it might be in others.
The man took it in mistake for Epsom Salts : a few minutes after, he
was violently sick and purged, and was excessively prostrated, so that he
had to be carried to his home; the following day he had cramps in the
legs, and felt weak, but was otherwise well.
In a criminal case related by Tardieu and Roussin, a large dose
of zinc sulphate, put into soup, caused the death of a woman sixty
years of age in about thirty hours.” The symptoms were violent
purging and vomiting, leading to collapse. From half of the soup a
quantity of zinc oxide, equal to 1:6 grim. of zinc sulphate, was separated.
Zinc was also found in the stomach, liver, intestines, and spleen—(see
also a case of criminal poisoning recorded by Chevallier). Í
$ 865. (c) Zinc Chloride.—Chloride of zinc is a powerful poison,
which may kill by its primary or secondary effects; its local action as a
caustic is mainly to be ascribed to its intense affinity for water, dehy-
drating any tissue with which it comes in contact. The common use of
disinfecting fluids containing zinc chloride, such as Burnett's fluid, leads
to more accidents in England than in any other European country. Of
twenty-six cases of poisoning by this agent, twenty-four occurred in
England, and only two on the Continent. Death may follow the ex-
ternal use of zinc chloride. Some years ago a quack at Barnstaple,
Devon, applied zinc chloride to a cancerous breast ; the woman died
with all the general symptoms of poisoning by zinc, and that metal was
found in the liver and other organs.
* Taylor notices this case, but adds that she died in three days. This is a mis-
take, as the soup was taken on the 12th of June, probably at midday, and the
woman died on the 13th, at 8 P.M.
+ “Observations toxicologiques sur le zinc,” Annales d'Hygiène Publique, J uly
1878, p. 153.
$ 866.] ZINC. 691
The symptoms observed in fatal cases of chloride of zinc poisoning are
—immediate pain in the throat, and burning of the lips, tongue, etc.
There is difficulty in swallowing, an increase in the secretion of saliva,
vomiting of bloody matters, diarrhoea, collapse, coma, and death. In
some cases life has been prolonged for days; but, on the other hand,
death has been known to occur in a few hours. In those cases in which
either recovery has taken place, or in which death is delayed, nervous
symptoms rarely fail to make their appearance. In a case recorded
by Dr. R. Hassal, 3 ozs. of Burnett's fluid were swallowed. The usual
symptoms of intense gastro-intestinal irritation ensued, but there
was no purging until the third day; after the lapse of a fortnight,
a train of nervous symptoms set in, indicated by a complete perver-
sion of taste and smell. In other cases, aphonia, tetanic affections
of groups of muscles, with great muscular weakness and impairment
of sight, have been noticed. Very large doses of zinc chloride have
been recovered from, e.g. a man had taken a solution equivalent to
about 13 grns. (200 grains) of the solid chloride. Vomiting came on
immediately, and there was collapse, but he recovered in sixteen days.
On the other hand, 38 grn. (6 grains) has destroyed life after several
weeks' illness.
$ 866. Post-mortem Appearances.—In poisoning by sulphate of
zinc, the appearances usually seen are inflammation, more or less intense,
of the mucous membrane of the stomach and bowels. In St. George's
Hospital Museum there is (ser. ix.43 and 198) the stomach of a man
who died from zinc sulphate, and whose case is reported in the Lancet,
1859. The mucous membrane is wrinkled all over like a piece of
tripe; when recent it was vascular and indurated, but uniformly of a
dirty grey colour; the lining membrane of the small intestine is very
vascular, and in the duodenum and upper part of the jejunum the colour
is similar to that of the stomach, but in a less marked degree; the
stomach and intestines are contracted.
The pathological appearances after chloride of zinc vary according to
the period at which death takes place. When it has occurred within a
few hours, the lining membrane of the mouth and gullet shows a marked
change in texture, being white and opaque, the stomach hard and leathery,
or much corrugated and ulcerated. In cases in which life has been pro-
longed, contractions of the gullet and stomach may occur very similar to
those caused by the mineral acids, and with a similar train of symptoms.
In a case which occurred under Dr. Markham’s “ observation, a person
died ten weeks after taking the fatal dose, the first symptoms subsiding
in a few days, and the secondary set of symptoms not commencing for
three weeks. They then consisted mainly of vomiting, until the patient
* Med. Times and Gazette, June 11, 1859, p. 595.
692 POISONS : THEIR EFFECTS AND DETECTION. [$ 867.
sank from exhaustion. The stomach was constricted at the pyloric end,
so that it would scarcely admit a quill.
In Guy's Hospital there is a good preparation, 17998”, from the case
of S. R., aged 22 ; she took a tablespoonful of Burnett's fluid, and died
in about fourteen weeks. There were at first violent vomiting and
purging, but she suffered little pain, and in a day or two recovered
sufficiently to move about the house; but the vomiting after food con-
tinued, everything being ejected about five minutes after swallowing.
Before death she suffered from pneumonia. The stomach is seen to be
much contracted—5 inches in length ; it is ulcerated both near the
pylorus and near the gullet ; at the latter part there is a pouch-like
portion of the mucous membrane of the stomach adherent to the spleen,
which communicates by a perforation with an abscess formed and bounded
by the stomach, diaphragm, and spleen ; it contained 3 ozs, of dirty-
looking pus. At the pylorus, in the centre, there is a second perforation,
but extravasation of the contents is prevented by the adherent omentum
and transverse colon. The muscular coats are thickened.
$ 867. Detection of Zinc in Organic Liquids or Solids.-In cases
where the poison has been expelled from the stomach by vomiting, the
muscles and bones would appear to be the best tissues to examine chemi-
cally; for Matzkewitsch investigated very carefully a dog poisoned by
100 parts of zinc, subcutaneously injected in the form of acetate, and
found it distributed over the several organs of the body in the following
ratios:–Muscles, 60:5; bones, 24'41 ; stomach and intestines, 4-63;
skin, 3.70; place of injection, 2:19; liver, l'75; lungs and heart, 1-68;
kidneys, bladder, and urine, 1:14.
Finely-divided organic solids should be partially oxidised by mitric
acid and then charred ; the charred mass is fused in a porcelain basin
with sodium carbonate and potassic nitrate, and the ash dissolved in
nitric acid. The first group of metals is thrown out by sulphuretted
hydrogen, the iron and aluminium by ammonia; a small excess of acetic
acid is added to the filtrate, and the zinc precipitated as sulphide by
hydric sulphide ; on the routine examination for metals the solution
will have been treated with hydrochloric acid, and already tested for
arsenic, antimony, lead, etc., and filtered from any precipitate. In such
a case the hydrochloric acid must first be replaced by acetic, which is
effected by adding a slight excess of sodic acetate ; the right quantity
of the latter is easily known if the hydrochloric acid originally added
was carefully measured, and its specific gravity ascertained—372 of
crystallised sodic acetate saturating one of HCl. In any of the above
cases, should a white, dirty white, or lightish-coloured precipitate (which is
not sulphur) be thrown down, zinc may be suspected; it will, however, be
absolutely necessary to identify the sulphide, for there are many sources
§ 868, 869.] NICKEL–COBAL.T. 693
of error. The most satisfactory of all identifications is the production
of Rinman's green. The supposed sulphide is dissolved off the filter
with hot nitric acid, a drop or more (according to the quantity of the
original precipitate) of solution of cobalt nitrate added, the solution
precipitated with carbonate of soda and boiled (to expel all carbonic
anhydride); the precipitate is then collected on a filter, washed, dried,
and ignited in a platinum dish. If zinc be present in so small a
proportion as 1:100,000 part, the mass will be permanently green.
$ 868. Other methods of procedure are as follows:—The supposed
zinc sulphide (after being well washed) is collected in a porcelain dish,
and dissolved in a few drops of sulphuric acid, filtered, nitric acid added,
evaporated to dryness, and heated to destroy all organic matter. When
cool, the mass is treated with water acidulated by sulphuric acid, and
again filtered. The solution may contain iron as well as zinc, and if the
former (on testing a drop with ferrocyanide of potash) appears in any
quantity, it must be separated by the addition of ammonia in excess to
the ammoniacal filtrate; sodic carbonate is added in excess, the liquid
well boiled, and the precipitate collected on a filter and washed. The
carbonate of zinc thus obtained is converted into zinc oxide by ignition,
and weighed. If oxide of zinc, it will be yellow when hot, white when
cold ; it will dissolve in acetic acid, give a white precipitate with sul-
phuretted hydrogen, and, finally, if heated on charcoal in the oxidising
flame, and moistened with cobalt mitrate solution, a green colour will
result. Zinc may also be separated from liquids by electrolysis. The
best results are obtained from alkaline solutions and a strong current
at a temperature of 50°.
2. NICKEL–COBALT.
$ 869. The salts of nickel and cobalt have at present no toxicological
importance, although, from the experiments of Anderson Stuart,” both
may be classed as poisonous. The experiments of Gmelin had, prior to
Stuart's researches, shown that nickel sulphate introduced into the
stomach acted as an irritant poison, and, if introduced into the blood,
caused death by cardiac paralysis. Anderson Stuart, desiring to avoid
all local irritant action, dissolved nickel carbonate in acid citrate of soda
by the aid of a gentle heat ; he them evaporated the solution, and
obtained a glass which, if too alkaline, was neutralised by citric acid,
until its reaction approximated to the feeble alkalinity of the blood; the
cobalt salt was produced the same way. The animals experimented on
were frogs, fish, pigeons, rats, guinea-pigs, rabbits, cats, and dogs—
in all 200. The lethal dose of nickelous oxide, when subcutaneously
* “Nickel and Cobalt : their Physiological Action on the Animal Organism,” by
T. P. Anderson Stuart, M.D., Journ, of Amat. and Physiol., vol. xvii., Oct. 1882.
694 POISONS : THEIR EFFECTS AND DETECTION. [$870.
injected in the soluble compound described, was found to be as follows:—
frogs, '08 grim. per kilogramme ; pigeons, '06; guinea-pigs, '030; rats,
-025; cats, '01; rabbits, '009; and dogs, 007. The cobaltous oxide
was found to be much less active, requiring the above doses to be
increased about two-thirds. In other respects, its physiological action
seems to be very similar to that of nickelous oxide.
§ 870. Symptoms—Frogs.-A large dose injected into the dorsal
lymph sac of the frog causes the following symptoms:—The colour of
the skin all over the body becomes darker and more uniform, and not
infrequently a white froth is abundantly poured over the integument.
In an interval of about twenty minutes the frog sits quietly, the eyes
retracted and shut ; if molested, it moves clumsily. When quiet, the
fore limbs are weak, and the hind legs drawn up very peculiarly, the
thighs being jammed up so against the body that they come to lie on
the dorsal aspect of the sides of the frog, and the legs are so much flexed
that the feet lie on the animal’s back, quite internal to the plane of
the thighs. Soon fibrillary twitchings are observed in the muscles of the
abdominal wall, then feeble twitchings of the fingers, and muscles of the
fore limbs generally ; lastly, the toes are seen to twitch, and then the
muscles of the hind limbs—this order is nearly always observed ; now
spasmodic gaping and incoördinate movements are seen, and the general
aspect is not unlike the symptoms caused by picrotoxin. After this,
tetanus sets in, and the symptoms then resemble those of Strychnine ; the
next stage is stupefaction and voluntary motor paresis; the respiratory
movements become feeble, and the paresis passes into paralysis. The
heart beats more and more slowly and feebly, and death gradually and
imperceptibly supervenes. The post-mortem appearances are well marked
—i.e. rigor mortis, slight congestion of the alimentary tract, the heart
with the auricle much dilated and filled with dark blood, the ventricle
mostly small, pale, and semi-contracted. For some time after death, the
nerve trunks and muscles react to the induction current.
Pigeons.—In experiments on pigeons the symptoms were those of
dulness and stupor, jerkings of different sets of muscles, and then death
quietly.
Guinea-pigs.—In guinea-pigs there were dulness and stupefaction,
with some weakness of the hind limbs. -
Rats.—The symptoms in rats were almost entirely nervous; they
became drowsy and apathetic, and there was paralysis of the hind legs.
Rabbits.—In rabbits, also, the symptoms were mainly those caused
by an affection of the nervous system. There was paralysis, which
affected either the hind legs only, or all four limbs. The cervical
muscles became so weak that the animal was unable to hold its head up.
Diarrhoea occurred and persisted until death. If the dose is not large
§ 871–873.] NICKEL–COBALT. 695
enough to kill rapidly, the reflex irritability is decidedly increased, so
that the slightest excitation may cause the animal to cower and tremble
all over. Now appear twitchings and contractions of single groups of
muscles, and this excitement becomes general. The respirations also
become slower and more difficult, and sometimes there is well-marked
dilatation of the vessels of the ears and fundi oculi. Convulsions close
the scene.
$ 871. Circulation.—The effect of the salt on the frog's heart was
also studied in detail. It seems that, under the influence of a soluble
Salt of nickel, the heart beats more and more slowly, it becomes smaller
and paler, and does not contract evenly throughout the whole extent of
the ventricle ; but the rhythm of the ventricular and auricular con-
tractions is never lost.
It is probable that there is a vaso-motor paralysis of the abdominal
vessels; the blood-pressure falls, and the heart is not stimulated by the
blood itself as in its normal state. In support of this view, it is found
that, by either pressing on the abdomen or simply inverting the frog,
the heart swells up, fills with blood, and for a time beats well.
Nervous System.—The toxic action is referable to the central
nervous system, and not to that of peripheral motor nerve-endings or
motor nerve-fibres. It is probable that both nickel and cobalt paralyse
to some extent the cerebrum. The action on the nerve-centres is similar
to that of platinum or barium, and quite different from that of iron.
§ 872. Action on Striped Muscle.—Neither nickel nor cobalt has
any effect on striped muscle. In this they both differ from arsenic,
antimony, mercury, lead, and iron—all of which, in large doses, diminish
the work which healthy muscle is capable of performing.
§ 873. Separation of Nickel or Cobalt from the Organic Matters
or Tissues.—It is very necessary, if any case of poisoning should occur
by either or both of these metals, to destroy completely the organic
matters. Both nickel and cobalt are thrown down, if in the form of
acetate, from a meutral solution by sulphuretted hydrogen; but the
precipitation does not take place in the presence of free mineral acid :
hence, in the routine process of analysis, sulphuretted hydrogen is
passed into the acid liquid, and any precipitate filtered off. The liquid
is now made almost neutral by potassic carbonate, and then potassic
acetate added, and a current of sulphuretted hydrogen passed through
it. The sulphides of cobalt and nickel, if both are present, will be
thrown down ; under the same circumstances zinc, if present, would
also be precipitated. Cobalt is separated from zinc by dissolving the
mixed sulphides in nitric acid, precipitating the carbonates of zinc and
cobalt by potassic carbonate, collecting the carbonates, and, after wash-
ing, igniting them gently in a bulb-tube in a current of dry hydrochloric
696 Poisons: THEIR EFFECTS AND DETECTION. [$ 874–876.
acid; volatile zinc chloride is formed and distils over, leaving cobalt
chloride.
§ 874. To estimate cobalt, sulphide of cobalt may be dissolved in
nitric acid, and then precipitated by pure potash; the precipitate
washed, dried, ignited, and weighed; 100 parts of cobaltous oxide
(Co3O4) equals 73'44 of metallic cobalt. Cobalt is separated from nickel
by a method essentially founded on one proposed by Liebig. The nitric
acid solution of nickel and cobalt (which must be free from all other
metals, save potassium or sodium) is nearly neutralised by potassic
carbonate, and mixed with an excess of hydrocyanic acid, and then with
pure caustic potash. The mixture is left exposed to the air in a shallow
dish for some hours, a tripotassic cobalticyanide (K3COCyg) and a
nickelo-potassic cyanide (2KCy, NiCy) are in this way produced. If
this solution is now boiled with a slight excess of mercuric nitrate,
hydrated nickelous oxide is precipitated, but potassic cobalticyanide
remains in solution, and may be filtered off. On carefully neutralising
the alkaline filtrate with nitric acid, and adding a solution of mercurous
nitrate, the cobalt may then be precipitated as a mercurous cobalti-
cyanide, which may be collected, washed, dried, decomposed by ignition,
and weighed as cobaltous oxide. After obtaining both nickel and cobalt
oxides, or either of them, they may be easily identified by the blowpipe.
The oxide of nickel gives, in the oxidising flame with borax, a yellowish-
red glass, becoming paler as it cools; the addition of a potassium salt
colours the bead blue. In the reducing flame the metal is reduced, and
can be seen as little greyish particles disseminated through the bead.
Cobalt gives an intense blue colour to a bead of borax in the oxidising
flame.
IV.—PRECIPITATED BY AMMONIUM SULPHIDE.
Iron — Chromium — Thallium — Aluminium – Uranium.
1. IRON.
$875. It was Orfila's opinion that all the salts of iron were poisomons,
if given in sufficient doses; but such salts as the carbonate, the phos-
phate, and a few others, possessing no local action, may be given in such
very large doses, without causing disturbance to the health, that the
statement must only be taken as applying to the more soluble iron
compounds. The two preparations of iron which have any forensic
importance are the perchloride and the sulphate.
§ 876. Ferric Chloride (Fe,Cld = 325).-Anhydrous ferric chloride
will only be met with in the laboratory. As a product of passing dry
§ 877,878.] IRON. 697
chlorine over red-hot iron, it sublimes in brown scales, is very deli-
quescent, and hisses when thrown into water. There are two very
definite hydrates—one with 6 atoms of water, forming large, red, deli-
quescent crystals; and another with 12 of water, less deliquescent, and
crystallising in orange stellate groups.
The pharmaceutical preparations in common use are:–
Stronger Solution of Perchloride of Iron (Liquor Ferri Perchloridi
Fortior).-An orange-brown liquid of specific gravity 1:42, and contain-
ing about 58 per cent. of ferric chloride.
Tincture of Perchloride of Iron (Tinctura Ferri Perchloridi),
made by diluting 1 part of the strong solution with 1 volume of
rectified spirit, and adding distilled water to measure 4.
Solution of Perchloride of Iron (Liquor Ferri Perchloridi).-
Simply 5 volumes of the strong solution made up to 20 by the addition
of water; hence, of the same strength as the tincture.
§ 877. Effects of Ferric Chloride on Animals.—A very elaborate
series of researches on rabbits, dogs, and cats was undertaken some
years ago by MM. Bérenger-Férraud and Porte * to elucidate the
general symptoms and effects produced by ferric chloride under varying
conditions. First, a series of experiments showed that, when ferric
chloride solution was enclosed in gelatine capsules and given with the
food of the animal, it produced either no symptoms or but trifling
inconvenience, even when the dose exceeded 1 grim. per kilogrm. ;
anhydrous ferric chloride and the ferric chloride solution were directly
injected into the stomach, yet, when food was present, death did not
occur, and the effects soon subsided. In animals which were fasting,
quantities, of the solution equal to 5 grn. per kilogrm. and above
caused death in from one hour to sixteen hours, the action being much
accelerated by the addition of alcohol—as, for example, in the case of
the tincture : the symptoms were mainly vomiting and diarrhoea, some-
times the vomiting was absent. In a few cases the posterior extremities
were paralysed, and the pupils dilated: the urine was scanty or quite
suppressed ; death was preceded by convulsions.
$878. Effects on Man.—Perchloride of iron in the form of tinc-
ture has been popularly used in England, from its supposed abortive
property, and is sold under the name of “steel drops.” It has been
frequently taken by mistake for other dark liquids; and there is at
least one case on record in which it was proved to have been used for
the purpose of murder. The latter case f is peculiarly interesting from
its great rarity; it occurred in Martinique in 1874–1876, no less than
* “Etude sur l'empoisonnement par le perchlorure de fer,” par MM. Bérenger-
Férraud et Porte,” Annales d’Hygiène Publique, 1879.
+ Fully reported in Bérenger-Férraud's paper, loc, cit.
698 POISONS: THEIR EFFECTS AND DETECTION. [$ 879, 880.
four persons being poisoned at different dates. All four were presumed
to have had immoral relations with a certain widow X , and to have
been poisoned by her son. In three of the four cases, viz., Char
Duf , and Lab , the cause of death seems pretty clear; but the
fourth, Ab , a case of strong suspicion, was not sufficiently in-
vestigated. All three took the fatal dose in the evening, between eight
and nine o'clock—Lab the 27th of December 1874, Duf the
22nd of February 1876, and Char on the 14th of May 1876.
They had all passed the day in tippling, and they all had eaten nothing
from midday, so that the stomach would not, in any of the three, con-
tain any solid matters. The chloride was given to them in a glass of
“punch,” and there was strong evidence to show that the son of the
}
widow X administered it. Char died after about thirteen
hours' illness, Duf and Lab after sixty-five hours' illness;
Ab lived from three to four days. With Char the symptoms
were very pronounced in an hour, and consisted essentially of violent
colicky pain in the abdomen, and diarrhoea; but there was no vomiting.
Duf had also great pain in the abdomen and suppression of the
urine. Lab--— had most violent abdominal pains; he was constipated,
and the urinary secretion was arrested ; there was, besides, painful
tenesmus. According to the experiments of Bérenger-Férraud and
Porte,” the perchloride in the above cases was taken under conditions
peculiarly favourable for the development of its toxic action, viz., on an
empty stomach and mixed with alcohol.
There have been several cases of recovery from large doses of the
tincture, e.g. that of an old man, aged 72, who had swallowed 85 c.c.
(3 ozs.) of the tincture; the tongue swelled, there were croupy respira-
tion and feeble pulse, but he made a good recovery. In other cases,f
28.3 c.c. (an ounce) and more have caused vomiting and irritation of
the urinary organs. The perchloride is not unfrequently used to arrest
haemorrhage as a topical application to the uterine cavity—a practice
not free from danger, for it has before now induced violent inflammation
and death from peritonitis.
§ 879. Elimination of Iron Chloride.—Most of the iron is excreted
in the form of sulphide by the faeces, and colours them of a black hue ;
a smaller portion is excreted by the urine. *
§ 880. Post-mortem. Appearances.—In the experiments on animals
already referred to, the general changes noted were dryness, pallor, and
parchment-like appearance of the cavity of the mouth, the mucous mem-
brane being blackened by the contact of the liquid. The gullet was pale
* Dub. Med. Press, February 21, 1849.
+ Provincial Journal, April 7 and 21, 1847, p. 180; see also Taylor's Principles
and Practice of Medical Jurisprudence, vol. i. p. 320, 2nd edition.
§ 881.] IRON. 699
and dry, not unfrequently covered with a blackish layer. The mucous
membrane of the stomach was generally healthy throughout, but, if the
dose was large and very concentrated, there might be one or more
hyperaemic spots; otherwise, this did not occur. The internal surface
of the intestines, similarly, showed no inflammation, but was covered
with a brownish coating which darkened on exposure to the air. The
liver, in all the experiments, was large and gorged with black and fluid
blood; there were ecchymoses in the lungs, and venous congestion. The
kidneys were usually hyperamic, and contained little haemorrhages.
There was also general encephalic engorgement, and in one experiment
intense congestion of the meninges was observed. Few opportunities
have presented themselves for pathological observations relative to the
effects produced by ferric chloride on man. In a case related by Christi-
son, in which a man swallowed 42.4 c.c. (1% oz.) of the tincture, and
died in five weeks, there was found thickening and inflammation of the
pyloric end of the stomach.
The case of Char , already alluded to, is that in which the most
complete details of the autopsy are recorded, and they coincide very fairly
with those observed in animals; the tongue was covered with a greenish
fur, bordered at the edges with a black substance, described as being like
“mud”; the lining membrane of the gullet was pale, but also covered
with this dark “mud.” The stomach contained a greenish-black liquid ;
the liver was large and congested; the kidneys were swollen, congested,
and ecchymosed; the cerebral membranes were gorged with blood, and
the whole brain hyperaemic.
$881. Ferrous Sulphate, Copperas, or Green Vitriol, FeSO,7H,O
= 152 + 126; specific gravity, anhydrous, 3-138; crystals, 1857; com-
position in 100 parts, Fe0, 25.92; SOs, 28.77; H,0, 45:32.-The salt
is in beautiful, transparent, bluish-green, rhomboidal prisms. The
crystals have an astringent, styptic taste, are insoluble in alcohol, but
dissolve in about 1.5 times their weight of water; the commercial
article nearly always responds to the tests, both for ferrous and ferric
salts containing a little persalt. The medicinal dose of this salt is
usually given as from 0648 to 324 grm. (1 to 5 grains), but it has
been prescribed in cases requiring it in gramme (14.5 grains) doses with-
out injury. Sulphate of iron has many technical applications—is em-
ployed by all shoemakers, and is in common use as a disinfectant. The
salt has been employed for criminal purposes in France, and in this
country it is a popular abortive. In recorded cases the symptoms, as
well as the pathological appearances, have a striking resemblance to
those produced by the chloride. There are usually colic, vomiting, and
purging ; but in one case (reported by Chevallier), in which a man gave
a large dose of sulphate of iron to his wife, there was neither vomiting
7OO POISONS : THEIR FFFECTS AND DETECTION. [$882.
nor colic ; the woman lost her appetite, but slowly recovered. Probably
the action of ferrous sulphate, like that of the chloride, is profoundly
modified by the presence or absence of food in the stomach. Anything
like 283 grms. (an ounce) of sulphate of iron must be considered a
dangerous dose, for, though recovery has taken place from this quantity,
the symptoms have been of a violent kind.
§ 882. Search for Iron Salts in the Contents of the Stomach, etc.
–Iron, being a natural component of the body, care must be taken not
to confound the iron of the blood or tissues with the “iron ’’ of a soluble
salt. Orfila attempted to distinguish between the two kinds of iron by
treating the contents of the stomach, the intestines, and even the tissues,
with cold acetic acid, and allowing them to digest in it for many hours
before filtering and testing for iron in the filtrate, and this is generally
the process which has been adopted. The acid filtrate is first treated
with sulphuretted hydrogen, which gives no precipitate with iron, and
then with sulphide of ammonium, which precipitates iron black. The
iron sulphide may be dissolved by a little hydrochloric acid and a drop
of mitric acid, and further identified by its forming Prussian blue when
tested by ferrocyanide of potash, or by the bulky precipitate of oxide,
when the acid liquid is alkalised by ammonia. In the case of Duf 2
the experts attempted to prove the existence of foreign iron in the liver
by taking 100 grims. of Duf 's liver and 100 grms. of the liver of a
non-poisoned person, and destroying each by nitro-muriatic acid, and
estimating in each acid solution the ferric oxide. Duf 's liver yielded
in 100 parts :08 mgrm. of ferric oxide, the normal liver 022—nearly
three times less than Duf 's.
To obtain iron from the urine, the fluid must be evaporated down to
a syrup in a platinum dish, a little nitric acid added, heated, and finally
completely carbonised. The residue is dissolved in hydrochloric acid.
Normal urine always contains an unweighable trace of iron ; and, there-
fore, any quantity, such as a mgrm. of ferric oxide, obtained by careful
precipitation of the hydrochloride acid solution out of 200 to 300 c.c. of
urine, would be good evidence that a soluble salt of iron had been taken.
The hydrochloric acid solution is first precipitated by ammonia and
ammonic sulphide. The precipitate thus obtained will not be pure
iron sulphide, but mixed with the earth phosphates. It should be
redissolved in HCl, precipitated by sodic carbonate, then acidified by
acetic acid and sodic acetate added, and the solution well boiled; the iron
will then be precipitated for the most part as oxide mixed with a little
phosphate of iron.
Since, as before mentioned, a great portion of the iron swallowed as a
soluble Salt is converted into insoluble compounds and excreted by the
facces, it is, in any case where poisoning by iron is suspected, of more
§ 883–885.] CHROMIUM. 7OI
importance to examine chemically the faeces and the whole length of the
alimentary canal, than even the contents of the stomach. In particular,
any black material lying on the mucous membrane may be sulphide of
iron mixed with mucus, etc., and should be detached, dissolved in a little
hydrochloric acid, and the usual tests applied.
In the criminal cases alluded to, there were iron stains on certain linen
garments which acquired an importance, for, on dissolving by the aid of
nitric acid, they gave the reactions of chlorine and iron. Any stains
found should be cut out, steeped in water, and boiled. If no iron is dis-
solved the stain should then be treated with dilute nitric acid, and the
liquid tested with ferrocyanide of potash, etc. It need scarcely be
observed that iron-mould is so common on shirts and any fabric capable
of being washed, that great care must be exercised in drawing conclusions
from insoluble deposits of the oxide.
2. CHROMIUM.
§ 883. The only salts of chromium of toxicological importance are the
neutral chromate of potash, the bichromate of potash, and the chromate
of lead.
Neutral Chromate of Potash, CrO, K2O = 1947, containing 56.7 per
cent. of its weight of chromic anhydride, CrO3–This salt is in the
form of citron-yellow rhombic crystals, easily soluble in water, but
insoluble in alcohol. Its aqueous solution is precipitated yellow by lead
acetate or basic acetate; the precipitate being insoluble in acetic acid.
If chromate of potash in solution is tested with silver nitrate, the red
chromate of silver is thrown down; the precipitate is with difficulty
soluble in dilute nitric acid.
$ 884. Potassic Bichromate, Cr,0K,O = 295-2, containing 68-07 per
cent. of its weight of chromic anhydride, CrOs. This salt is in beautiful
large, red, transparent, four-sided tables; it is anhydrous and fuses below
redness. At a high temperature it is decomposed into green oxide of
chromium and yellow chromate of potash. It is insoluble in alcohol, but
readily soluble in water. The solution gives the same precipitates with
silver, lead, and barium as the neutral chromate. On digesting a solu-
tion of the bichromate with sulphuric acid and alcohol, the solution
becomes green from the formation of chromic oxide.
$ 885. Neutral Lead Chromate, PbCrO, = 323-5, composition in 100
parts, PbO, 6894, CrO3, 31-06.-This is technically known as “Chrome
Yellow,” and is obtained as a yellow precipitate whenever a solution of
plumbic acetate is added, either to the solutions of potassic chromate or
bichromate; by adding chrome yellow to fused potassic nitrate, “chrome
red” is formed ; it has the composition CrO321'bO. Neutral lead
7O2 POISONS: THEIR EFFECTS AND DETECTION. [$886–888.
chromate is insoluble in acids, but may be dissolved by potassic or sodic
hydrates.
$ 886. Use in the Arts.-Potassic bichromate is extensively used in
the arts—in dyeing, calico-printing, the manufacture of porcelain, and in
photography; the neutral chromate has been employed to a small extent
as a medicine, and is a common laboratory reagent ; lead chromate is a
valuable pigment. , *
$ 887. Effects of some of the Chromium Compounds on Animal
Life.—In the chromates of potash there is a combination of two poison-
ous metals, so that it is not surprising that Gmelin found the chloride
of chromium, CrCls, less active than the neutral chromate of potash;
19 grm. of the last, administered to a rabbit by the stomach, caused
death within two hours, while 3 grms. of chromous chloride had no
action. Subcutaneous doses of 2 to 4 grim. of neutral chromate (accord-
ing to the experiments of E. Gergens “ and Carl Posneri) act with great
intensity on rabbits. Immediately after the injection the animals are
restless, and show marked dyspnoea; death often takes place within a
few hours.
Diarrhoea does not seem, as a rule, to follow when the salt is admin-
istered by subcutaneous injection to animals; but Gmelin's rabbits had
considerable diarrhoea when 19 grm. was introduced into the stomach.
The same quantity, injected beneath the skin of a dog, caused loss of
appetite, and, after six days, there was a dry exanthem on the back, and -
the hair fell offin patches; there was, however, neither diarrhoea nor vomit-
ing. Bichromate of potash causes (according to the researches of Pelikan)f
symptoms similar to those produced by arsenic or corrosive sublimate ; it
acts as a powerful irritant of the stomach and intestinal canal, and may
even cause inflammation ; on its absorption a series of symptoms are
produced, of which the most prominent are albuminuria, bloody urine,
and emaciation. From '06 to 36 grn. (1–5; grains) is fatal to rabbits
and dogs.
§ 888. Effects of some of the Chromium Salts on Man—Bichro-
mate Disease.—In manufacturing potassic bichromate, the workmen
exposed to the dust have suffered from a very peculiar train of symptoms,
known under the name of “bichromate disease.” It was first described
in England by Sir B. W. Richardson.S. It appears that if the workmen
inspire the particles chiefly through the mouth, a bitter and disagreeable
taste is experienced, with an increase of saliva. This increase of the
* Arch. f. eacperiment. Pathol. w. Pharmakol., Bd. vi., Hft. 1 and 2, § 148, 1875.
+ Virchow's Archiv f. path. Amat., Bd. lxxix., Hft. 2, § 333, 1880.
: Beiträge zur gerichtl, Medicin, Toa'ikol. v. Pharmakodymannik, Würzburg,
§ Brit, and For. Med. Chirurg. Review, Oct. 1863. See also a paper by the same
writer, read before the Medical Society, reported in the Lancel, March 11, 1882.
§ 889.] CHROMIUM. 7O3
buccal secretion gets rid of most of the poison, and in that case but little
ill effect is experienced; but those who keep the mouth closed and inspire
by the nose, suffer from an inflammation of the septum, which gradually
gets thin, and ultimately ulcerated; finally the whole of the septum is in
this way destroyed. It is stated that when a workman has lost his nasal
septum, he no longer suffers from nasal irritation, and has a remarkable
immunity from catarrh. The Chemical Works Committee of Inquiry
report (1893) that the manufacture of bichromate of potash or soda is
practically in the hands of three firms at Glasgow, Rutherglen, and Fal-
kirk, and that they visited all of them, and found “that almost all the
men working where dust was prevalent, more especially between the fur-
naces and the dissolving tanks, had either perforation of the septum of
the nose, or had lost the septum altogether.” The bichromate also causes
painful skin affections—eruptions akin to eczema or psoriasis; also very
deep and intractable ulcerations. These the workers call “chrome holes.”
These cutaneous maladies start from an excoriation ; so long as the skin
is not broken, there seems to be little local effect, if any. The effects of
the bichromate are also seen in horses employed at the factories; the
Salt getting into a wound or crack in the leg, produces ulceration : horses
may even lose their hoofs.
$ 889. Acute poisoning by the chromates is rare. In the ten years
ending 1903, in England and Wales, 14 accidental and 2 suicidal deaths
are ascribed to preparations of chromium. Falck has, however, been
able to find in medical literature 17 cases, 6 of which were suicidal, 10
accidental, and in one the bichromate was used as an abortive. In a
case of poisoning by the chromate of potash (related by Maschka),” in
which a woman, aged 25, took for a suicidal purpose a piece of potassic
chromate, which she described as the size of a hazel-nut (it would pro-
bably be at least 6 grns. in weight), the chief symptoms were vomiting,
diarrhoea, pain in the stomach, and rapid collapse ; death took place
fourteen hours after swallowing the poison.
In poisoning by potassic bichromate, there may be much variety in
the symptoms, the more usual being those common to all irritant
poisons, i.e. vomiting, diarrhoea, and collapse, with cramps in the limbs
and excessive thirst ; and the rarer affecting more especially the nervous
system, such as narcosis, paralysis of the lower limbs, and dilatation of
the pupils; occasionally there is slight jaundice.
In a case recorded by Dr. Macniven,i a man took a lump of bichro-
* Prager Vierteljahrsschr, f, d. prakt. Heilk., Bd. 131, § 37, 1877; Schmidt’s
Jahrb. 1878, Bd. 178, § 237. See also Schuchardt in Maschka's Handbuch, Bd. ii.
p. 3.
t “On a case of Poisoning with Bichromate of Potash,” by Ed, O. Macniven,
M.B., Lancet, Sept. 22, 1883.
7O4 POISONS: THEIR EFFECTS AND DETECTION. [$ 890.
mate of potash, estimated to be over 2 drachms (7-7 grms.). The
symptoms commenced in fifteen minutes, and consisted of lightness in
the head, and a sensation of great heat in the body, which was followed
by a cold sweat ; in twenty minutes he vomited; he then suffered from
great pain in the stomach, giddiness, specks before the eyes, a devouring
thirst, and there was loss of power over the legs. These symptoms,
again, were followed by severe rigors and great coldness of the ex-
tremities. On the patient's admission to hospital, two hours after
taking the poison, it was noted that the pupils were dilated, the face
pale and cold, and the pulse feeble. He complained of intense
epigastric pain, and a feeling of depression ; there was some stupor;
the stomach was emptied by emetics and by the stomach-pump, and
the patient treated with tepid emollient drinks, whilst subcutaneous
doses of sulphuric ether were administered. He made a good recovery.
In a case recorded by Mr. Wilson,” a man, aged 64, was found dead
in his bed twelve hours after he had gone to rest. During the might he
was heard to snore loudly; there were no signs of vomiting or purging,
and bichromate of potash was found in the stomach.t
§ 890. Chromate of lead has also caused death. In one case ; the
breathing of chromate of lead dust seems to have been fatal; and there
is also a double poisoning recorded by Dr. Linstow, $ of two children,
aged three and a half and one and three-quarter years respectively, who
ate some yellow ornaments, which were used to adorn a cake, and
which contained chrome yellow (chromate of lead). The younger died
in two and the elder in five days. The symptoms were redness of the
face, dulness, and an inclination to sleep; neither complained of pain ;
the younger one had a little diarrhoea, but the elder neither sickness nor
purging.
In Guy's Hospital Reports for 1897, Dr. Watson Smith records the
poisoning of a grocer, aged 31, by lead chromate supposed to have been
taken in home-made wine which had been standing in a lead-glazed
earthenware pan. The man became jaundiced; the urine was of a dark
colour, but gave no bile reaction. There was vomiting and obstinate
constipation. The tongue showed bluish-black pigmentation along the
* Med. Gazette, vol. xxxiii. 734. -
| See also cases recorded by Dr. M'Lachlan, Glasgow Med. Journ., July 1881 ;
Dr. M'Crorie, ibid., May 1881; Dr. R. A. Warwick, Lancet, Jan. 31, 1880; and
Dr. Dunbar Walker, ibid., Sept. 27, 1879—a summary of all of which may be found
in Dr. Macniven's paper, loc. cit.
†: Ueber todtliche Vergiftung durch Einath men des Staubes vom mit Chromsöwren
Blei-Owyde gefärblem Garme—Vierteljahrsschr. f. ger. Med., 1877, Bd. xxvii. Hſt.
i. p. 29.
§ Ibid., Bd. xx. s. 60, 1874.
| The ornaments were imitations of bees ; each contained 27 grim. gum traga-
canth, '0042 grnm, neutral lead chromate,
§ 891.] CHROMIUM. 705
left margin of the dorsum resembling “somewhat the appearance
of an ill-shaven chin in a person of dark complexion.” The man
recovered.
§ 891. Post-mortem. Appearances.—We possess some very exact
researches * upon the pathological changes induced by subcutaneous
injections of solutions of potassic bichromate on animals, and especially
on the changes which the kidneys undergo. If the animal is killed, or
dies a few hours after the injection, there are apparently no striking
appearances; but a closer microscopical examination shows considerable
changes. The epithelium of the tubuli contorti exhibits a yellow
cloudiness, and the outline of the cells is irregular and jagged.
The glomeruli are moderately injected, and their capsules contain
an albuminous exudation; the canaliculi are filled with round cells
imbedded in a fluid which, on heating, coagulates, and is therefore
albuminous or fibrinous—probably this is the first stage of the forma-
tion of fibrinous casts.
In the case quoted of the woman who poisoned herself with potassic
chromate, very striking changes were found in the stomach and intes-
tines. The stomach contained above a litre of dark chocolate fluid of
alkaline reaction; the mucous membrane, in the neighbourhood of the
cardiac and pyloric extremities, was swollen and red in sharply defined
patches; portions of the epithelial layer were detached, the rest of the
mucous membrane was of a yellow-brown colour, and the whole intestine,
from the duodenum to the sigmoid flexure, was filled with a partly
bloody, partly treacly-looking fluid ; the mucous membrane, throughout
its entire extent, was swollen, with numerous extravasations, and in
places there were losses of substance. Similar appearances to these have
been found in other instances; the anomalous case recorded by Mr.
Wilson (ante) is an exception. In this instance a pint of inky, turbid
liquid, which yielded to analysis potassic bichromate, was found in the
stomach ; but there were no marked changes anywhere, save a slight
redness of the cardiac end of the gullet. In Linstow's two cases of
poisoning by lead chromate, there were found in both fatty degeneration
of the liver cells, and red points or patches of redness in the stomach
and intestines. In the elder boy the changes in the duodenum were
very intense, the mucous membrane was swollen and easily detached, in
the upper part strongly injected with blood; in one place there was a
perforation, and in several places the membrane was extremely thin.
In the younger boy the kidneys seem to have been normal, in the
elder congested and containing pus. Although it was clear that
the two children died from lead chromate, a chemical analysis gave
no result,
* C. Posner, op. cit.
45
7O6 POISONS : THEIR EFFECTS AND DETECTION. [$ 892.
§ 892. Detection of the Chromates and Separation of the Salts
of Chromium from the Contents of the Stomach, etc.—If in the
methodical examination of an acid liquid, which has been already
filtered from any precipitate that may have been obtained by sulphur-
etted hydrogen, this liquid is made alkaline (the alkali only being
added in slight excess), and hydrated chromic oxide is thrown down
mixed, it may be, with other metals of the second class, the pre-
cipitate may then be fused with nitre and potassic carbonate, and will
yield potassic chromate, soluble in water, and recognised by the red
precipitate which it gives with silver nitrate, the yellow with lead
acetate, and the green colour produced by boiling with dilute
sulphuric acid and a little alcohol or sugar. If by treating a com-
plex liquid with ammonium hydrosulphide, sulphides of zinc, manga-
nese, and iron are thrown down mixed with chromic oxide, the same
principles apply. If a chromate is present in the contents of the
stomach, and the organic fluid is treated with hydrochloric acid and
potassic chlorate, chromic chloride is formed, and dissolving imparts a
green colour to the liquid—this in itself will be strong evidence of the
presence of a chromate, but it should be supplemented by throwing
down the oxide, and transforming it in the way detailed into potassic
chromate. &
A general method of detecting and estimating both chromium and
barium in organic matters has been worked out by L. de Koningh.*
The substances are burned to an ash in a platinum dish. The ash is
weighed; to the ash is added four times its weight of potassium sodium
carbonate and the same amount of potassium nitrate ; and the whole is
fused for fifteen minutes. The fused mass is boiled with water and
filtered; if chromium is present, the filtrate is of a more or less pro-
nounced yellow colour, but manganese may produce a green colour and
mask the yellow ; this colour is removed by boiling with a little
alcohol. The liquid is concentrated down to 20 c.c., filtered into a
test-tube, and a colorimetric estimation made of the chromium present
by imitating the colour by a solution of potassium chromate of known
strength. To prove that the colour is really due to chromium, acetic
acid and lead acetate are added, when the yellow chromate of lead is
at once thrown down. (If lead was in the ash, a yellow precipitate
may appear on the addition of acetic acid.) To the portion of ash
insoluble in water strong hydrochloric acid is added, and to the acid
solution a large excess of calcium sulphate is added; this precipitates
barium as sulphate free from lead sulphate, for, if the latter should
be present, it does not, under the circumstances, come down, being
soluble in strong hydrochloric acid.
* Arch. Pharm. (3), xxvii. 944.
§ 893–896.] THALLIUM. 707
3. THALLIUM.
§ 893. Thallium was discovered by Crookes in 1861. Its atomic weight is 204;
specific gravity, 11'81 to 1191; melting-point, 290°. It is a heavy diamagnetic
metal, very similar to lead in its physical properties. The nitrate and sulphate of
thallium are both soluble in water; the carbonate less so, requiring about 25 parts
of water for solution ; while the chloride is sparingly soluble, especially in hydro-
chloric acid.
$ 894. Effects.--All the salts of thallium are poisonous. One of the earlier
experimenters on the physiological action, Paulet, found 1 grm. (15.4 grains) of
thallium carbonate sufficient to kill a rabbit in a few hours; there were loss of mus-
cular power, trembling of the limbs, and death apparently from asphyxia. Lamy.”
used thallium sulphate, and found that dogs were salivated, and suffered from
trembling of the limbs, followed by paralysis. The most definite results were
obtained by Marmé,t who found that '04 to ‘06 grm. of a soluble thallium salt,
injected subcutaneously or directly into the veins, and 5 grim. administered through
the stomach of rabbits, caused death. The action is cumulative, and something
like that of mercury; there are redness and swelling of the mucous membrane of the
stomach, with mucous bloody discharges ; haemorrhage may also occur from the
lungs. Thallium is eliminated through the urine, and is also found in the faeces; it
passes into the urine from three to five minutes after injection: the elimination is
slow, often taking as long as three weeks. It has been found in the milk, in the
tears, in the mucous membrane of the mouth, of the trachea, in the secretion of the
gastric mucous membrane, and in the pericardial fluid ; and in these places, whether
the poison has been introduced by subcutaneous injection, or by any other channel.
It seems probable that the reason of its being detected so readily in all the secretions
is the minute quantity which can be discovered by spectroscopic analysis.
$ 895. Separation of Thallium from Organic Fluids or Tissues.—The salts of
thallium, if absorbed, would only be extracted in traces from the tissues by hydro-
chloric acid, so that, in any special search, the tissues are best destroyed by either
sulphuric or nitric acid, or both. In the ordinary method of analysis, when an acid
liquid is first treated with sulphuretted hydrogen, and then made alkaline by
ammonia and ammonic sulphide, thallium would be thrown down with the manganese
and iron of the blood. From the mixed sulphides, thallium may be separated by
oxidising and dissolving the sulphides with nitric acid, evaporating off the excess of
acid, dissolving in a very little hot water, and precipitating thallous chloride by
solution of common salt. The ease, however, with which thallium may be separated
from solutions of its salts by galvanism is so great as to render all other processes
unnecessary : the best way, therefore, is to obtain a deposit of the metal on platinum
by a current from one or more cells, and then to examine the deposit spectroscopically.
Thallium gives, when heated in a Bunsen flame, a magnificent green line, the centre
of which corresponds with wave length 534.9; a second green line, the centre of
which coincides with W. L. 568, may also be distinguished.
4. ALUMINIUM.
$ 896. Aluminium and its Salts.-A strong solution of acetate of
alumina has irritant properties, and has given rise to accidents. The
term alum, in a chemical sense, is given to a class of bodies of the
type of AlKSO. Common alum is at the present time ammonia alum,
Chem. News, 1863.
f Göttinger Gelehrt. Nachrichten, Aug. 14, No. 20.
708 POISONS : THEIR EFFECTS AND DETECTION. [$897.
NH, Al(SO4)2 + 12H2O ; when made anhydrous by heat it is known by
the name of burnt alum, and possesses caustic properties.
§ 897. Action of Alum Salts.-Death or illness has hitherto only
taken place from the ingestion of large doses of alum or the acetate, and
the symptoms in these cases have been those of an irritant poison ; we
are, however, indebted to Paul Siem * for a research on the absorbed
substance, in which the local effects as far as possible have been
reduced.
Siem's research was made on frogs, cats, and dogs. For frogs he
employed a double salt, consisting of sodic and aluminic lactate, to which
he ascribed the formula Al2(CAH3O3)3(CH, NaOs)s, equal to 15.2 per
cent. of Al,0s. Twenty to thirty mgrims, administered by subcutaneous
injection to frogs, caused death in from ten to twenty-four hours. After
the injection there was restlessness, and, ultimately, general paralysis of
the central nervous system. The circulation was not affected ; the heart
was the last to die.
For warm-blooded animals he used the double tartrate of sodium and
aluminium. Beginning with a small dose subcutaneously administered,
he gradually increased it, and found, under these circumstances, that
the lethal dose for rabbits was 0.3 grm. per kilo. of body weight; for
dogs 0-25 grim., and for cats 0.25 to 0-28 grim. ; if, however, a single
dose was administered, then cats could be killed by 0-15 grnm. per kilo.
The symptoms commenced ten to twelve hours after the injection of a
large dose, but with a medium dose the symptoms might be delayed for
from three to four days; then there was loss of appetite, constipation,
emaciation, languor, and a disinclination to move. Womiting and loss
of sensation to pain followed, the power of swallowing even saliva was
lost, and a condition supervened similar to bulbar paralysis. However
true this picture may be when large doses are given subcutaneously, it
does not follow that hydrate of alumina in small doses, given by the
mouth, mixed with food, produces any symptoms whatever.
Alum baking-powders, containing from 30 to 40 per cent. of alum
mixed with carbonate of soda, used to be found in commerce, and for a
long time many tons were sold yearly ; it is not usual at present to
meet with an alum baking-powder. When water is added to such
powders decomposition takes place, the result being sodic sulphate and
aluminic hydrate, carbonic acid being given off. Were the hydrate, in
small doses, capable of producing indigestion or disease of the central
nervous system, it seems astonishing that, considering the enormous
number of persons who have used alum baking-powders, there should
not be some definite evidence of its effect. The senior author and his
* Ueber die Wirkungen des Alwminiums w. Berylliums, Inaug. Diss., Dorpat,
1886; Schmidt’s Jahrbuch, vol. ccxi. 128.
§ 898, 899.] ALUMINIUM. 709
family for months together once used alum baking-powders without any
apparent injury; and there is little doubt that alumina hydrate passes
out of the system mainly by the bowel, without being absorbed to any
great extent. In a trial with regard to an alum baking-powder at
Pontypridd (1893), the prosecution advanced the theory, and supported
it by eminent scientific opinion, that aluminium hydrate was dissolved
by the hydrochloric acid of the gastric juice, forming chloride of
aluminium, some of which might be absorbed and enter the circulation ;
that which was not absorbed in the stomach passed on, and, meeting
the alkaline fluids of the intestines, was again separated as aluminium
hydrate, and as such absorbed.
If this does occur, still there is no direct evidence of its toxic influ-
ence in the small quantities used in baking-powder. It may be pointed
out, also, that with regard to the possible lethal effect of a non-corrosive
salt of alum, presuming that the lethal dose for man is the same as that
for a cat, the amount of alumina to kill a 68-kilogramme man would
have to be equal to 17 grms., or about 3 ozs., of ammonia alum. This
important question can only be settled by careful feeding of animals
carried on for a long period of time.
$898. Post-mortem Appearances.—In the few cases in which
persons have been killed by large doses of alum or its salts there have
been found corrosion of the mouth, throat, and stomach, and hyperaemia
of the kidneys and intestine. In the animals experimented upon by
Paul Siem, hyperamia of the intestine, ſatty degeneration of the liver,
and hyaline degeneration of the kidneys were the chief changes noted.
§ 899. Detection of Alumina.-In all operations for the detection
of alumina, glass and porcelain vessels are to be avoided. The sub-
stances should be burned to an ash in a platinum dish, the ash treated
with hydrochloric acid, the acid driven off by heat, and a few drops of
nitric acid added, and dissolved in hydrochloric acid, and the solution
boiled and filtered. If organs of the body are operated upon, iron and
phosphoric acid will be present in the ash; this will, indeed, be the case
with most organic substances. The filtered solution is boiled, and,
while boiling, poured into a strong solution of sodic hydrate contained
in a silver or platinum dish ; the iron will now separate as oxide, and
can be filtered off. To the filtrate is added a little sodic phosphate ; it
is then feebly acidified with hydrochloric acid, and ammonia added just
sufficient to render it alkaline ; a light whitish cloud of alumina phos-
phate, should alumina be present, is thrown down, and can be collected,
thoroughly washed, dried, ignited, and weighed as alumina phosphate.*
The alumina phosphate is then fused with sodic sulphate in a platinum
* One part of al. phosphate is equal to 0°42 Al2O3, 3’733 ammonia alum, and
4'481 potash alum.
7 Io POISONS: THEIR EFFECTS AND DETECTION. [$ 900–902.
dish or crucible, and the fused mass treated with hot water; the sodic
phosphate dissolves, and the alumina oxide may be filtered off and
dissolved in a little hydrochloric acid or sulphuric acid.
A solution thus prepared has the following properties:–
Ammonium sulphide; white precipitate of hydroxide.
Potash or soda ; white precipitate, soluble in excess.
Ammonia; white precipitate, only slightly soluble in excess.
There is also a blowpipe-test: if a little of the hydroxide be collected,
moistened with cobalt mitrate, and heated on charcoal by the oxidising
flame, alumina, under these circumstances, becomes of a blue colour.
5. URANIUM.
$900. Uranium.—The salts of uranium are intensely poisonous. The nitrate of
uranium is used in photography and the arts, and is a common reagent in chemical
laboratories.
According to Kowalewsky,” the acetate of uranium possesses an unusual power
of uniting with albumin ; the other soluble uranium salts act also in a similar way.
Hence concentrated solutions of uranium salts corrode the mucous membranes, trans-
forming, for example, the walls of the stomach into a dead uranic albuminate. If a
non-corrosive salt of uranium is injected subcutaneously, glycosuria is produced, with
fatty degeneration of the walls of the blood-vessels, and fatty changes in the kidneys,
liver, etc. The animal wastes and ultimately dies; 0'5 to 2-0 mgrms. of UO3 per
kilogrim. will kill a cat, dog, or rabbit, if injected subcutaneously. The nitrate or
acetate, when given by the mouth, produces gastro-enteritis and nephritis, with
haemorrhages in the substance of the kidney. Uranium is not used in medicine.
§ 901. Detection and Estimation of Uranium.—Uranium forms uranous and
uranic salts. Both classes of salts are not precipitated by SH2, but are precipitable
by ammonium sulphide, and, therefore, in toxicological analyses are likely to be met
with in conjunction with iron.
The sulphides of iron and uranium may be dissolved in strong hydrochloric acid,
boiled to expel SH2, and the solution then oxidised with a little nitric acid ; the solu-
tion is now alkalised with ammonium carbonate, which precipitates the iron as oxide
and leaves the uranium in solution. On now acidifying with nitric acid in slight
excess, a solution of sodic phosphate will precipitate uranium phosphate as a white
precipitate, alkalies will give a yellow precipitate, alkaline carbonates a yellow pre-
cipitate soluble in excess. Barium carbonate also gives a precipitate, and is useful
in separations. Uranium oxide gives a green glass in the oxidising flame with borax
or with sodic metaphosphate.
W.—ALKALINE EARTHS.
Barium.
$902. The soluble salts of barium are undoubtedly poisonous, and
are of frequent occurrence in the arts. The chloride of barium is used
in the staining of wool, the nitrate and the chlorate in the green fires of
* Zeitschr. f. anal. Chemie, xxiv., 1885, p. 551.
§ 903–906.] BARIUM. 7 II
the pyrotechnist, the oxide and the carbonate in the manufacture of
glass. The chromate is used by artists under the name of “yellow
ultramarine,” while the sulphate, technically known as “permanent
white,” is, on account of its weight and cheapness, occasionally used as
an adulterant of white powders and other substances. Barium sulphide,
under various names, such as Bottcher's depilatory, Thompson's hair
destroyer, Poudre epilatoire, and other names, is in commerce, and has
caused poisonous symptoms.”
§ 903. Chloride of Barium, BaCl,2H,0=208 + 36—anhydrous, Ba,
65.86 per cent.; Cl, 34°14; specific gravity, 3-75—is in commerce in the
form of white, four-sided, tabular crystals; water dissolves about half its
weight at ordinary temperatures, three-fourths at 100°. Its solution
gives a white precipitate with sulphuric acid, quite insoluble in water
and nitric acid.
The salt imparts a green hue to an otherwise colourless flame ;
viewed by the spectroscope, green bands will be visible. We may
note that chloride of barium gives two different spectra—the one
at the moment of the introduction of the salt, the other when the
substance has been exposed for some time to a high temperature.
This is caused by a rapid loss of chlorine, so that the first spectrum
is due to BaCl2, with a variable mixture of BaCl, the second to
BaCl alone.
$904. Baric Carbonate, BaCO3 = 197—specific gravity, 4:3; PaO,
77-69 per cent. ; CO2, 22.31—in its native form termed Witherite, is a
dense, heavy powder, insoluble in pure water, but dissolving in acetic,
nitric, and hydrochloric acids, the solution giving the reactions of
barium. -
A rat-poison may be met with composed of baric carbonate, sugar,
and oatmeal, flavoured with a little oil of aniseed and caraway.
$905. Sulphate of Barium, BaSO-specific gravity, 4:59; Ba0,
65-66 per cent.; SOs, 34'34 per cent.—is a pure white powder when
recently precipitated, absolutely insoluble in water, and practically
insoluble in cold dilute acids. It is quite unalterable in the air
at a red heat ; on ignition with charcoal it may be converted almost
entirely into sulphide of barium, and by ignition with CaCl2 into
chloride.
§ 906. Effects of the Soluble Salts of Barium on Animals.—One
of the early notices of the poisonous characters of barium compounds
was by James Watt,t who found that Witherite, given to dogs, produced
* Barium carbonate and sulphate are usually enumerated as occasional adulter-
ants of bread, but there is no modern authentic instance of this.
t Memoirs of the Literary and Philosophical Society of Manchester, 1790, vol. iii.
p. 609.
7 I2 POISONS : THEIR EFFECTS AND DETECTION. [$ 906.
vomiting, diarrhoea, and death in a few hours. Sir Benj. Brodie “
administered barium chloride, and noticed its paralysing effect on the
heart. Orfila i made several experiments, and observed that 4 grims. of
the carbonate produced death in dogs in periods varying from one to
five hours; but in these experiments the gullet was tied. The later
investigators have been Gmelin, Onsum, Cyon, and Böhm.f Gmelin
found barium carbonate and barium chloride act in a very similar
manner; and, indeed, it is improbable that barium carbonate, as
carbonate, has any action, but, when swallowed, the hydrochloric and
other acids of the stomach form with it soluble compounds. J. Onsum
made eight experiments with both barium carbonate and chloride on
animals. The respiration was quickened and, at the same time, made
weak and shallow; the heart's action was accelerated ; the animals
became restless; and there was great muscular prostration, with
paralytic symptoms; convulsions did not occur in any one of the eight
animals. He found, on post-mortem examination, the right side of the
heart full of blood from backward engorgement; he describes a plugging
of the small arteries with little fibrinous coagula, having an inorganic
nucleus, with constant hamorrhagic extravasations. Onsum seems to
have held the theory that the baryta salts circulated in the blood,
and then formed insoluble compounds, which were arrested in the
lungs, causing minute emboli, just in the same way as if a finely-
divided solid were introduced directly into the circulation by the
jugular vein.
Onsum stands alone in this view. Cyon found no emboli in the
lungs, and refers the toxic effect to a paralysing influence on the heart
and voluntary muscles, and also on the spinal chord. Cyon, to settle
the embolic theory, injected into the one jugular vein of a rabbit barium
chloride, and into the other sodic sulphate, but the small arteries and
capillaries of the lungs remained clear. Böhm, operating on frogs, found
a great similarity between the action of small doses of barium salts and
that of certain organic poisons, as, for example, cicutoxin ; 012 to 02
grm. Subcutaneously injected into frogs, acted as a heart-poison. So also
Blake $ found the heart slowed, and concluded that barium chloride
had a direct action on the cardiac muscle, and also a toxic influence on
the nervous system. F. A. Falck, in experiments on rabbits, found a
great reduction of temperature after poisoning with barium chloride
(3° to 12.6°).
* Phil. Trams., 1812. + Traité des Poisons, 3rd ed., t. i., Paris, 1826.
† Gmelin, C. G., Versuché über die Wirkwºngen des Baryts, Stromtians, Chroms,
Molybdāns, Wolframs, Tellurs w. S. w. auf dem thierischen Organismus, Tübingen,
1824; Onsum, J., Virchow's Archiv, Bd. ii. 1863; Cyon, M., Archiv f. Anatomie,
Physiologie, etc., 1866; Böhm, Archiv f. eacperiment. Pathol., Bd. iii. 1874.
§ Journ. of Amat, and Physiol., 2nd series, 1874.
§ 907, 908.] BARIUM. 7 I 3
§ 907. Effects of the Salts of Barium on Man.—There were about
fifteen cases of poisoning by barium salts on record by the end of 1883
—three of which were suicidal, but most of them were due to accident
or mistake; one accidental death is also recorded in the ten years ending
1903. In three cases, barium chloride was taken instead of Glauber's
salts; in one, instead of Carlsbad salts; in another, a mixture of barium
nitrate and sulphur, instead of pure sulphur; in a sixth case, a mixture
of barium acetate and raspberry syrup, instead of sodic ethylsulphate ;
in a seventh, a chemist put a larger dose than was ordered by the pre-
scription; and in four cases barium carbonate had been mixed with
flour, and this flour used in the making of pastry. Of the cases, 60 per
cent, proved fatal.
Fatal Dose.—The recorded cases of poisoning have not satisfactorily
settled the question as to the least fatal dose of the barium salts: 6-5
grns. (about 100 grains) of the chloride have destroyed the life of an
adult woman in fifteen hours; 14 grims. (; oz.) of the nitrate of baryta
have killed a man in six and a half hours; and the carbonate of baryta
has destroyed a person in the relatively small dose of 3-8 grms.
(60 grains). On the other hand, certain Continental physicians have
prescribed barium chloride in large medicinal doses; for example,
Pirondi “ and Lisfranc f have gradually raised the dose of barium
chloride from 4 decigrams up to 3 grms. (48 grains) daily, given, of
course, in divided doses. Pirondi himself took in a day 7-7 grims. (119
grains) without bad effect.
§ 908. Symptoms.-The local action of barium salts must be sharply
distinguished from the action of the absorbed salts. Kobert divides the
symptoms into seven groups : —
(1) Local, consisting in malaise, nausea, salivation, vomiting, and
pain in the stomach. This group merges so much into the next as
hardly to admit of precise separation.
(2) Excitation of the alimentary canal, both of the nervous
and muscular apparatus; hence vomiting, painful colic, and acute
diarrhoea. All these phenomena may be produced in animals by
subcutaneous injection, and, therefore, do not depend alone upon
local action.
(3) Excitation of the brain motor centres, which leads to convulsions,
or may result in paralysis. About half the recorded cases of barium
poisoning in the human subject have been convulsed; the other half
paralysed. In one case mania resulted.
(4) Weakness or destruction of the power of muscular contraction ;
this produces in frogs, when the muscular test movements are recorded
* De la Twmeur Blanche de Gemow, ed. 2, Paris, 1836.
+ Gaz. Méd. de Paris, 1835, No. 14.
7 I4 POISONS : THEIR EFFECTS AND DETECTION. [$ 909.
graphically, a veratrin-like convulsion curve. In the human subject the
effect is that of great muscular weakness.
(5) Digitalin-like influence on the heart and blood-vessels, showing
itself in great slowing of the pulse, praecordial anxiety, and strong
beating of the heart (not only sensible to the patient, but which
can be heard and felt by the bystanders). The arteries are incom-
pressible and rigid, the blood-pressure strikingly raised. The blood-
vessels of old people do not stand the pressure, hence haemorrhages
in the lungs, stomach, and other organs. Frogs die with the heart
in systole.
(6) Catarrhal affection of the conjunctiva, the mucous membrane of
the respiratory tract, and the nose.
(7) Formation of insoluble baryta salts in the blood-vessels, accord-
ing to Onsum. This has not been observed in man, and the fact is
disputed (see ante).
In Dr. Tidy's case,” in which a man, suffering from rheumatism, but
otherwise healthy, took a mixture of barium nitrate, flowers of sulphur,
and potassic chlorate, instead of sulphur, the symptoms were blisters on
the tongue, a burning pain in the gullet and stomach, with vomiting,
diarrhoea, convulsions, aphonia, and coldness of the extremities. A case,
copiously detailed by Seidel,i in which a pregnant woman, 28 years
old, took carbonate of baryta for the purpose of self-destruction, is in-
teresting. She probably took the poison some little time before six in
the evening; she vomited and had great pain in the stomach, but slept
during the night without further sickness. The next morning, after
drinking some coffee, the sickness was renewed; nevertheless, at 7 A.M.,
she repaired to her employment, which was distant an hour's walk; she
probably suffered much on the way, for she did not arrive until 9 A.M.
The vomiting, accompanied by diarrhoea, continuing, she was sent to
bed at 2 P.M. She was very cold, and complained of great weakness;
the vomiting now ceased. At 8 P.M. she shivered violently, could
scarcely swallow, and the respiration was oppressed. At 11 she
seemed a little improved ; but at 3 A.M. she was found much worse,
breathing rapidly, but fully conscious; at 4 A.M. she was again seen,
but found dead: she thus lived about thirty-four hours after taking
the fatal dose. -
§ 909. Distribution of Barium in the Body.—Neumann has shown
that after repeated injection of insoluble barium sulphate into the veins
of rabbits, barium is to be found in the liver, kidneys, spleen, and
spinal cord, but not in the muscles, thymus, or brain. G. Linossier i
* Pharm. Journ., June 1868. *
+ Eulenberg's Vierteljahrsschrift f. ger. Med., Bd. xxvii., § 213.
# Compt. rend. Soc. Biol. (8), iv. 122–123.
§ 910, 91 I.] BARIUM. 7I 5
has made a similar series of experiments, but with th ecarbonate, and
this salt was injected into animals for a period of thirty days. All the
organs contained some barium : lungs, muscles, and the heart only con-
tained traces; the liver rather more ; the kidneys, brain, and spinal cord
still more ; and, lastly, the bones a considerable quantity, as much as
0-056 per cent.
§ 910. Post-mortem Appearances.—The post-mortem appearances
are usually changes in the stomach and intestinal tract, but there are
only rarely traces of great inflammation. It is true that in a case
recorded by Wach” perforation of the stomach was found; but, since
there was old-standing disease of both liver and stomach, it is not clear
that this is to be attributed entirely to poison. In the case of suicide
just detailed, the mucous membrane of the stomach was much
ecchymosed; over the whole were strewn little white grains, sticking
to the mucous membrane, and there were also ecchymoses in the
duodenum.
§ 911. The Separation of Barium Salts from Organic Solids or
Fluids, and their Identification.—In the usual course of examination
of an unknown substance, the matter will already have been extracted
by hydrochloric acid, and the solution successively treated with hydric
and ammonic sulphides. The filtrate from any precipitate, after
being boiled, would in such a case give a precipitate if treated with
sulphuric acid, should a salt of barium soluble in hydrochloric acid
be present.
If there, however, should be special grounds to search for baryta in
particular, it is best to extract the substances with pure boiling water, to
concentrate the solution, and then add sulphuric acid, collecting any pre-
cipitate which may form. If the latter is found to be sulphate of baryta,
it must be derived from some soluble salt, such as the nitrate or the
chloride. The substances which have been exhausted with water are
now treated with hydrochloric acid, and to the acid filtrate sulphuric
acid is added. If sulphate of baryta is thrown down, the baryta present
must have been a salt, insoluble in water, soluble in acids—probably the
carbonate. Lastly, the organic substances may be burned to an ash, the
ash fused with carbonate of soda, the mass, when cool, dissolved in HCl,
and the solution precipitated with sulphuric acid. Any baryta now
obtained was present probably in the form of sulphate; nevertheless, if
obtained from the tissues, it would prove that a soluble salt had been
administered, for (so far as is known) sulphate of barium is not taken up
by the animal fluids, and is innocuous.
The sulphate of barium is identified as follows:–
(1) A part of the well-washed precipitate is boiled with distilled
* Henke's Zeitschrift f. Staatsarzneik., 1835, Bd. xxx., Hft. 1, § 1.
716 POISONS: THEIR EFFECTS AND DETECTION, [$ 91 1.
water, filtered, and to the filtrate a solution of chloride of barium added.
If there is no precipitate, the sulphate can be none other than baric
sulphate, for all the rest, without exception, are soluble enough to give
a slight cloud with baric chloride.
(2) The sulphate may be changed into sulphide by ignition on char-
coal, the sulphide treated with HCl, the solution evaporated to dryness,
and the resulting chloride examined spectroscopically; or, the sulphide
may be mixed with chloride of calcium, taken up on a loop of platinum
wire, heated strongly in the flame of a Bunsen burner, and the flame
examined by the spectroscope.
(3) A solution of the chloride of barium obtained from (2) gives
a yellow precipitate with neutral chromate of potash, insoluble in water,
but soluble in nitric acid.
A PPENDIX.
Treatment by Antidotes or otherwise of Cases of Poisoning.
§ 912. All medical men in practice are liable to be summoned hastily
to cases of poisoning. In such emergencies not a moment is to be lost,
for valuable lives have ere this been sacrificed simply from the delay
caused by searching for medicines and instruments, and visiting the
patient unprovided with suitable remedies. Hence it is far the safest
plan for every medical man to provide himself with an “antidote baſſ,”
which, to be complete, should be furnished with the following
requisites:—
I. INSTRUMENTS:—
(1) A stomach pump or tube,” with proper mouth-gags.
(2) A hypodermic syringe.
(3) An ordinary bleeding lancet.
(4) A glass-syringe with suitable canula, which may, in case of
necessity, be used for transfusion.
(5) Bistoury, forceps, and tubes suitable for performing tracheotomy.
A small battery (interrupted current).
* The stomach-tube is simply a tube of india-rubber, from 6 to 8 feet in length,
one end of which should be a little stiff, and have a solid rounded extremity pierced
with two lateral oval holes—catheter-like ; but, on an emergency, any india-rubber
tube of a suitable length will do. It is used by passing the proper end gently down
the throat into the stomach ; if the patient is insensible, or, as in some determined
suicides, obstinate, the jaws must be forcibly opened by the handle of a spoon, and
some solid substance placed between the teeth so as to give sufficient room for the
entry of the tube. If the tube is now passed in the median line well into the grasp
of the pharynx, it is actually drawn down into the stomach by the pharyngeal
muscles, so that the operator has, as it were, only to “pay out” a sufficient quantity
of the tubing. Holding the tube in a perpendicular position, it may then be filled
with water by means of a small funnel. When full, the end must be pinched and
brought down to the ground to deliver in a basin ; it will then act as a syphon, and
the contents of the stomach will be syphoned off. The tube is elevated again above
the body, and the stomach filled with water ; this syphoned off, and the process
repeated. Coffee, also, or antidotes may be conveniently introduced. If the recum-
bent position is necessary, the patient must, of course, be placed on a bed or table, in
order that there should be sufficient fall for the syphon.
717
718 POISONS: THEIR EFFECTS AND DETECTION. [$ 912.
II. EMETICS :—
(1) Sulphate of zinc.
(2) Apomorphine.
(3) Mustard.
(4) Ipecacuanha.
The sulphate of zinc may either be carried in 30-grain powders or
in the ordinary solid crystalline state, together with a little measure
made out of a small pill-box which, when exactly full, is found to con-
tain from 25 to 30 grains.
A still more convenient form is that of the compressed tablets, sold
as a speciality by one or more firms. The same remarks apply to
'pecacuanha.
The apomorphine hydrochlorate should be in solution ; a suitable
strength is 2 per cent. A few drops of this substance, injected hypo-
dermically, will cause vomiting in a few minutes.
Besides the above list, the bag should be furnished with a selection
of the so-called antidotes.
ANTIDOTES:—
(a) Chemicals neutralising the poison.
Acetic acid and calcined magnesia.
(b) Precipitants of alkaloids.
Tannin.—A solution of iodine in potassic iodide.
(c) Narcotics, or anaesthetics, for the treatment of the tetanic class.
Chloral—chloroform.
(d) Substances which act physiologically.
French oil of turpentine.—A solution of atropine sulphate for
hypodermic use (strength 8 per cent.); hypodermic dose from 5 to 6
drops.
Solution of nitrate of pilocarpine (strength 5 per cent.); dose, 10
drops or more.
Muscarine.—A solution in water (strength 5 per cent.); dose, 10
drops.
Morphine meconate in solution (strength 10 per cent.); dose, from
5 drops.
A solution of nitrate of strychnine (strength 2 per cent.); hypo-
dermic dose, from 2 to 3 drops. -
Potassium Permanganate in crystals. *
To these may be added a bottle of Wyeth's dialysed iron for use
in arsenic poisoning, a flask of brandy, some chloric ether, aromatic
spirits of ammonia, and some really good extract of coffee.
§ 913.] APPENDIX . TREATMENT— ANTIDOTES. 7 IQ
z' T R. E. A. T M E N T.
4n. ACID, CARBOLIC.
Use the stomach tube or pump, unless there is great destruction of
the mucous membrane. In the latter case, excite vomiting by injecting
subcutaneously from 5 to 6 drops of the apomorphine solution ; or give
an emetic of zinc sulphate, ipecacuanha, or mustard.
The stomach may, by the aid of the tube, be washed out with a
weak alkaline solution of soda ; albumen may also be given, and such
stimulants as brandy and water, chloric ether, and aromatic spirits of
ammonia.
It is important to apply warmth to the extremities.
Inject subcutaneously from 2 to 3 drops of the atropine hypodermic
solution.
Nitrite of amyl by inhalation is said to have been useful.
In desperate cases bleeding, followed by transfusion, is to be con-
sidered.
A ACIDs—MINERAL, including SULPHURIC, NITRIC, HYDROCHLORIG, GLACIAL
ACETIC ACIDs.
Stomach tube or pump, inadmissible.
Neutralise by calcined magnesia, lime, chalk, or soda, but not with
potash, if there is choice.
If no neutralising agent can be immediately procured, then dilute
with plenty of water.
Other remedies are—oil, milk, white of eggs, gruel.
It is often recommended in such cases to administer hypodermically
a little morphine. **
WAconite—Acontine.
Use at once the stomach tube or pump, or give emetics of sulphate
of zinc, or hypodermic solution of apomorphine.
Keep the patient in the recumbent posture.
After the stomach has been emptied, give atropine, either by hypo-
dermic injection or by the mouth, say 4 drops of the P.B. solution;
failing atropine, 20 drops of the tincture of belladonna. The dose may
be repeated more or less frequently according to the condition of the
patient.
If there is great tendency to heart-syncope, tincture of digitalis in
#-drachm doses by the mouth, or in hypodermic doses of from 10 drops
upwards. -
Apply a mustard poultice to the pericardium; aid vomiting and
72O POISONs: THEIR EFFECTS AND DETECTION. [$ 913.
elimination of the poison by plenty of water, to which may be added
brandy or any form of alcohol.
Inhalations of nitrite of amyl are said to have been useful. If the
breathing stops, try artificial respiration. -
ALCOHOL.
Empty the stomach by the tube or pump, and then wash it out with
warm coffee; if the stomach-tube is not at hand, them empty the stomach
by hypodermic injection of 5 drops of apomorphine, or by a mustard
emetic, or sulphate of zinc. Keep the body very warm, but the cold
douche may be applied to the head.
Endeavours should be made to rouse the patient, if insensible, by
shaking, shouting at him, etc.
Inhalations of amyl nitrite are said to be useful.
ALKALIES.–AMMONIA—POTASH-SODA.—Stomach pump or tube not to
be used.
Womiting nearly always present, or may be produced by administer-
ing plenty of lukewarm water, after which give dilute vinegar, or the
juice of lemons or oranges; olive oil, the white of eggs, barley-
water, arrowroot, and always plenty of water may be administered.
There may be oadema of the glottis, especially if ammonia has been
taken. In such a case, and death threatening from suffocation, perform
tracheotomy. In poisoning by ammonia, with croupous respiration,
keep the room warm, and fill it with steam by means of a bronchitis
kettle.
Relieve pain by small doses of morphine injected subcutaneously.
AMMONIA.—See ALKALIES.
ANTIARIN.—See DIGITALIS,
ANTIMONY–TARTAR-EMETIC–ANTIMONIAL WINE, ETC.
The stomach will generally have been emptied by vomiting. In those
rare cases in which this does not take place, use the stomach pump or
tube, or give hypodermic injection of apomorphine.
Follow this with doses of strong tea, or give half a drachm of tannin
or gallic acid in warm water.
Give also demulcent drinks, and stimulants in small doses, frequently
repeated.
Reep the patient very warm by hot blankets and wraps.
The interrupted galvanic current to the heart may be useful.
APOCYNIN.—See DIGITALIS.
§ 913.] APPENDIX : TREATMENT—ANTIDOTES. 721
1/ ARSENIC.
Use the stomach pump or tube, or empty stomach by emetics, such
as hypodermic solution of apomorphine, or give mustard or sulphate of
zinc. The stomach should then be washed out by large quantities of
water, most conveniently administered by the pump or tube.
If the tube or pump is not at hand, then administer at once either
dialysed iron, or the freshly-precipitated hydrated oxide of iron,
obtained by precipitating the ordinary perchloride by means of
carbonate of soda or ammonia, avoiding excess of the latter. If the
operator has sufficient chemical knowledge to precipitate the iron with
fair exactness, so that there is no great excess of ammonia, or of sodic
carbonate, then filtration is unnecessary. In other cases, filter through
a handkerchief.
Oil, mucilaginous drinks, the white of eggs, and, if faintness exists,
small doses of stimulants may all be given.
- If the skin is cold, warmth must be applied to the body by means of
hot blankets, etc.
Pain may be relieved by morphine.
V. ATROPINE–BELLADONNA—TINCTURE OF BELLADONNA.
Empty the stomach by means of the stomach pump or tube.
Give an enema of coffee. -
Administer half a grain of pilocarpine nitrate ; or, if that is not at
hand, morphine or opium in suitable doses will act to a certain extent
antagonistic to the poison.
A subcutaneous dose of muscarine may be administered instead of
pilocarpine, but is not quite so good.
Hot water to the feet, alternate douches of cold and hot water are
found useful. - *
If the respiration seems likely to stop, artificial respiration must be
practised.
BELLADoNNA.—See ATROPINE.
BENZENE.
If swallowed, then empty the stomach by pump or tube, or by the
hypodermic injection of apomorphine ; or give emetics, such as zinc
sulphate, mustard, or ipecacuanha.
If the vapour has been inhaled, this is unnecessary.
Plenty of fresh air.
A subcutaneous dose of atropine, say 1-60th of a grain, or from 30
to 40 drops of belladonna tincture.
Alternate douches of hot and cold water to the chest, artificial
46
722 POISONS : THEIR EFFECTS AND DETECTION. [$ 913.
respiration, if necessary. The heart to be maintained by mild inter-
rupted shocks of the battery over the region of the heart.
BICHROMATE OF POTASH.-See CHROMIUM.
BRUCINE.—See STRYCHNINE,
CALABAR BEAN–PHYSOSTIGMINE.
Use stomach pump or tube, or emetics, such as sulphate of zinc,
mustard, or ipecacuanha; or, better still, hypodermic solution of
apomorphine.
Give hypodermic doses of 1-60th grain atropine until the pupils
dilate. This treatment seeming to fail, chloral in 10-grain doses, every
quarter of an hour, has been recommended.
In certain cases Strychnine has been used in hypodermic doses of
1-12th of a grain. -
Stimulants and artificial respiration will probably be necessary in
SODO € C3S6S.
CAMPHOR.
Use stomach pump or tube, or empty the stomach by emetics.
Hypodermic injections of brandy, inhalations of ether, the alternate
hot and cold douche, warmth to the extremities by hot blankets, etc.,
seem to be the best methods of treatment.
CANTHARIDEs—CANTHARIDINE.
Use stomach pump or tube, if the mucous membrane of the throat
is not inflamed ; or, administer hypodermic dose of apomorphine, or
give emetics—sulphate of zinc, mustard, or ipecacuanha.
Allay pain with morphine. Give plenty of water and demulcent
drinks,
CHLORAL.
Use stomach pump or tube, and, when the stomach is emptied,
introduce by the same means warm coffee, or give a hypodermic
injection of apomorphine, or administer emetics of sulphate of zinc,
or mustard, or ipecacuanha.
An enema of coffee will be useful.
Keep the limbs warm. -
Administer hypodermically 2 or 3 drops of the solution of Strychnine
at intervals of from fifteen to twenty minutes.
Rouse the patient by various means, such as shouting, shaking,
flapping the skin with a wet towel, etc. -
Inhalations of amyl nitrite are recommended.
Artificial respiration may be necessary.
§ 913.] APPENDIX : TREATMENT—ANTIDOTES. 723
CHLoRATE OF POTASH.
Use the same treatment as for nitrate of potash (which see, p. 728).
CHLORIDE of ZINC.—See ZINC.
// CHLOROFORM-(Inhaled).
Give plenty of fresh air, pull the tongue forward, and commence at
once artificial respiration. If the heart has stopped, strike the chest
two or three times very hard over the region of the heart; this has been
found occasionally to restore its beat. Apply the battery, but with a
weak current only; one pole may be placed on the larynx, the other at
the pit of the stomach.
Inhalations of nitrite of amyl are useful. The hot and cold douche
may also be used.
v. CHLoROFORM-(Swallowed).
Empty the stomach by pump or tube, or by emetics, such as 5 drops
of the hypodermic solution of apomorphine, or sulphate of zinc, or
mustard. -
Give an enema of hot coffee.
Administer large draughts of water, which may advantageously
contain a little sodic carbonate in solution.
Attempt to rouse the patient. Nitrite of amyl inhalations, and, if
necessary, artificial respiration may be used.
CHROMATE OF POTASH.-See CHROMIUM.
CHROMIC ACID.—See CHROMIUM.
CHROMIUM-BICHROMATE OF POTASH–CHROMATE OF POTASH–CHROMIC
ACID.
Empty the stomach by pump or tube; administer a subcutaneous
injection of apomorphine, or give sulphate of zinc, mustard, or
ipecacuanha as emetics. Follow up by administering, suspended in
water, calcined magnesia, or carbonate of magnesia, or chalk.
Demulcent drinks, such as barley-water, etc. .
CocCULUs INDICUs.-See PICROTOxIN.
* ColchioUM–MEADow SAFFRON-CoLCHICUM WINE, TINCTURE, ETC.
Use stomach pump or tube, or empty the stomach by emetics, such
as sulphate of zinc, or mustard, or ipecacuanha; or, better than all,
give a hypodermic injection of 4 or 5 drops of the solution of apo-
morphine.
Give tannin or gallic acid in #-drachm doses, or strong tea or coffee.
724 POISONS: THEIR EFFECTS AND DETECTION. [$ 913.
Allay the pain in the bowels and purging by small doses of opium
or morphine.
Keep the extremities warm, apply hot fomentations to the abdomen;
stimulants may be used, give plenty of water and demulcent drinks.
CoLocyNTH.
Treatment on the same lines as that for CoICHICUM.
CONIUM-HEMLOCK.
Empty the stomach by the pump or tube, or give a hypodermic
injection of 4 or 5 drops of the solution of apomorphine, or emetics of
sulphate of zinc, or mustard.
Keep up the temperature of the body by hot wraps.
Administer, as a drink, strong tea, tannin, gallic acid, or any
harmless vegetable decoction containing tannin.
Stimulants may be administered.
If necessary, use artificial respiration.
COPPER—SALTs of.
Empty stomach by pump or tube, and either inject by the same means
or administer white of egg in solution in water; if no white of eggs can
be had, substitute milk; give plenty of water and emollient drinks.
Pain may be allayed by opium or morphine.
CoRROSIVE SUBLIMATE — PERCHLORIDE OF MERCURY — NITRATE OF
MERCURY.
Empty the stomach by the tube or pump, and wash the organ out
with plenty of white of egg, dissolved in water or milk. If the stomach-
pump is not at hand, then give emetics, such as the solution of apomor-
phine, hypodermically, in from 4- to 5-drop doses, or a zinc sulphate
emetic, or mustard, or ipecacuanha. Probably violent vomiting is
already present, then stomach-tube or emetics are unnecessary: but, in
any case, give plenty of albuminous fluids, such as white of egg in
water or milk. If neither of these is at hand, chop any fresh meat up
as finely as can be done in a short space of time, diffuse in water, and
administer. Follow up with demulcent drinks, such as barley-water,
flour and water, etc. - -
Pain may be allayed with a little opium or morphine.
Stimulants are admissible, if necessary.
CROTON OIL. -
Empty stomach by means of tube or pump, or give emetics of
mustard or sulphate of zinc, or administer hypodermic injection of
apomorphine. * *
§ 913.] APPENDIX: TREATMENT—ANTIDOTES. 725
Give 10 drops of laudanum every twenty minutes or half hour,
until the pain and purging are somewhat abated, or else inject sub-
cutaneously small doses of morphine at intervals.
Give plenty of demulcent drinks.
Two or three drops of essence of camphor in milk are useful.
Stimulants, such as brandy, ammonia, or chloric ether, are
admissible.
CYTISINE.—See LABURNUM.
CURARINE–WooRARI—URARI. -
The poison is, of course, introduced by a wound: if any is likely to
be still in the wound apply a ligature, suck the wound, and then wash
it with a slightly alkaline solution of potassic permanganate.
Keep up the respiration artificially, give plenty of water and a
dose of spirits of nitre, apply warmth to the loins. By these means the
poison will be rapidly separated by the urine; and, if the patient can
only be kept alive by artificial respiration for a little time, he may
recover, for elimination is very rapid.
CYANIDE OF POTASSIUM.–See PRUSSIC ACID.
/~ DIGITALIS GROUP OF HEART Poisons, including, besides the DIGITALINs,
ANTIARIN, APOCYNIN, NERIIN, OLEANDRIN, EvoNYMIN, THEVETIN,
SCILLAIN, STROPHANTIN, and ERYTHROPHLEIN.
Empty the stomach by the tube or pump, or administer a sub-
cutaneous dose (4 drops) of apomorphine, or give a tablespoonful of
mustard in water, or sulphate of zinc. -
Follow up with strong tea, or half a drachm of tannin, or gallic
acid in aqueous solution.
A very small dose of aconitine nitrate in solution (say 1-200th of a
grain) may be injected subcutaneously and the effect watched; if in a
little time it seems to do good, repeat the dose. On no account let the
patient rise from the recumbent posture, or he may faint to death.
Stimulants in small doses may be given frequently by the mouth,
or, if there is vomiting, by the bowel.
ERGOT.
Use stomach pump or tube, or empty the stomach by a mustard
or sulphate of zinc emetic, or give a subcutaneous injection of apo-
morphine.
Give a purgative, such as a drop of Croton oil, and assist its action
by plenty of warm drinks. -
726 POISONS : THEIR EFFECTS AND DETECTION. [$ 913.
Tannin and gallic acid have also been recommended, but are
probably of but little use.
After the bowels have well acted, and the stomach has been emptied,
give small doses of opium at intervals.
Dr. Murrell recommends 1-50th of a grain of nitro-glycerin every
fifteen minutes.
The recumbent position is necessary, and the circulation should be
maintained by warmth, and, if necessary, by friction.
ERYTHROPHLEIN.—See DIGITALIS.
Eman-The same treatment as with CHLOROFORM.
EVONYMIN.—See DIGITALIS.
l: UNGI.—See MUSHROOMS.
GELSEM.ININE.
If seen soon after taking the dose, use the stomach pump or tube,
or give a tablespoonful of mustard.
Administer a small dose of atropine subcutaneously, or give by the
mouth tincture of belladonna in 20-drop doses.
Stimulants are admissible.
If necessary, use artificial respiration.
Rouse the patient by hot and cold douches.
HEMLOCK.—See CoNIINE—CONIUM.
HENBANE–HYOSCYAMINE.—The same treatment as for ATROPINE.
HYDROCHLORIC ACID.—See ACIDS, MINERAL.
HYDROCYANIC ACID.—See PRUSSIC ACID.
Hyoscy AMINE.—The same treatment as for ATROPINE.
IODINE. -
Empty the stomach by pump or tube, or administer emetics, such as
the hypodermic solution of apomorphine, or give by the mouth mustard
or sulphate of zinc. -
Give plenty of starch diffused in warm water, or in the form of a
dilute paste; or give any farinaceous substance whatever, such as
arrowroot, boiled rice, or flour, or thin gruel. -
Inhalations of amyl nitrite have been recommended.
Pain may be relieved by morphine or opium.
JABORANDI.—Treatment the same as PILOOARPINE.
§ 913.] APPENDIX : TREATMENT—ANTIDOTES. 727
LABURNUM SEEDs—CYTISINE.
Empty stomach by tube or pump, and wash it out with tea or coffee,
or give (as an emetic) a hypodermic dose of apomorphine, or (by the
mouth) mustard or zinc sulphate; follow up this treatment by an
enema, or a brisk purgative. --
Stimulants may be administered; the patient may be roused by the
hot or cold douche.
LAUDANUM.—See MoRPHINE.
LAUREL WATER.—See PRUSSIC ACID.
y LEAD, SALTs of.
Empty stomach by pump or tube, or administer subcutaneously a dose
of apomorphine, 4 to 5 drops; or give by the mouth a sulphate of zinc
or mustard emetic. Follow up with half a drachm of dilute sulphuric
acid, or half an ounce of magnesic or sodic sulphate.
Milk and albuminous fluids may be given.
Allay pain with opium or morphine. Treat colic with hot fonmen-
tations.
MEADow SAFFRON.—See ColchioUM.
MERCURY, SALTs of.-See CoRROSIVE SUBLIMATE.
MONKSHOOD.—See ACONITE.
* MoRPHINE–OPIUM-Laudanum and preparations in which the OPIUM
ALKALOIDS predominate.
If taken by the mouth, give at once a solution of potassium per-
manganate and then empty the stomach; but, if taken by hypodermic
injection, both these would be useless. The stomach in opium-poisoning
is best relieved by the pump or tube, and should then be well washed out
with hot coffee, leaving in the organ a pint or more. If the stomach
pump or tube is not at hand, a large subcutaneous dose of apomorphine
(say 10 minims) may be given, or mustard or zinc sulphate ; but there
may be difficulty in obtaining vomiting from any emetic.
Attempt to rouse the patient by the battery, if at hand; by flips with
a towel, and by shaking. In all books will be found the usual direction
that you are to keep walking the patient about ; but this treatment is
questionable, and likely to favour the toxic action of morphine on the
heart. -
Ammonia may be applied to the nostrils.
Hot coffee may also be introduced into the bowels by an enema
apparatus, or by a simple tube.
728 POISONS : THEIR EFFECTS AND DETECTION. [$ 913.
The alternate cold and hot douche to the head is good, but the body
should be kept warm with hot wraps.
Small subcutaneous doses of atropine (say 1-20th of a grain) may be
administered, repeating the dose every twenty minutes, and watching the
effect. *
If necessary, apply artificial respiration.
Inhalations of nitrite of amyl have been used.
MUSCARINE.-See MUSHROOMS.
MUSHROOMs—MusCARINE–Poisonous FUNGI GENERALLY.
Empty stomach by Stomach pump or tube, or give a subcutaneous
dose of apomorphine, or administer by the mouth either mustard or
zinc sulphate. *
Inject as soon as possible a subcutaneous dose of 2 to 4 drops of the
solution of atropine; or, after the stomach has been emptied, give
tincture of belladonna every half-hour, in from 20- to 30-minim doses.
It is equally important to remove the remains of the fungi from the
intestines, and for this purpose it is well to give a dose of castor oil, and
to use an ellema. e *.
Stimulants may be given. The body should be kept warm.
NERIIN.—See DIGITALIS.
NICOTINE—TOBACCO.
Unless the stomach has been already emptied by vomiting, use
stomach pump or tube, or give an emetic of mustard and plenty of
Water.
Inject subcutaneously a small dose of strychnine (say 1-25th of a
grain of the nitrate), or give half a drachm of tincture of nux vomica.
Stimulants, such as brandy, chloric ether, etc., may be given.
Keep the body warm, but the cold douche may be applied to the
head.
Tannin and vegetable infusions containing tannin may also be given,
but it is questionable if they are of much use, unless any remnants
remain in the stomach. -
Keep the patient lying down for fear of fatal syncope,
NITRE–NITRATE OF POTASH.
Empty the stomach immediately by the pump or tube, or give a
subcutaneous dose of apomorphine (from 2 to 3 drops), or administer by
the mouth a tablespoonful of mustard, or a scruple of sulphate of zinc.
Dilute the poison, and attempt to wash it out of the system by giving
plenty of water or mucilaginous drinks. \
[$ 913. APPENDIX : TREATMENT—ANTIDOTES. 729
Apply hot fomentations to the loins, and keep the patient as warm
as possible.
Stimulants that are likely to increase the kidney congestion are to
be avoided.
Inhalations of nitrite of amyl have been recommended.
NITRIC ACID.—See ACIDs, MINERAL.
NITRO-BENZENE.
Empty the stomach at once by the stomach pump or tube, and wash
the organ out with plenty of warm water, to which advantageously a
little spirit may be added; or give emetics, such as zinc sulphate or
mustard.
Administer stimulants, either by the stomach-tube, as an enema, or
by subcutaneous injection.
Keep up the respiration artificially, if necessary, and maintain the
heart's action by application of weak, interrupted shocks to the chest-
wall, by means of the battery.
Rouse the patient by the douche.
Atropine subcutaneously has been recommended.
NITROUs OxIDE GAs.
The treatment is the same essentially as for chloroform (which see).
Inhalations of oxygen may do good, but oxygen is very rarely at hand.
NUx WomicA.—-See STRYOHNINE.
OLEANDRIN.—See DIGITALIS.
OPIUM.–See MoRPHINE.
v OxALIC ACID—BINOXALATE OF POTASEI—SoDIC OxALATE.
Unless the patient has already vomited freely, empty the stomach at
once by emetics of zinc sulphate or mustard; or the stomach pump or
tube may, in most cases, be used. If the acid has been taken, neutral-
ise by chalk, lime-water, or, better, by Saccharated lime-water; but
on no account neutralise by carbonate of soda or any alkali, for the
alkaline oxalates are extremely poisonous.
Assist elimination by the kidneys by giving plenty of water; apply
hot fomentations to the loins.
An enema may be given, if necessary, to empty the bowels well.
ly PHOSPHORUS,
Empty the stomach by tube or pump, and, at the same time, wash
the organ out with water to which has been added a drachm of
73O POISONS: THEIR EFFECTS AND DETECTION. [$ 913.
French turpentine, or give emetics. The best emetic for phosphorus is
said to be sulphate of copper, 4 or 5 grains dissolved in water, and
given every ten minutes until vomiting is produced.
In default of sulphate of copper, then sulphate of zinc or mustard.
Give #-drachm doses of turpentine, floating on water or on mucil-
age, every half-hour. Inhalations of turpentine vapour, much diluted,
are also of service. The American and German turpentines are said to
be of no avail. Probably the turpentine will freely purge the patient ;
but, if not, the bowels should be opened by a suitable purgative, such,
for instance, as magnesic sulphate.
PHYSOSTIGMINE.-See CALABAR BEAN.
PICROTOxIN–CoCCULUs INDICUs.
Use stomach pump or tube, or empty stomach by usual emetics,
e.g. mustard, zinc sulphate, or apomorphine, subcutaneously.
Chloral, in doses of from 10 to 20 grains, may be given every half-
hour to allay or prevent tetanus, the effects being, of course, watched.
For the same purpose bromide of potassium has been recommended.
In severe cases, it may be combined with chloral, 1 drachm of the
bromide with 20 grains of chloral.
PILOCARPINE.
The best treatment is a subcutaneous dose of atropine (say 1-60th
of a grain) or tincture of belladonna by the mouth in 20-minim doses,
to be repeated every twenty minutes until the pupils dilate.
POTASH.-See ALKALIES.
PRUSSIC ACID.” &
Use stomach pump or tube, or, if not at hand, an emetic of mustard
or sulphate of zinc. -
If the breathing has stopped, try artificial respiration and weak
shocks to the heart. -
* J. Kossa, considering that potassium permanganate ought, theoretically, to act
as a chemical antidote to potassium cyanide, by checking the paralysis of the
respiratory centres, has performed some experiments. Rabbits were shown to be
fatally affected in a few minutes by 0:01 grm. of the poison, but if, at the time of
administration, 0.5 grm. of permanganate dissolved in 50 c.c. of water was also
introduced into the stomach, doses of cyanide up to 0-1 grm. failed to cause death.
Larger quantities (0.2 grm.) proved fatal under similar conditions, but the action of
the poison was much delayed. Successful experiments were also performed with
aqueous solutions of hydrocyanic acid containing 0°1 per cent. It is suggested,
therefore, that, in cases of cyanide poisoning, 3 to $ litre of a 3 to 5 per cent.
solution of permanganate should be administered immediately (Pratch, through
Nowv, rem., ix. 567).
§ 913.] APPENDIX . TREATMENT—ANTIDOTES 73 I
1-60th of a grain of atropine subcutaneously is recommended to
assist the heart's action.
A brandy enema may be given, or brandy injected under the skin.
The body must be kept warm, but the cold douche may be advan-
tageously applied to the head.
SALTS OF SORREL.-See OxALIC ACID.
SAVIN. *
If the patient has not already emptied the stomach by repeated
vomiting, and the throat is not inflamed, use the stomach pump or
tube, and wash the organ out with water, or give any one of the usual
emetics—such as mustard, sulphate of zinc, or ipecacuanha.
If the bowels have not acted well, give a dose of castor oil; allay
pain with small doses of morphine.
SCILLAIN.—See DIGITALIS.
SNAKES, BITE of.
Suck the wound, and apply an alkaline solution of permanganate
of potash.
In severe cases of cobra poisoning and other extremely venomous
snakes, death threatening, the only likely means of saving life would
be bleeding at one arm and transfusing blood by the other.
Ammonia may be given by the mouth, and also smelt.
In cobra poisoning and venoms which kill mainly through the
respiration, the breathing must be kept up artificially; and, should
there be signs of the heart failing, weak, interrupted galvanic shocks
may be applied to the walls of the chest. *
Lacerda's plan of injecting permanganate of potash under the skin
is not only useless but even mischievous, for it takes up time which
might be more valuably employed.
SODA CAUSTIC.—See ALKALIES.
SoLANINE – SoLANUM DULCAMARA — BITTER SWEET – WooDY NIGHT-
SHADE.-The same treatment as for ATROPINE (which see).
STRAMONIUM.–The same treatment as for ATROPINE.
STROPHANTIN.—See DIGITALIS.
STRYCHNINE–BRUCINE–NUx WoMICA. -
Empty the stomach as quickly as possible by an emetic of mustard
or zinc sulphate, or by a hypodermic solution of apomorphine (4 drops).
732 POISONS : THEIR EFFECTS AND DETECTION. [$ 913.
The stomach pump or tube inadmissible : for, if tetanus is present,
it cannot be applied; or, if absent, it is likely to excite a spasm.
Place patient at once under chloroform or ether, and keep up a
gentle narcosis for several hours, if necessary.
Darken the room, stifle all noise; if in a town, and opportunity
permit, have straw or peat placed at once before the house to deaden
noise.
If the spasms threaten the respiration, artificial respiration is
absolutely necessary; and, to facilitate this, it would be justifiable,
in a dangerous case, to perform tracheotomy—of course under
chloroform.
Chloral may be given in place of chloroform, but the latter is best ;
the dose of chloral should be, at least, half a drachm, and if no effect is
produced in half an hour, then doses of 20 grains should be given at
intervals of a quarter of an hour.
If neither chloroform nor chloral is at hand, the juice from a
recently-smoked pipe may be diffused in a little water and a few drops
injected subcutaneously, and the effect watched. If there is a marked
improvement the treatment may be persevered in.
Bromide of potassium in combination with chloral has been recom-
mended.
Nitrite of amyl inhalations are said to be of use.
Curarine in a subcutaneous dose of one-third of a grain is antagonistic
so far that it paralyses the voluntary muscles.
SULPHURIC ACID.—See ACIDS, MINERAL.
TARTAR EMETIC.—See ANTIMONY.
TARTARIC ACID.—The same treatment as for OXALIC ACID (which see).
THEVETIN.—See DIGITALIS.
ToBACCo.—See NICOTINE.
TURPENTINE. - º
Empty stomach by tube or pump, or administer the usual emetics,
such as mustard, or sulphate of zinc, or ipecacuanha, or give hypoder-
mically 3 or 4 drops of the solution of apomorphine.
If purging is not already present, empty the bowel by enema; give
plenty of water and demulcent drinks to aid elimination by kidneys.
Apply hot fomentations to the loins.
Allay pain with opium or morphine.
§ 914.] APPENDIX DOMESTIC REMEDIES. 733
WERATRINE.
Empty the stomach by the tube or pump, or give any one of the
usual emetics, such as mustard, or zinc sulphate, or ipecacuanha.
Keep the patient lying down.
Stimulants may be administered.
An enema of hot coffee has been recommended.
Keep the body warm with wraps, hot blankets, etc.
WHITE PRECIPITATE.—The same treatment as for CORROSIVE SUBLIMATE.
WASPs, BEES, HoRNETs—STING OF.
# An onion immediately applied to the part stung is a favourite
popular remedy; but ammonia is better.
Extract the sting, if it remains in the wound.
Give stimulants, if necessary.
ZINC.
The only salt likely to cause poisonous symptoms is the chloride
which is used in the arts, and is the active principle of Burnett's dis-
infecting fluid.
Stomach pump or tube inadmissible. Give plenty of water, in
which carbonate of soda is dissolved ; or, if that is not at hand,
carbonate of potash.
Eggs and milk should also be given. -
Solutions of tannin, strong tea, and the like, also, to some extent,
neutralise the poison.
The pain in the abdomen is to be allayed in the usual way—by
hot formentations, and small frequent doses of morphine or opium.
DOMESTIC READY REMEDIES FOR POISONING.
§ 914. Large households, more especially those in which no one
possesses any special medical knowledge, would do well to furnish an
ANTIDots cupboard, for use in cases of emergency. This cupboard may
contain :-
(1) The Multiple Antidote, which consists of saturated solution of
sulphate of iron 100 parts, water 800, magnesia 88, animal charcoal 44
parts. It is best to have the animal charcoal and magnesia mixed
together in the dry state and kept in a well-corked bottle; when required
for use, the Saturated solution of sulphate of iron is mixed with eight
times its bulk of water, and the mixture of charcoal and magnesia added
with constant stirring. The multiple antidote may be given in wine.
glassful doses, frequently repeated, in poisoning by arsenic, zinc, opium,
734 POISONS: THEIR EFFECTS AND DETECTION. [$ 914.
digitalis, mercury, or strychnine; it is of no use in phosphorus poisoning,
or in poisoning by the caustic alkalies or antimony.
(2) Calcined Magnesia, for use in poisoning by acids.
(3) French Turpentine, for poisoning by phosphorus.
(4) Powdered ipecacuanha in a well-corked bottle ; the bottle con-
taining a small pill-box which is cut down, so that when full it contains
30 grains—the proper dose as an emetic. A similar small supply of
sulphate of zinc may also be provided.
(5) A tin of mustard.
(6) A bottle of vinegar.
If, then, provided with such a supply, any member is known to
have taken poison, and yet the precise poison is not known, give a
sulphate of zinc or ipecacuanha emetic, and follow it up by the mul-
tiple antidote, which is in itself not poisonous, -
If PHOSPHORUs has been taken, then give the French turpentine as
directed under Phosphorus (p. 730).
If ACIDs, neutralise by the calcined magnesia (see Acids, Mineral,
p. 719).
If ALKALIES, neutralise with vinegar (see Alkalies, p. 720).
IND EX.
ABEL and Crawford,
505.
and Field's test for bismuth in
copper, 655.
Abrus precatorius, 478.
Abrus, The toxalbumin of, 478.
Acetaldehyde, 170.
Acetanilide, 90.
Acetic acid, 116.
Aceto-nitrile, 223.
Acetyl group, 41.
3 3 y #. 305.
Acetylphenylhydrazine, 40.
Achscharumow, Action of aconitine on
birds, 369.
Acidity due to acid salts, 106.
Acids and alkalies, 81.
Acids, Internal effects of, 88.
,, Mineral. See Hydrochloric acid,
Sulphuric acid, etc.
Hilger's test for, 94.
Tests for, 105.
Treatment in cases of
poisoning by, (App.)
719.
Treatment of poisoning
by, 89.
Aconite, Derivation of name, 4.
$ 5 extract, 360.
3 5 Fatal dose of, for cats, 366.
group of alkaloids, 360–377.
,, liniment (linimentum aconiti),
360.
y 3 ointment, 360.
,, pharmaceutical
360.
2 3 tincture, 360.
Treatment in cases of poisoning
by, (App.) 719.
Aconitine, 250, 265, 269,360, 361, 362.
3 * Action on birds, 369.
mammals, 369.
2 3 2 man, 370–376.
2 3 Effects of, on animals, 366,
367.
3 3 Melting and subliming tem-
peratures, 260.
5 2. Physiological action of, 375,
5 3 Post-mortem appearances after
poisoning by, 375.
3 2 Properties of, 363.
on epinephrin,
3 2
preparations,
2 3
Aconitine, Separation of, from stomach,
etc., 376.
2 3 Statistics of poisoning by,
370.
5 3 Tests for, 363.
3 5 Treatment in cases of poison-
ing by, (App.) 719.
Aconitines, 361.
5 * Fatal dose of, 365.
Aconitum napellus, 360.
Acqua Toffana, 11.
Adenine, 263.
Adler, Effects of picric acid, 471.
Adonidin, 448.
Adonis vernalis, 440.
Adrenalin. See Epinephrin.
AEthyl-urethane, 37.
Agaricus pantherinus, 430.
3 3 phalloides, 429.
Post-mortem appear-
ances after poison-
ing by, 430.
2 3 ruber, 430.
Agarythrine, 430.
Agrostemma-Sapotoxin, 450.
Ahrens on the decomposition of cevadine,
404.
Albers on dose of coniine, 271.
Alcohol, Amylic. See Amyl Alcohol.
5 5 Ethylic, 142.
Criminal or accidental
poisoning by, 142.
Excretion of, 146.
Fatal dose of, 144.
in brain, 146.
in chloroform, Detec-
tion of, 152.
Post-mortem appear-
ances after poisoning
by, 145.
Statistics of poisoning
by, 142.
Symptoms of poisoning
by, 144.
Toxicological detection
of, 147.
5 * Treatment in cases of poisoning
by, (App.) 720.
Alcohols, 142–149.
5 5 Identification of, 147.
Aldehyde group, 41.
2 3 2 3
735
736
INDEX,
Alexander VI., Death of 7.
Ali Ahmed's treasures of the desert, 619.
Alkalies and acids, 81.
Alkalies, Detection of, 126.
5 3 Caustic, 122–127.
2 3 Effects on animal and vegetable
life, 124.
3 3 Estimation of, 127.
3 ) Local action on skin, etc., 124.
2 3 Museum specimens illustrating
poisoning by, 126. -
5 3 Post-mortem appearances after
poisoning by, 125.
5 3 Salts of the, Toxicological de-
tection of, 127-133.
3 3 Symptoms of poisoning by, 125.
Treatment in cases of poison-
ing by, (App.) 720.
Alkaloids, 248–431.
2 3 Colour tests for, 251.
3 2 containing oxygen, 263.
y 3 2 3 methoxyl groups,
264.
3 y 5 3 nitrogen, 264.
2 3 Discovery of, 16.
2 3 Estimation of, 264.
General tests for, 248.
3 5 Identification of, 257.
Identification of, by organic
analysis, 263.
3 3 Melting-points of, 262.
5, 2 Purification of, 253.
3 3 Separation of, from organic
matter, 252–257.
,, . Sublimation of, 258–262.
Alkyls replacing hydrogen, 35.
Allantoin, 39.
Allen, A. H., Assay of carbolic acid
powders, 193.
on lead in drinking
water, 630.
on bromine test for
carbolic acid, 187.
on distinction between
naphthas, 136.
on the composition of
vermin-killers, 332.
Alloxantin, 39.
Almen, on the physiological action of
oxalic acid, 539.
Alumina, Detection of, 709.
Aluminium, 707–710.
Alum salts, Action of, 708.
3 y Post-mortem appearances in
poisons by, 709.
Amanita muscaria, 426.
Amarin, 40.
Amblard, on the action of morphine,
303.
Amido-phenols, 34, 35.
Amines, 510.
Ammonia, 116–122.
3 y Action on human beings and
animals, 119.
Ammonia, Chronic poisoning by, 119.
Estimation of, 122.
Fatal dose of, 120.
in solution, Action on plants,
119.
Officinal preparations of 117.
poisoning, Museum specimens
by, 121.
Post-mortem appearances after
poisoning by, 121.
Properties of, 116.
Spectroscopic appearance of
blood in poisoning by, 120.
Separation from organic
matters, etc., 121.
Statistics of poisoning by,
118.
Symptoms in poisoning by,
118.
Treatmentin cases of poisoning
by (App.), 720.
|Uses of, 117.
3 3 vapour, Poisoning by, 118.
Ammoniae liquor fortior, 117.
2 3 carbonati, 117.
Ammonic cyanide, 221.
Ammonium salts, Neutral, 128–134.
Toxicological detection
of, 134.
3 5 3 5
- Amphibia, Poisonous, 483-486.
Amygdalin, 204.
Amylal, 37.
Amyl alcohol, 148.
5 3 Detection of, 148.
Amyl nitrite, 148.
3 3 ,, Post-mortem appearances
after poisoning by,
149.
Anaesthetics. See Chloroform, Chloral,
etc.
3 3 Minor, 170.
Anderseck, on a case of poisoning by
mercuric chloride ointment, 676.
Anderson, H. T., on the alkaloid of
aconite plants, 361.
Androctonus funestus, 486.
Androctonus occitanus, 486.
Aniline, 250, 284, 285.
Detection of, 285.
Fatal dose of, 285.
Properties of, 284,
Spectrum of colour reactions,
58.
Symptoms and effects of
poisoning by, 284.
Animal toxines, 507–529.
3 3 ,, Isolation of, 507–510.
Anson, Hon. Mrs., poisoned by laudanum,
307.
Antiarin, Effects of, 445.
Separation of, 445,
Treatment in case of poisoning
by, (App.) 720.
Antidotes, (App.) 718.
3 ;
3 3
INDEX.
737
Antimonial wine, Treatment in cases of
poisoning by (App), 720.
Antimonium nigrum purificatum, 602.
3 y sulphuratum, 602.
Antimoniuretº hydrogen, 614. See
Stibine, 613.
Antimony, 600–615.
Alloys containing, 604.
chloride, Effects of, 610.
Chronic poisoning by, 607.
Compound used in pyrotechny
containing, 604.
5 § Detection of, in
matter, 611.
9 3 Dose of, 605.
2 3 Elimination of, 610.
Estimation of, 614.
medicines, chiefly veterinary,
603.
9 3 Metallic, 600.
Mirrors of, 583.
oxide, Effects of, on animals,
605.
Patent and quack pills con-
taining, 603.
Pharmaceutical preparations
2 3
9 3
2 3
5 J
organic
of, 602.
3 y Pigments containing, 605.
,, . Post - mortem appearances
after poisoning by, 609.
3 × Sulphide of, 600.
} } Treatment in cases of poison-
ing by, (App.) 720.
Ants, 491.
Aplysia, 3.
Apocodeine, 298.
Apocynin, 449.
Treatment in cases of poisoning
- by, (App.) 720.
Apocynum cannabinum onabam, 449.
Apollodorus, 3.
Apomorphine, 298, 323.
Test for, 329.
2 3 Dose of 324.
Aqua Lauro-cerasi, 203.
Aquetta de Perugia, 11.
Araki, T., on the physiological action of
5 2.
3 3
arsenic, 576,
Aretaeus, Effects of lead on the nervous
system, 626.
Aribine, 263.
Arnold’s case of prussic acid poisoning,
207.
Arseniates, 553, 579.
Arsenic, 547—600.
chloride, 551.
compounds used in pyrotechny,
$ 2
Detection of, 577.
Doses of, 557.
eaters, 560.
Effects of, on animals, 558.
man, 560, 564–569.
plants, 558.
3 y } %
3 3 7 3
Arsenic, Elimination of, 577.
Estimation of, 591.
3 3 3 y by electrolysis,
592.
Imbibition of, after death, 587.
in beer, 571,
in glycerin, 585.
in hydrochloric acid, 98.
in organic matter, 585.
in the arts, 552.
Introduction of, 561.
in wall-papers, 564, 590.
,, iodide, 551.
(arsenious anhydride), Properties
of, 547.
Law relating to, 557.
Localisation of, in the body,
586.
Metallic, Properties of, 546.
Mirrors of, 583.
Pharmaceutical preparations of,
552.
Physiological action of, 576.
Pigments containing, 555.
poisoning, Absence of symptoms
in, 568.
Antidotes for, 577.
by external applica-
tion, 562.
Forms of, 564–569.
Microscopical appear-
ances of liver in,
575.
Museum preparations
illustrative of, 573.
Post-mortem appear-
ances of, 572, 573.
Quack nostrums containing, 554.
Rat and fly poisons containing,
554.
Sheep-dips containing, 555.
,, Slow poisoning by, 568. ,
Soaps containing, 556.
Solubility of, 547.
Statistics of poisoning by, 556.
sulphide, 551, 579.
,, tersulphide, Estimation by
iodine, 596.
Estimation as
magnesian ar-
seniate, 596.
Estimation as
arsenomolyb -
date of am -
monia, 598.
Estimation as
metallic arsen-
ic, 598.
Precipitation of,
595-600.
Treatment of poisoning by,
(App.) 721.
Veterinary medicines contain-
ing, 553.
3 3 33
9 3 5 3
47
738
INDEX.
Arsenious acid. See Arsenic.
Arsenites, 579.
Arsen-methyl chloride, 36.
Arseniuretted hydrogen, 548. See Arsine.
Arum maculatum, 481.
Arsine, 548. • *
,, Effects of, on animals and man,
549.
,, in the arts, 549.
Aselline, 528.
Asiatic knowledge of poisons, 4.
Aspidium Filix mas, 481.
Aspidosamine, 353.
Aspidospermatine, 353.
Aspidospermine, 353,
Assamin, 450.
Astier, L., The active principles of
Lathyrus sativus, 480.
Atkinson’s infant preserver, 293.
Atropa belladonna, 378.
Atropamine, 378, 396.
Atropine, 250, 264, 265,377, 378.
> 5 Accidental and criminal poison-
ing by, 385.
3 2 Action on animals, 386.
3 3 5 3 the iris, 384.
2 3 2 3 man, 387.
5 y Constitution of, 380.
$ 2 Diagnosis of poisoning by, 390.
3 3 Fatal dose of, 386.
2 3 Melting and subliming temper-
atures, 261.
3 y Physiological action of, 389.
5 2. Post-mortem appearances after
poisoning by, 390.
3 2 Properties of, 381.
Separation of, from organic
matter, 391.
5 y Statistics of poisoning by, 384.
5 3 Tests for, 381–384.
s Treatment of poisoning by, 390
(App.), 721.
Atroscine, 396.
Attalus Phylometer, 2.
Autal’s (J.) antidote for prussic acid, 213.
BAKER on ergot epidemic, 461.
Bamberger, Urine in sulphuric acid
poisoning, 95.
Banded Krait (Bungarus fasciatus), 503.
Baptisia tinctoria, 398.
Bardach's (B.) method of separating
mercury, 689.
Barium, 710–716.
3 2 carbonate, 711.
; 2 chloride, 711.
3 5 pºtion of, in the body,
4.
2 3 Effects of salts of, on animals,
711.
} 3 9 3 on man, 713.
3 3 Fatal dose of salts of, 713.
3 5 Post-mortem appearances in
poisoning by, 715.
Barium, Separation and detection of,
5
5 J sulphate, 711.
9 3 Symptoms in poisoning by Salts
of, 713.
Barker on the action of strychnine, 338.
Barrier on the nervous form of arsenic
poisoning, 568.
Barth on the poisonous nature of sodic
nitrate, 129.
Bartholow, Antidote for physostigmine,
412.
Basic method for destroying organic
matter, 53.
Bauman and Kast on relation between
narcotic power and ethyl groups, 171.
Baumann, E., on excretion of carbolic
acid, 184.
separation of animal
toxines from urine,
510.
separation of guani-
dine from urine,
521.
Baum, H., and Seeliger, R., on copper
oleate, 634.
Baxt on the effects of papaverine, 322.
2 3 5 5 thebaine, 322.
Bécoeur's arsenical soap, 556.
Beef, Poisoning by, 530.
Beer, Arsenic in, 571.
,, Poison of, 491.
Behren's method for identifying alkaloids,
257.
Belgian commission on injurious effects
of hydrochloric acid on vegetation,
100.
Belladonna, Pharmaceutical preparations
3 5. 3 5
5 5 3 3
of, 380.
2 y . alkaloid — discs (lamellae
atropinae),380.
3 3 5 3 solution of at-
ropine sul-
phate, 380.
} 3 2 3 ointment, 380.
3 * leaves—juice (succus bella-
donnae), 380.
3 5 ,, tincture, 380.
3 5 root—alcoholic extract, 380.
liniment, 380.
ointment, 380.
plaster, 380.
5 5 2 3
2 3 5 3
y 5 9 3
2 3 Treatment of poisoning by,
(App.) 721.
Belladonnine, 378, 396. ſº
Bembo on nitric acid poisoning, 111.
Bennet on effects of coniine on man, 271.
Benz-aconine, Fatal dose of, for cats, 306.
Benzene, 138.
2 3 Detection and separation of,
138. w
5 y Treatment
in poisoning by,
(App.) 721. -
Benzoic acid, Test for, 365.
INDEX.
739
Benzoline, 135.
Benzo nitrile, 223.
Benzopurpurin test for mineral acid, 105.
Benzoyl-aconine, 364.
chloride method for isolating
animal toxines, 509.
ecgonine, 34, 356.
,, morphine, 305.
Benzyl nitrile, 223.
Berberine, 250, 265.
Bérenger-Férraudand Porte'sexperiments
on the poisonous effects of ferric
chloride, 697.
Bergeron and Hote, L. L., on copper in
the human body, 640.
Bernard, Claude, hydrochloric acid in
gastric juice, etc.,99.
5 5
3 3
35 2 3 on the effects of
codeine, 318.
2 3 5 3 on the effects of
narceine, 320.
3 × 5 3 on the poisonous
action of mercuric
cyanide, 222.
on the effects of
papaverine, 321.
Bernatzic on the poisonous effects of
copper, 645.
Bernhardt on effects of CS2, 173.
Berntrop's method of detecting lead in
drinking water, 631.
Berthelot’s bomb, 52.
Bertrand, G., on arsenic, 52.
- on bufonin, 485.
on estimation of arsenic,
594. -
on silico-tungstic salts of
alkaloids, 251.
Berzelius, Test for arsenic, 578, 580–584.
Besnou's estimation of alcohol in chloro-
form, 153.
Betaine, 522, 523.
Bettelheim on sequelae after phosphorus
poisoning, 232.
Bexold, Antidote for physostigmine, 412.
Biacetylaconitine, Fatal dose of, for cats,
366.
Bibliography of chief works on toxicology,
3 y
3 5
2 3
16.
Bibra and Schuchardt on the blood in
phosphorus poisoning, 235.
Bichromate disease, 702.
Bidder on excretion of curare, 420.
Bikhaconitine, 362, 363.
Physiological effects of,
369.
Billroth on death under chloroform, 159.
Binnendijk on excretion of carbolic acid,
185.
Binx on action of chloroform on man,
S.
on the physiological action of
arsenic, 576.
Biological test for human blood, 66.
5 9
3 5
Bird, Dr. Golding, A case of aconitine
poisoning, 372.
Bishop Stortford cases of food poisoning,
530.
Bismuth, 652–657.
citrate solution, 653.
Estimation of, 655, 656.
electrolytically,
657.
Extraction and detection of,
654.
in the arts, 653.
2 3 lozenges, 652.
Medicinal doses, 653.
nitrate, 652, 653.
3 3 oxide, 653.
5 3 oleate, 653.
peroxide, 652.
pharmaceutical
652.
potassium iodide, 249.
Properties of, 652.
Separation of, 654.
3 3 Subgallate, 653.
3 3 subiodide, 653.
3 2 sulphide, 652.
3 5 Tests for, 655.
2 3 Toxic effects of, 653.
Bismuthic potassic iodide reagent, 249.
Bisulphide of carbon. See Carbon
bisulphide.
Bitter almonds, Post-mortem appearances
after poisoning by, 220.
Black bryony, 461.
Black drop, 292.
Blair's gout pills, 424.
Blanchard, The poison of the scorpion,
487.
Blas, A case of poisoning by white helle-
bore, 407.
Blondlot and Bernard, Hydrochloric acid
in gastric juice, 99.
3 5 and Dusart on the detection of
phosphorus, 243.
5 5 ., on the Marsh-Berzelius
test, 581.
Blood and blood-stains, Examination of,
59–67.
,, corpuscles, 65.
human and animal, biological test,
66.
Sodium and potassium in, 66.
,, Spectroscopic appearances of, 60.
,, ... in sulphuric acid poisoning, 96.
Blossfield on the composition of nux
vomica, 329.
Blue ºil), 663.
Blyth's (A. W.) definition of poison, 23.
Bocarmé, Count, 278.
Bocklisch, Methylguanidine, 521.
Bocklisch's apparatus, 508.
Boerhaave's odontalgic essence, 293.
Boehm and Wartmann on the action of
acomitine, 375.
5 5 3 2
preparations,
74O
INDEX.
Bogoslowsky on chronic poisoning by
nitrate of silver, 660.
Böhm on contraction of the gullet in
alkali poisoning, 125.
,, on the action of aconitine on frog's
heart, 367. -
effects of barium salts on
animals, 712
influence of digitalis on the
heart, 442.
isolation of cicutoxin, 472.
mentaleffects of chloroform,
159.
Bois on the fatal dose of strychnine, 335.
Boisbaudran on the spectrum of phos-
phorus, 244.
Boletus Satanas, or luridus (Lenz), 431.
Bollinger, O., on sequelae after phos-
phorus poisoning, 232.
Bonaparte as a poisoner, 8. e
Bonaparte's (Prince Lucien) viperin, 504.
Bondzynski's method of separating mer-
cury, 683.
Borchers, Physiological action of taxine,
416.
Bossey, Poisoning by water hemlock, 474.
Boström, The effects of the common
morelle, 431.
Bothus afer, 486.
Bott on the composition of opium, 286.
Bottard on the poison of Synanceia
brachio, 487.
Bottcher's depilatory, 711.
Bouchardat on the excretion of mor-
phine, 313.
Bouchardat’s case of poisoning by phos-
phorus vapour, 233.
Boufanti, T., effects of cantharides, 495.
Boullay discovers picrotoxin, 466.
Boussingault, 82. e
Bradbury on the effects of papaverine, 322.
Braconnot, Hydrochloric acid in gastric
juice, 99. - - - •
Braine, C., on the antiseptic action of
HCN, 214.
Brampton, Baron, on the Palmer case,
333.
Brasch, O., on spectroscopy of poisons, 57.
Braun's º of estimating HCl in
stomach, 107. *
Brauner, The estimation of arsenic, 597.
Brawn, Poisoning by, 530
Brenner on effects of breathing phos-
phine, 236. . . • & ſº º
Brieger on ethylidenediamine in putrid
haddock, 514.
methylguanidine, 521.
mydaleine, 520.
mydratoxine, 526.
neurine, 523.
peptotoxine, 524.
saprine, 522.
the isolation of neuridine,
3 3 5 y
3 3 3 3
2 3 } %
3 y 3 3
Brieger's mytilotoxine, 527.
3 3 process for the isolation of
animal toxines, 507, 510.
2 3 process for isolating muscarine,
429.
5 3 “spasmotoxine,” 525.
Brighton green, 644.
Brinvilliers, Madame de, 11.
Brittanicus, Death of, by poison, 6.
Brodie, Sir Benj., on the effects of barium
Salts on animals, 712.
on the effects of arsenic,
561, 567, 574.
5 y 2 3
Bromine, 187.
} % test for copper, 651.
Brouardel and L’Hote on a case of
potassic chlorate poisoning,
131.
5 5 on a ptomaine like veratrine,
408
Brown, A case of chloral poisoning, 165.
Brown (Crum) and Fraser on the effects
of thebaine,
323.
5 5 } } on toxicity, 35.
Browne, Crichton, Physiological action of
picrotoxin, 468.
Brucine, 250, 264, 265, 349—352.
,, Fatal dose of, 351.
,, in Strychnine, Detection of, 331.
, Melting and subliming tempera-
tures, 261.
, nitrate, fatal dose for rabbits,
351.
,, Physiological action of, 350.
,, Properties of, 399.
,, Quantitative estimation of 348.
, Spectrum of colour reactions,
58.
,, Tests for, 351.
,, Treatment in poisoning by,
(App.) 731.
Brugnatelli's (E.) method of detecting
mercury, 682.
Brunner, A., on the effects of phosphorus,
22
Brunnich, J. C., on deaths amongst
cattle from dhurrin, .204.
Brunswick green, 644,
Brunton, L., on the influence of digitalis
on the heart, 442, 443.
Buchanan on dose of ether, 150.
Buchner, A case of chronic poisoning by
chloroform, 159.
Buchner's (C. A.) case of nitric acid
poisoning, 111.
Buchner, M. L. A., on the solubility of
arsenious acid, 547.
Buchwald, Poisoning by Agaricus ruber,
431.
Buckheim on the active principle of
mezereon, 456.
Budd, C., on a case of colchicine poison-
ing, 425.
INDEX.
74 I
Bufonin, 485.
Bufotalin, 485.
Bufo vulgaris, 484.
Bulbocapnine, 359.
Burkart, A case of chloroform poisoning,
154.
Burnett's disinfectant fluid, 687.
Busscher, Dr. Albert, Cases of aconitine
poisoning, 372.
Butylamine, 528.
Butylal, 37.
Butyl chloral hydrate, 37.
Butylchloral, 168.
Bynssen, A., on the elimination of
mercury, 679.
CADAVERINE, 516.
Cadmium, 615.
O3 Fatal dose of, 615.
35 in the arts, 615.
,, . Medicinal preparations of, 615.
5 3 oxide, 615.
2 3 Separation and detection of,
616.
3 3 sulphide, 615.
Caffeine, 40, 41. -
,, Spectrum of colour reactions, 58.
Cahn on hydric sulphide poisoning, 79.
Cahours on strychnine, 327.
Caillol and Livon’s experiments with
antimony oxide on cats, 606, 610.
Calabar bean, Treatment in poisoning by,
(App.) 722.
Calabarine, 409. -
Calmette, A., The poisonous action of
cobra's blood, 500. -
Calmette's cobra antitoxin, 502.
Calomel, 662, 665.
Calvert's carbolic acid powder, 176.
Cambier, Isolation of an albumose from
the locust tree, 481.
Campbell, Dr., Lead poisoning from wine,
622.
Camphene, 139.
Camphor, 141.
3 5 Compound liniment of, 117.
3 3 2 3 tincture of, 141,
290.
3 3 liniment, 141.
2 3 Minimum fatal dose of, 142.
3 3 Pharmaceutical preparations
of, 141.
2 3 Post-mortem appearances after
poisoning by, 142.
5 y Rubini's essence of, 141.
2 3 Separation of, from contents of
stomach, 192.
3 y Spirit of, 141.
$ 3 Symptoms of poisoning by,
141.
3. Treatment in poisoning by
2 (App.) 722. 3.
2 3 water, 141.
*
Cantharides, 491–497.
Effects on animals, 493.
2 3 2 3 man, 494.
5 5. Fatal dose of, 493.
5 5 Pharmaceutical preparations
of, 493.
5 3 Post - mortem appearances
after poisoning by, 495.
5 3 Tests for, 495–497.
Treatment in poisoning by,
(App.) 722.
Cantharidin, Melting and subliming
temperatures, 262.
5 3 Properties of, 492.
3 y Separation of, 496.
Cantharis vesicatoria, 491.
Capparelli, The poison of the water
salamander, 484.
Capsicum seeds, 379.
Carbolic acid, 174.
2 3 Estimation of, 187, 191,
192.
3 3 Examination of urine for,
190.
3 x excreted by the skin, 185.
j 3 Fatal dose for animals, 179.
2 3 Fatal dose of, 178.
5 3 Internal administration,
Poisonous effects of, 182.
5 y Pharmacopoeia solution of,
175.
2 3 Physiological action of,
I85.
3 5 poisonous effects on animals,
178.
3 3 poisonous effects on fish,
178.
5 5 poisonous effects on frogs,
5 3 poisonous effects on in-
5 3 fusoria, 178.
3 3 poisonous effects on warm-
blooded animals, 179.
y 5 powders, 191, 192.
2 3 Post-mortem appearances
after poisoning by, 186.
3 3 preparations, Privy Council
order relating to, 176.
2 3 Properties of, 175.
3 3 Separation of, from organic
matters, 190.
3 5 soaps, 176, 193.
3 y Statistics as to poisoning
by, 176.
3 3 Symptoms in man of
poisoning by, 180.
3 y Tests for, 187, 188.
3 y Treatment in cases of
poisoning by, (App.)
719.
5 : Uses of, 176.
2 3 Urine in poisoning by,
183.
Carbon atoms, Linking of, 41.
742
INDEX.
Carbon bisulphide, 172-174.
Detection and separa-
tion of, 174.
Poisoning by, 172.
poisoning (chronic),
173.
3 3 2 3
Post-mortem appear-
ances after poison-
ing by, 174.
3 } 5 5 Properties of, 172.
Carbon monoxide, 68–76.
Blood in poisoning by,
62
Detection of, 75, 76.
Estimation of, 76.
haemoglobin, 61, 62.
Mass poisoning by,
72.
Penetration of 74.
Post-mortem appear-
ances after poisoning
by, 71.
x 3 3 * Properties of, 68.
3 5 Symptoms of poison-
ing by, 69.
Carbon sulphide. See Carbon bisul-
phide.
Carbon tetrachloride, 170.
Carboxyl group, 41.
Carlisle cases of food poisoning, 520.
cº case of prussic acid poisoning,
207. -
Carson on antimony sulphide, 612.
Cash, J. T., on the fatal dose of aconitine,
366.
5 y Physiological effects of inda-
conitine, 369.
Casper, A case of hydrochloric acid
poisoning, 103.
5 3 Cases of sulphuric acid poison-
ing, 96.
5 y Family poisoned by veratrum,
408.
3 y nitro-benzene as a poison, 193.
2 3 on the acute form of arsenic
poisoning, 565.
3 on arrest of putrefaction after
poisoning by acids, 90.
5 y on the detection of HCN after
death, 220.
2 y on the inflammatory effects of
arsenic, 575.
3 5 on post-mortem appearances
after poisoning by alcohol,
145,
2 3 on the post-mortem appearances
after poisoning by colchicine,
425.
on post-mortem examination in
HCN poisoning, 214.
Cass, W. C., on morphine taking, 311.
Casson, F., on the composition of aconite
extract, 360.
Castor-oil seeds, The toxalbumin of, 478.
Catalytic poisons, Loew's, 41,
Cataplasma conii, 270.
Caventou on brucine, 349.
Cedrenes, 139.
Cephalopoda, Action of poisons on, 44.
Cerbera odallam, 447.
Cevadilline, 401.
Cevadine, 401, 402, 404.
Chadderton case of food poisoning, 530,
531.
“Chandoo,” 311.
Chapman, A. C., and Law, H. D., The
estimation of arsenic, 594.
Chapman, A. C., and Law, H. D., on the
insensitiveness of zinc, 581.
Chapman, The, poisoning case, 608.
Charles IV. as a poisoner, 8.
Chastaing, P., on the solubility of
morphine, 296.
Cheiranthin, 449.
Chelidonin spectrum of colour reactions,
58.
Chenot poisoned by carbon monoxide, 69.
Chevallier, Action of fluids on zinc, 688.
Chever, A case of opium poisoning, 309.
Chevers, Dr., An Indian case of atropine
poisoning, 387.
5 5 on a case of aconite poison-
ing, 371.
5 § on atropine poisoning, 386.
Children, Hydrochloric acid in gastric
juice, 99.
Chilognathen, 203.
Chittenden on the localisation of arsenic
in the body, 586.
Chloral, 161–170.
Chloral cyanhydrine, 223.
Chloral hydrate, 37, 161.
Chronic poisoning by,
167.
Detection of, 162.
Estimation of, 162.
Excretion of, 168.
Fatal dose of, 165.
Poisonous effects of, on
animals, 163.
Poisonous effects of, on
man, 164.
Properties of, 161.
Separation of, from
organic matter, 168.
Statistics of poisoning
by, 162.
Symptoms of poisoning
by, 166.
Tests for, 169.
Treatment in poisoning
by, 166, 722 (App.).
Chlorate of potash, Treatment in poison-
ing by, (App.) 723. *
Chlorcodeine, 305.
Chlorime, 76–78.
2 3 Detection of free, 77.
,, Estimation of, 78.
INDEX.
743
Chlorine, Post-mortem appearances after
poisoning by, 77.
,, Properties of, 76. -
,, . Symptoms of poisoning by, 77.
Chlorodyne, 293.
Chloroform, 151–161.
3 5 Detection and estimation of,
160, 161.
3 3 Detection of impurities in,
152.
33 Fatal dose of, 155.
5 3 General effects of liquid,
154. º
35 Hyderabad Commission re-
searches on, 158.
2 3 Local action of, 153.
9 3 Manufacture of, 153.
35 Methylated, 152.
2 3 Poisoning by liquid, 156.
2 3 Post - mortem appearances
after poisoning by, 159.
3 2. Properties of, 151.
5 5 Statistics of poisoning by
liquid, 153.
3 5 Suicidal and criminal pois-
oning by, 157. -
3 3 Symptoms of poisoning by
liquid, 155.
3 3 Treatment in poisoning by
(App.), 723.
2 3 vapour, 156.
Chronic
by, 159.
Fatal dose of, 159.
Physiological effects
of, 157.
Post-mortem ap-
pearances after
poisoning by, 159.
Symptoms of
poisoning by, 158.
Chloroxalmethyline, 545.
Chodomisky, K., on the solubility of
arsenious acid, 548.
Choline, 41, 522.
,, group, 522.
Christison, A case of ammonia poisoning,
12
poisoning
2 3 A case of cytisine poison-
ing, 409.
2 3 A case of nicotine poisoning,
279.
y 5 Effect of digitalis on man,
437
oxalic acid on ani-
mals, 536.
oxalic acid on man,
538.
physostigmine on
man, 412.
y 2 Minimum lethal dose of sul-
phuric acid, 85.
on post-mortem appearances
after lead poisoning, 632.
Christison on the fatal dose of strych-
nine, 335.
3 3 on the non-fatal dose of sugar
of lead, 633.
Chrome red, 619.
,, yellow, 619.
Chromium, 701–706.
2 3 compounds, Effects of, 702.
3 2 Detection of, 706.
5 5 Post - mortem appearances
after poisoning by, 705.
33 Separation of, 706.
2 3 Statistics of poisoning by,
703.
Treatment in poisoning by,
(App.) 723.
Chryso-toxin, 458,
Cicuta, 3.
,, virosa, 471.
Cicutoxin, 471.
5 3 Effects on animals, 472.
5 y 3 3 man, 472.
3 y Separation of, from organic
matter, 473.
Cinchonidine, 265.
Cinchonine, 250, 265.
Cinnabar. See Mercuric sulphide.
Cinnamomum camphora, 141.
Cinnamyl cocaine, 356.
Clapton, Dr., on chronic poisoning by
copper, 648.
Clark, John, on Reinsch's test, 585.
Clarke, F. G., on effects of veronal,
172.
Clausmann on arsenic taken as food,
587.
Claviceps purpurea, 456.
Clemen’s solution, 553.
Cleopatra’s asp (Naja haje), 503.
Cloetta, Max, on digitonin, 432.
Clupea thrissa, 488.
,, venenosa, 488.
Coal-gas, poisoning by, 68.
Coal-tar creasote. See Carbolic acid.
Cobait and nickel, 693-696,
Estimation of, 696.
Poisoning by, Action
on circulation, 695.
Poisoning by, Action
on nervous system,
695.
Poisoning by, Action
on striped muscle,
695.
Poisoning by, Symp-
toms of, 694.
Separation and de-
tection of, 695.
Cobra di capello, The poison of the, 498.
,, poison antitoxin, 502.
Effects on animals, 500.
3 3 9 3 man, 50l.
2 3 ,, Fatal dose of, 500.
Coca alkaloids, 356–359.
2 3 3 3
5 3
744
YNDEX.
Cocaine, 264, 356.
Estimation of, 358.
Fatal dose of, 359.
hydrochlorate, 357.
tures, 260.
pharmaceutical preparations,
Post-mortem appearances after
poisoning by, 359.
Properties of, 356.
Separation of, 357.
Symptoms of poisoning by, 358.
3 3 Tests for, 357.
Cocculus indicus (Indian berry, Levant
nut), 465–469.
Codamine, 286.
Codeine, 250, 264, 266, 286.
Constitution of, 298.
Effects of, 318.
nitrate, Fatal dose for rabbits,
351.
Properties of, 317.
y 2 Spectrum of colour reaction, 58.
Colchicine, 250, 421–426.
Effects on animals, 423.
3 3 man, 424.
extraction of, 421.
2 3 Fatal dose of, 423.
Patent and quack medicines
containing, 423.
Pharmaceutical preparations
of, 422.
3 3 Post - mortem appearances
after poisoning by, 425.
3 y Properties and constitution
of, 422.
Separation of, from organic
matters, 425.
5 y Statistics of poisoning by,
424
3 y Tests for, 422,
3 y Treatment in poisoning by,
(App.) 723.
Colchicum autumnale, 421.
5 § wine, 423.
Coleman, W., A case of trional poisoning,
171.
Collas, Dr., on poisoning by the goby,
489.
Collidine, 40.
Collie on the spectroscope, 57.
Collie, J. N., Estimation of cocaine, 358.
Colocynth, Treatment in poisoning by,
(App.) 724.
Cologne yellow, 619.
Colophene hydrocarbons, 139.
Coltmann, Poisoning by locust - tree
leaves, 481.
Colubridae venenosae, 498, 503.
Conessine, 263.
Confectio opii, 291.
Congo red test for mineral acid, 105.
Conhydrine, 266, 269. tº
Melting and subliming tempera-
Coniceine, 263, 266, 269.
Coniceines, 268.
Conièrbe and Orfila, Arsenic in bones,
588.
Coninck, O. de, An alkaloid from the
cuttle fish, 524.
Coniine, 250, 263, 264, 265, 266–272.
Constitution of, 268.
Effects on animals, 270.
Effects on man, 271.
Fatal dose of, 271.
Pharmaceutical preparations of,
269.
Physiological action of, 271.
Post-mortem appearances after
poisoning by, 271.
Properties of, 266.
2 3 Separation of, from organic
matter, 272.
Statistics of poisoning by, 270.
Tests for, 267.
Treatment in poisoning by,
(App.) 724.
Conium maculatum, 266.
Convallamarin, 440.
Conyrine, 268.
Coote, Barrington, A case of poisoning
by antimony chloride, 611.
Copper, 637–652.
carbonate, 648.
Chronic poisoning by, 648.
Deaths from, 29.
Detection of, 650, 651.
Effect of salts of, on animals,
644.
Electrolysis of salts of, 650.
Estimation of, 650.
in the animal and vegetable
kingdom, 640.
in the arts, 643.
leguminate, 645.
Medicinal dose of, 644.
nitrate, 643.
oleate, 639.
oxide, 637.
phyllocyanate, 642.
pigments, 644.
poisoning, Statistics of, 647.
Post-mortem appearances in cases
of poisoning by, 648.
Properties of metallic, 637.
salts, Toxic dose of, 646.
Separation of, 650.
Solubility of, in various fluids,
638.
subacetate, 648.
subchloride, 648.
sulphate, 643.
sulphide, 637.
tartrate, 644. *
Treatment of poisoning by,
(App.) 724.
Volumetric process for estima-
tion of, 651.
INDEX.
745
Cuttle fish, Apyridine alkaloid from, 524.
Cyanide, Potassic, Estimation of, 220.
Poisoning by, 215.
Statistics of poisoning
by, 206.
3 5 Tests for, 215.
Cyanides, Double, 221.
3 y in vegetable kingdom, 203.
3 3 3 3
5 y y 3
5 y Separation of, from organic
matter, 217.
5 y Sodic and ammonic, 221.
Cyanmethaemoglobin, 214.
Cyanogen chloride, 222
y 3 iodide, 222.
Cyanuric acid, 222.
Cyclamin, 450.
Cymogene, 135.
Cyon on the effects of barium salts on
animals, 712.
,, on the physiological action of
oxalic acid, 539.
Cytisine, 398-401.
2 3 Effects on animals, 400.
,, Effects on man, 400.
,, Properties of, 399.
,, Tests for, 399,
Cytisus laburnum, 398.
DAKIN, H. D., Epinephrin, 505.
Dalby's carminative, 292.
Da Silva's test for physostigmine, 410.
Datura alba, 379.
,, atrox, 379.
,, fastuosa, 379.
Daturine, 378.
Datura stramonum, 379, 393.
Davidson, Dr., A case of ergot poisoning,
463
Non-fatal dose of carbolic
acid, 178.
Davidson’s cancer remedy, 554.
Davie, Margaret, Execution of, 9.
Davison, H., on the effects of fool's
parsley, 473.
Davy, Dr. Edmund, on the arsenic
absorbed by plants, 558.
Debray's experiment on arsenious anhy-
dride, 547.
Delezinerei, A. M., on a ptomaine like
veratrine, 408.
Delpech on effects of CS2, 173.
Delphinine, 250, 266.
$ 2 Melting and subliming
temperatures, 262.
Delphinoidine, 266.
3 3 Spectrum of
reactions, 58.
De Martiny on the effects of Santonin,
454.
De Pauw poisoned by digitalin, 443.
Derrid, 418.
Desgranges on poisoning by the external
application of arsenic, 563.
5 y
Copperas, 699.
Coppering of vegetables, 641.
Coqueret, Dr., on the nervous form of
arsenic poisoning, 568.
Coriamyrtin, 469.
Coriaria Sarmentosa, C. arborea, and C.
Tutu, 469.
Cornutin, 458, 465.
Corrigan on chronic poisoning by copper,
649.
Corrosive sublimate, 664, 669, 675.
Corybulbine, 359.
Corycavamine, 359.
Corycavine, 359.
Corydaline, 359.
Corydalis cava, 359.
Corydine, 359.
Corytuberine, 359.
Cotton seeds, 479.
Coullon on the action of hydrocyanic acid
on a dog, 210.
Couty, M., on the action of curare, 420.
Cox's method of estimating nicotine in
- tobacco, 274.
Crawford on epinephrin, 505.
Cream, Thomas Neill, the poisoner, 333.
Creasote, 189.
,, Carbolic acid in, Test for, 189.
Cresol, Commercial, 188.
,, Examination of urine for, 190.
,, Excretion of, 184.
Cresols, 34, 174, 176, 177, 179, 188.
,, Fatal dose to animals, 179.
Cresylic acid. See Cresol.
Criminal Consolidation Act, 1861, 20.
Cross on the poisonous properties of
amyl alcohol, 148.
Crotalinae (pit vipers), 498.
Croton oil, 476.
Dose of, 477.
2 3 Effects of, 477.
Post-mortem appearances after
poisoning by, 477.
3 y Separation and identification
of, 477.
Treatment in poisoning by,
(App.) 724.
Croton tiglium, 476.
Cryptopine, 286, 323.
Cuprous chloride, Preparation of, 75.
Cuprum aluminatum, 643.
Curare alkaloids, 418–420.
,, Commercial, 418.
,, Elimination of, 420.
,, Physiological effects of, 419.
Curarine, 263, 266, 418.
Separation of 420.
Treatment in poisoning by,
(App.) 725.
Curci on the effects of silver nitrate on
animals, 659.
Cuscohygrine, 356.
Cushman’s method for
strychnine, 343.
2 3
3 y
separating
colour
746
INDEX.
Deutsch, A case of sulphuric acid
poisoning, 84.
De Walanguis’solutio solventes mineralis,
553.
De Vry on antiarin, 445.
Dhurrin, 204.
Diacetin, 37.
Diacetyl morphine, 305.
Diamines, 514.
Diaphoretic antimony, 604.
Diazobenzol. See Tyrotocicom.
Dibenzoyl morphine, 305.
Diethylamine, 513.
Diethylamino-aceto nitriles, 223.
Diethylamino-phenyl-aceto nitrile, 223.
Diethylenediamine, 511, 519.
Diethyl-malonyl carbamide, 172.
Diethyl-sulphon-methane, 37.
Digitalacrin, 434.
Digitaleretin, 434.
Digitaletin, 433.
Digitalein, 432, 434.
Digitalin, 432.
2 3 Action of, on common blow-
fly, 442.
2 3 Fatal dose of, 435.
y 5 Pharmaceutical preparations
of, 434.
5 3 Spectrum of colour reactions,
58.
Digitalins, Action of, on frog's heart,
442, 444.
3 y Physiological action of, 439–
442.
} } Post - mortem appearances
after poisoning by, 443.
Separation of, from animal
matter, 444.
5 * Tests for, 439.
Digitalis, effects on man, 436–439.
5 y group, 431–445.
3 5 group of heart poisons, Treat-
ment on poisoning by, (App.)
725.
2 3 preparations, Maximum doses
of, 436.
9 3 purpurea (foxglove), 431.
3 5 Statistics of poisoning by, 436.
Digitin, 434.
Digitogenin, 432.
Digitonin, 432, 450.
Digitoxin, 433.
5 y Estimation of, 433.
5 3 Separation of, from organic
matters, 433.
Dihydrolutidine, 528.
Dillaberger's auto-experiments
coniine, 271.
Dimethylamine, 513.
Dimethyl-sulphon,
37.
Dinitro-benzoate, Preparation of, 147.
Dinitro - benzoates, Melting - points of,
148.
with
dimethyl-methane,
Dinitro-benzol, 198.
y 5 Detection of, 201.
} } Effect of, on blood, 200.
5 * Fatal dose of, 199.
5 3 Influence on the sight,
200.
3 3 Poisonous effects of, 199.
3 y Properties of, 198.
5 * Tests for, 199.
Dioscorides, 3.
5 y Effects of lead on the nervous
system, 626.
Diphenyl-carbazide test for copper, 651.
Diphenyl diethyl sulphone ethane, 171.
Disinfectants, 191.
Disinfecting powders, 176.
Distillation in vacuum, 49.
Dobbie and Lauder, Constitution of cory.
daline, 360.
Dolbeau on the anaesthesis of a sleeping
person, 157.
Dolium galea, 82.
Domestic remedies for poisoning, 733.
Donovan's solution of arsenic, 553.
Dott on physiological action of morphine,
305.
Dott's method of assaying opium, 288.
,, tests for purity of chloroform, 153.
Douzard's method of assaying opium, 289.
Dover powder, 291.
Dragendorff on blood-stains, 64, 65.
5 § on cantharides, 496.
} } on digitalin, 435.
2 3 on the colour reactions of
strychnine, 347.
3 y on the composition of nux
vomica, 329, 330, 331.
5 y on the constituents of ergot,
457.
3 3 on the detection of HCN long
after death, 220.
} ) on thedetection of strychnine,
345.
3 3 on the excretion of curare, 420.
} } on the excretion of morphine,
y 3 on the extraction of que-
bracho alkaloids, 353.
3 3 on the separation of curarine,
420.
} } on the separation of gelsemine,
355.
3 3 on the separation of physos-
tigmine, 412.
3 y on the separation of Solanine,
398.
) y on the solubility of strych-
nine, 327.
y 5 on the treatment of dried
blood, 59.
Dragendorff’s experiments on cats with
coniine, 270.
} } process for separating alka-
loids, 254.
INDEX.
747
Elliott, Fatal dose of cobra poison, 500.
,, Poison of sea-snake, 498.
Emetics, (App.) 718.
Enletine, 250, 266.
Emplastrum plumbi, 618.
2 3 ,, iodidi, 618.
Engel on excretion of carbolic acid, 186.
Engelhardt on aniline poisoning, 284.
Engravers’ acid, 109.
Enhydrina bengalensis, Poison of, 498.
Enhydrina valakadien, 498.
Epeira diadema, 490.
Epinephrin, 505.
5 3 Physiological action of, 506.
Erb, W., action of epinephrin, 506.
Erdmann's reagent, 422.
Ergot of rye, 456-465.
Active constituents of, 456,
459.
5 § Detection of, in flour, 460.
3 3 Dose of, 460.
5 5
Dregendorff's reagent for alkaloids, 251.
. . . . » sclerocrystallin, 459.
Duboia Russellii, 504.
Duboisia Hopwoodii, 283.
Duflos' prussic acid, 203.
-Dulcamarin, 450.
Duncan, Dr., a case of hydrochloric acid
poisoning, 103.
Dunstan, W. R., and Cash, J. T., on the
5 j fatal dose of aconitine,
366.
2 3 and Cash, Physiological
effects of indaconi-
tine, 369.
2 3 and T. Anderson Henry,
on the alkaloids of
aconite plants, 361.
2 3 and Henry, on prussic
acid yielding glu-
cosides, 204.
3 3 on the composition of
- aconitine gold chlor-
ide, 365. .
Dunstan, Prof., on the estimation of
tartar emetic, 601.
2 3 on the melting-point of
aconitine, 365.
• ? on the solubility of
aconitine, 363.
Dupré on copper in the human liver,
640.
,, on excretion of alcohol, 146.
,, on separation of aconitine from
contents of the stomach, 376.
Duroy on alcohol in the brain, 146.
Durdufi, Action of aconitine on the heart,
368.
Dusart on the detection of phosphorus,
243.
Dutch pink, 619.
Dworzak's auto-experiments with coniine,
271.
Dybskowsky on solubility of phosphorus
in blood, 236.
Dyer’s acid, 109.
EASTFIELD and Aston on tutin, 469.
Eau de Javelle, 124. -
Eberty on the action of ergot, 463.
Ecboline, 457.
Ecgonine, 357.
Echujin, 449.
Eczemua arsenicale, 569.
Eel blood, 489.
Egyptian knowledge of poisons, 2.
Ehrlich on poisoning by cocaine, 359.
Elapinae, 503.
Elaps corallinus, 503.
Ellenberger and Hofmeister on the excre-
tion of hippuric acid in lead
poisoning, 629.
3 3 and Hofmeister on the local-
isation of lead, 624.
Ellinger, Effects of cantharides, 493.
5 3 Pharmaceutical preparations
of, 460.
y 3 Physiological action of, 463.
3 3 Separation of active princi-
ples of, from organic
matters, 465.
3 y Symptoms of acute poison-
ing by, 463.
3 3 Treatment in poisoning by,
(App.) 725.
Ergotinine, 457.
Ergotism, Convulsive form of, 461.
5 J Gangrenous form of, 462.
Erythrocytes, 43.
Erythrophlein, 440, 449.
Erythrophloeum guineense, 449.
Eserine. See Physostigmine.
Esser on the physiological action of
arsenic, 576.
Ether, 149.
,, as an anaesthetic, 150.
,, Fatal dose of, 150.
,, Poisonous properties of, 149.
,, Properties of, 149.
2 3 sºion of, from organic fluids,
150.
5 y Tººnt in poisoning by, (App.)
26.
Ethiops of antimony, 604.
Ethylamine, 41, 513.
Ethylenediamine, 511.
Ethylic ether. See Ether.
Ethylidenediamine, 514.
Ethyl sulphide as a poison, 33.
Eucaine, 356.
Euchlorine test for carbolic acid, 188.
Eulenberg on chronic poisoning by anti-
mony, 607.
2 3 on chronic poisoning by CS2,
173.
} } on the dose of coniine, 272.
2 3 on the effects of benzene
vapour, 138.
748
INDEX.
Eulenberg on the effects of lead poison-
ing, 627.
5 on the effects of mercurial
vapour on animals, 670.
5 3. on the effects of phosphine, 235.
2 3 on the fatal dose of strychnine,
335.
3 y on the poisonous effects of
hydrochloric acid, 101.
3 y on the poisonous effects of
petroleum, 136.
5 x on the poisonous properties of
amyl alcohol, 148.
3 y on the vapour of ammonic
cyanide, 221.
Eulenberg's experiments on animals with
creasote, 189.
3 3 experiments on pigeons with
arsenic, 559.
2 3 experiments on pigeons with
oxalic acid, 537.
5 3 experiments with methyl
- cyanide, 222.
3 * experiments with phosphorus
vapour, 233, 234.
Euonymin, 447.
Euonymotoxin, 440.
Euonymus atropurpureus, 447.
Extractum physostigmatis, 411.
Eykmann on the poison of Illicium
religiosum, 470.
FABER, Cows poisoned by veratrum, 408.
Fabris, L., A case of poisoning with
strychnine and atropine, 383.
Fagge on the action of digitalin on the
frog's heart, 442.
Falck, C. Ph., and Vietor, L., Local action
of sulphuric acid, 85.
Falck, F. A., on ammonia poisoning,
118
3 3 on cases of poisoning
by Agaricus phal-
loides, 429.
5 3 on criminal cases of
alkali poisoning, 124.
2 3 on deaths from atropine,
390,
3 3 on poisoning by cicuta,
472.
3 J. on poisoning by cytisine,
400.
3 y on poisoning by San-
-tonin, 453.
2 3 on poisoning by yew,
416.
3 5 on the effects of barium
salts on animals, 712.
3 3 on the effect of copper
salts on animals, 644.
3 2 on the effects of silver
nitrate on animals, 659.
3 3 on the effects of tartar
emetic, 606.
Falck, F. A., on the fatal dose of
atropine for rab'ºits,
386.
2 3 on the fatal dose of
brucine, 350.
y 3 on fatal dose of chloro-
form, 155.
y 3 on the effects of codeine,
5 3 on the fatal dose of
picrotoxin, 467.
} } on the fatal dose of
strychnine, 334.
3 3 on the poisonous effects
of chloral hydrate,
163.
Falck’s statistics as to rapidity of death
from carbolic acid,
183.
of carbolic acid poison-
ing, 177.
of chloroform poisoning,
153. -
of colchicine poisoning,
424
of coniine poisoning,
of cyanide poisoning,
of mercuric chloride
poisoning, 675.
of phosphorus poison-
ing, 228.
sulphuric
poisoning, 83.
False angustura bark, 326.
Faust, E. S., on the poison of the cobra,
} } 3 3 of acid
499.
} } on the poison of the
salamander, 483, 484.
3 3 on the poison of the toad,
484
Favolle, M., Test for hydrochloric acid,
105.
Felletar on blood-stains, 64.
,, . on poisoning by hellebore, 447.
Ferrari on poisoning by hellebore root,
446.
Ferric chloride, 187, 697, 698.
Ferrous sulphate, 699.
Field, Test for bismuth in copper, 655.
Filho's caustic, 123.
Fischer, A base like muscarine, 428.
Fish, Action of metals on, 42.
,, Poisonous, 487–489.
Fitzwalter, Maud, poisoning of, 8.
Fleming's tincture of aconite, 361, 366.
Fleury's method of assaying opium, 289.
Fröhde's reagent for alkaloids, 251.
Flourens on action of chloroform, 158.
Flowers of antimony, 604.
Flückiger on the colour reactions of
strychnine, 346.
3 5 on the tests for atropine, 383.
INDEX.
749
Flückiger's test for brucine, 352.
carbolic acid in
creasote, 189.
9 3 ,, cocaine, 357.
3 3 2 3 coniine, 268.
Foetid spirit of ammonia, 117.
Foderé, Poisoning by arsenical enemata,
563.
Fool's parsley (AEthusa cynapium), 473.
Food poisoning, 529–532.
2 3 Statistics of, 531.
Formal cyanhydrine, 223.
Formaldoxime test for copper, 651.
Formanek, J., Researches on guinea-pigs,
62.
5 y on the spectrum of blood,
60
33 3 3
Fougnies, M., the poisoning of, 278.
Fowler's solution, 552.
Fraenkel, E., and Reiche, F., on effects
of sulphuric acid on kidney, 91.
Francis on prussic acid in cassava root,
205.
Frankforter on the
narceine, 319.
Fraser on strophantin, 447.
5 3 the action of atropine, 387.
3 3 the effects of thebaine, 323.
5 y the fatal dose of cobra poison,
500.
9 3 toxicity, 35.
Fraser and Bartholow, Antidote for
physostigmine, 412.
2 3 and Elliott, Poison of sea-snake,
498. -
Frères Come's cancer paste, 554.
Fresenius and Hintz on the detection of
arsenic, 590.
2 3 on ordinary phosphorus in red
phosphorus, 225.
Freund and Friedmann on the melting-
point of methylene dicytisine,
399.
3 3 and Frankforter on the consti-
tution of narceine, 319.
Fugu-poison, 487.
Fungi, Poisonous, 426, 429, 430, 431.
Furst on the poisonous properties of
amyl alcohol, 148.
constitution of
GALIPPE, Effects of cantharides, 493.
Garcia, Rate of formation of diamines,
4.
Garsed, W., and Collie, J. N., Estimation
of cocaine, 358.
Gases, Poisonous, 68–80.
Gasolene, 135.
Gautier, A., and Clausmann, on arsenic
taken in food, 587.
3 × ... on destruction of organic
matter, 53.
2 3 Test for CO, 76.
The separation of arsenic,
594
Gautier's process for the isolation of
animal toxines, 507.
Gay on the detection of strychnine, 395.
Gehlen poisoned by arsine, 549.
Gelsemine, 363. *
3 2 Fatal dose of, 354.
3 3 Separation of, from organic
matter, 355.
3 J Physiological action of, 354,
355.
Treatment in poisoning by,
(App.) 726.
Gelseminine, 353.
Gelsemium sempervirens, 353.
Geppert on carbon monoxide, 71.
,, on the action of prussic acid on
the blood, 209.
Gergens, E., and Posner, C., on the effects
of chromium on animals, 702.
Gergers and Baumann on the separation
of guanidine from urine, 521.
German Sausage poisoning, 532.
5 5 poisoning, Post-morten
appearance after, 532.
Gescheidlen on the physiological action
of morphine, 305.
Geysers and carbon monoxide, 68.
Gipsies, Knowledge of poisons possessed
by, 5.
Girºud, Dr. H., on Datura delirium, 388.
Glass of antimony, 604.
Glauber, Preparation
acid, 97.
Glenard on arsenic in hydrochloric acid,
98.
Glucosides, 431–453.
Gmelin, L., Hydrochloric acid in gastric
of hydrochloric
juice, 99.
,, on the effects of barium salts
on animals, 712.
2 3 on the effects of chromium
on animals, 702.
Gmelin's experiments on nickel sulphate,
693.
Gnoscopine, 286.
Goby, Poisoning by, 489.
Godeffroy, Dr. R., on silico-tungstic acid,
250.
Godfrey’s cordial, 292.
Gold chloride reagent, 249.
Goldschmiedt on the constitution of
papaverine, 321.
Goodart, G. F., on the microscopical
appearances of the liver after phos-
phorus poisoning, 239.
Gorup-Besanez on the arsenic absorbed
by plants, 558.
Gosio on the liberation of diethylarsine
by Mucor mucedo, 564.
Goulard's balsam, 619.
,, water, 618.
Grandeau's test for digitalin, 434.
Grandval and Lajoux's process for
separating alkaloids, 257.
75O
INDEX.
Grasset and Amblard on the action of
morphine, 303.
Grate on the composition of nux vomica,
3.31.
Greek knowledge of poisons, 2.
Green verditer, 644.
Grehant (N.) and Martin's (E.) experi-
ments on opium smoke, 311.
Grehant, N., on carbon monoxide in
blood, 63.
Greshoff's amygdalin like glucoside, 204.
Griepenkerl on ergot epidemics, 461.
Grimm on the effects of santonin, 455.
Grinrod's remedy for spasms, 292.
Grundmann on the composition of nux
vomica, 329.
Guaiacum test for blood, 65.
Guanidine, 520.
Guareschi and Mosso's hydrocollidine,
528.
Guilbert on the nervous form of arsenic
poisoning, 567.
Guinard on the action of morphine on
goats and cats, 304.
Gunn’s (Alexander) method of detecting
and estimating oxalic acid, 543.
Gunther on alkaloids in Belladonna
plant, 378.
Günzburg's test for mineral acid, 105.
Gussermo's experiments on animals with
lead, 622.
Gutzeit test for arsenic, 579.
Guy, Dr., on a case of prussic acid poison-
ing, 212.
5 2 on the chromate test for strych-
nine, 346.
5 5 on the fatal dose of strychnine,
336.
3 3 on the microscopical appear-
ance of strychnine, 327.
Guy’s(Dr.) methodof subliming alkaloids,
258.
Gynocardin, 204.
Gypsophila-Sapotoxin, 450.
HAAGEN, A case of sulphuric acid poison-
ing, 84.
Hackford, J. E., Lead electrodes, 594.
Haematin, 60, 61, 63.
Haematoporphyrin, 61, 62.
Haemochromogen, 60, 61.
Haemoglobin, 60, 61.
Hager's test for phosphorus, 245.
Hahneman’s soluble mercury, 666.
Haidlen on morphine in blood, 314.
Hair dyes, 658
Hall, Marshal, on a death from smoking,
280.
Hamodryad (Naja bungarus), 503.
Hamberg on the localisation of arsenic in
the body, 586.
Hamlet and Plowright, Oxalic acid in
fungi, 533.
Harland, R. H., on carbonate of lead,
618.
Harley, J., on the action of aconitine,
369.
3 × on the effects of fool's
parsley, 473.
Harnack, Isolation of a base like mus-
carine, 428.
5 2 on the effect of copper salts on
animals, 644.
Harnack's experiments on animals with
lead, 622.
Harnack and Witkowsky’s calabarine,
409.
Harnack and Witkowsky, Effect of
physostigmine on animals, 411.
Hartmann, J., Solubility of phosphorus
in water, 224.
Harvey’s statistics on arsenic poisoning,
573.
Hassal, Dr. R., A case of poisoning by
Burnett's fluid, 691.
Hauff on the liver in phosphorus poison-
ing, 238.
Haywood, Mr., poisoned by nitric acid
vapour, 110.
Heart of cold-blooded animals, Effect of
poisons on, 45.
Heart poisons, 439–440.
Hebrew knowledge of poisons, 5.
Hecker on tarantism, 491.
Hehner, O., Auto-experiments on potas-
sic chlorate, 132.
Hehner's method for purifying wine,
580. -
Heinrich, Effects of cantharides, 494.
Heinrich's auto-experiments with coniine,
271.
Heisler on jaundice in phosphorus poison-
ing, 230.
Hellebore root, Poisoning by, 446.
Helleboretin, 446.
Helleborin, 446.
Helleborus foetidus, 446.
9 3 niger (the Christmas rose),
446.
2 3 viridis, 446.
Helmholtz on the effects of santonin,
454.
Heloderma, Poison of, 485.
2 3 horridum, 485.
y 2 suspectum, 486.
Helwig on deaths from smoking, 280.
Helwig's method of subliming alkaloids,
258.
Hemlock. See Comime.
Hempel's method for detecting CO, 76.
Henderson’s (Dr.) experiments with
phosphine, 236.
Henry VIII., 12.
Hermann, L., on opium taking, 311.
2 3 on the action of ergot, 464.
5 ; Physiological action of
oxalic acid, 539.
INDEX.
75 I
Hermiari-saponin, 450.
Herscher, Biological test for human
blood, 66.
Hertwig on poisoning by chlorine, 77.
Herzig and Meyer, Method for determin-
ing N-methyl groups, 264.
Hesse, Isolation of physostigmine, 409.
Hesse, O., melting - point of cocaine
hydrochlorate, 357.
5 y on the quebracho alkaloids,
353.
Hesse's (O.) atroscine, 396.
Heubel on the localisation of lead, 634.
Heubel’s experiments on animals with
lead, 622.
Heunefeld’s turpentine solution, 65.
Heusinger on ergot epidemic, 461.
Hexamethylene diamine, 519.
Hildebrand on poisoning by tobacco
through the skin, 280.
Hilger, A., and Markens, W., purification
of crude Solanine, 396.
3 2 and Markens, W., on solane-
ine, 398.
Hilger on the solubility of copper in
soap, 639.
Hilger's test for mineral acids, 94.
Hind's sweating ball, 604.
Hinsberg and Treupel, 35.
Hintz on the detection of arsenic, 590.
Hirne on elimination of potassic chlorate,
132.
Hirt on the absorption of mercury by
the skin, 672.
Hoffman on a case of poisoning by
chloroform, 156.
Hoffmann's (A. W. v.) “piperazine,”
520.
Hofman, Action of curare, 420.
Hofman’s test for CS3, 174.
Hog cholera, Toxines of, 528.
Holland on the electrolytic method of
separating lead, 636.
Holmes on the action of ergot, 463.
Homatropine, 384.
Homolle’s digitalin, 435.
Hopkins, F. G., on the effects of phos-
phorus poisoning, 234.
Hoppe-Seyler on the physiological action
of carbolic acid, 185.
- 3 3 on the separation of car-
bolic acid from organic
matter, 190.
Hoppe-Seyler's formula for haematin,
64.
Hote, L. L., on copper in the human
body, 640.
Hottot's aconitine, poisoning by, 374.
Houston, Dr., on lead in drinking
waters, 630.
Hºl. J., a horse poisoned by nicotine,
278.
Hüber, A., on poisonous effects of dinitro-
benzol, 199, 200,
Hufeland on the effects of Santonin, 454.
Hufner and Helmholtz on the effects of
Santonin, 454.
Hugo, P., on the effects of arsenic on
mammals, 560, 576.
2 3 on the post-mortem appear-
ances in arsenic poison,
572.
Hunt, Reid, on the fatal dose of nitriles,
22
3.
2 3 on the fatal dose of potassic
xanthogenate, 174.
Hurt, a case of taxine poisoning, 417.
Husband on a case of rash following
chloral, 167.
Husemann on ergot epidemics, 461.
Husemann's cases of digitalis poisoning,
436.
5 y definition of poison, 22.
Huss, Magnus, a case of poisoning by
phosphorus vapour, 233.
Hydrazin as a solvent for blood, 61.
Hydrazine sulphate test for copper, 651.
Hydric sulphide, 78–80.
Chronic poisoning by,
8
Detection of, 80.
Post - mortem appear-
ances after poisoning
by, 79.
Properties of, 78.
Symptoms of poisoning
by, 78.
Hydric sulphocyanide, 222.
Hydrobenzamide, 40.
Hydrocarbons, 135.
Hydrochloric acid, 97–108.
Action on cloth, etc.,
101.
Detection and estima-
tion of, 105.
Estimation of, 106.
Fatal dose of, 99.
Influence of, on vege-
tation, 100.
in gastric juice, 99.
Law as to quantity
in air, etc., 100.
poisoning, Museum
specimens, 104.
Poisonous effects of,
101.
Poisonous effects of
solution of, 102.
Post-mortem appear-
ances after poison-
ing by, 103.
Properties of, 97.
Purification of, from
arsenic, 581.
Statistics of poisoning
by, 99.
Hydrocollidine, 528.
Hydrocotarnine, 286, 316.
9 3 5 5
752
INDEX.
Hydrocotarmine nitrate, Fatal dose for
rabbits, 351.
Hydrocyanic acid, 202–221.
Accidental and crimi-
nal poisoning by,
207.
y 3 , , Action of, on lower
* organisms, 209.
and cyanides, Action
on living organisms,
208
Chronic poisoning by,
213.
Commercial, 203.
Estimation of, 220.
Fatal dose of, 208, 223.
Impurities in, 202.
y 5 ,, in oil of bitter
almonds, 203.
in the vegetable king-
dom, 203–206.
Length of time after
death, it can be
detected, 219.
3 y 3 3 Medicinal prepara-
tions of, 202.
Poisoning by, 203.
Post-mortem appear-
ances after poison-
ing by, 214.
Properties of, 202.
Separation of, from
organic matter, 217.
Statistics of poisoning
by, 206.
Symptoms of poison-
ing by, in animals,
209.
Symptoms of poison-
ing by, in man, 211.
2 3 ,, Tests for, 215.
Hydropotassic oxalate, 535.
Hygrine, 356.
Hymenodictine, 263.
Hyoscine, 377, 395.
Hyoscyamine, 250, 266, 377, 391.
3 × Dose of, 395.
5 3 Effects of, 395.
5 § Melting and subliming
temperatures, 261.
5 5 Pharmaceutical prepara-
tions of, 393.
3 3 Properties of, 393.
3 * Separation of, from organic
matter, 395.
; : Tests for, 382, 383.
3 3 Treatment in poisoning
by, (App.) 726.
Hyoscyamus albus, 392,393.
3 3 muticus, 393.
3 y niger, 391, 392.
Hypaphorine, 348.
Hypaphorus subumbrans, 348.
Hypochlorite test, 187.
Hypoquebrachine, 353.
Hydroxylamine method of separating
mercury, 683.
IBSEN on the detection of strychnine, 345.
Icthyismus gastricus, 489.
Ictrogen, 479.
Illicium religiosum, The poison of, 470.
Imido groups, Action of, 40, 41.
Indaconitine, 361, 363.
} } Physiological effects of,
369.
Indicators for titration of alkaloids, 264.
Inée, 447.
Infusoria, Action of poisons on, 43.
Inoko on fugu-poison, 487.
Insects, Action of poisons on, 44.
Iodic acid test for morphine, 300.
Iodine in hydriodic acid (reagent), 248.
,, in potassic iodide (reagent), 249.
,, Treatment in poisoning by,
(App.) 726.
Iodised parethoxyphenyl succinimide,
249.
Ipecacuanha and morphine lozenges, 291.
x 3 Compound powder of 291.
Iris, Effect of poisons on, 48.
Iron, 696–701.
,, chloride, 696.
2 3 Pºion and estimation of salts of,
00.
,, Effect of chloride of, on animals,
697.
,, Effect of chloride of, on man, 697.
,, Elimination of chloride of, 698.
* } rºatial preparations of,
697.
,, Post-mortem appearances
poisoning by salts of, 698.
,, Dinitrosulphide preparation of, 152.
Isaconitine, 364.
Isambert and Hirne on elimination of
potassic chlorate, 132.
Iso-amylamine, 514.
Iso-amyl ester nitrite, 148.
Isocorybulbine, 359.
after
JABORANDI, Treatment in poisoning by,
(App.) 726.
Jacobi, Dr., on cases of potassic chlorate
poisoning, 131
9 3 on the active principles of
ergot, 458.
Jacobi's apparatus, 46.
Jaksch on benzopurpurin as a test for
mineral acid, 105.
3 3 Hºmoi acid in gastric juice,
Jaksch's method of estimating HCl, in
stomach, 107.
Jānecke's (E.) method of separating
mercury, 684.
Jannasch's (Paul) method of separating
mercury, 683.
INDEX.
753
Japaconitine, 361, 362.
Javelle water, 124.
Jeannel’s test for copper, 638.
Jeffer's purification of hydrochloric acid,
582.
Jequirity, 478.
Jervine, 250, 402, 404.
,, Spectrum of colour reactions, 58.
Jobst and Hesse isolate physostigmine,
409. -
Johnson, G., Cases of camphor poisoning,
141.
Jowett, H. A. D., Epinephrin, 505.
Jubell's statistics of nitro-benzene poison-
ing, 193.
Jumelle on action of chloroform on
plants, 157.
Juny, Detection of mercury in urine, 684.
Jurgens, A., on the solubility of aconi-
tine, 363.
KAHLBAUM's prussic acid, 203.
Kappeler on deaths under chloroform
vapour, 159.
Kara-Kurt, The, (Lathrodectes lugubris),
490.
Karing on the composition of nux
vomica, 331.
Karitschoner on chronic HCN poisoning,
214.
Kassner, G., Solanine in
potatoes, 396.
Kast, Relation between narcotic power
and number of ethyl groups, 171.
Katipo, The, 491.
Kauzmann on the excretion of morphine,
313.
Keller on the reactions of cornutin, 459.
Keller's method of estimating brucine
and strychnine, 349.
of estimating digitoxin,
433.
of estimating nicotine
in tobacco, 273.
of nux vomica analysis,
330.
Kelynack and Kirby on the symptoms
from drinking arsenical beer, 571.
Kermes mineral, 601.
Kerosine, 136.
Kiliani, H., on antiarin, 445.
3 y on digitonin, 432.
2 3 Formula of digitoxin, 433.
King on opium smoking, 312.
King's yellow, 555.
Kino, Compound powder of, 290.
Kionka, Experiments on carbon mon-
oxide, 71.
Kippenberger on indicators for titration
of alkaloids, 264.
diseased
3 y 3 5
y 5 5 y
2 3 3 2.
2 3 on the decomposition of
chloroform, 169.
3 y on the solubility of allºa-
loids, 255.
Kippenberger's iodine process for purifi-
cation of alkaloids, 253.
3 5 process for separating
alkaloids, 252, 255.
Kirby, Case of poisoning by arsenical
beer, 571.
Kirschgasser on the symptoms of poison-
ing by arsenical wall-papers, 569.
Kitasato and Weyl on the separation of
tetanine, 525.
Klein, Dr., on the cause of food poison-
ing, 531.
Kloswsti or Chapman case of antimony
poisoning, 608.
Kober, Detection of ergot in flour, 460.
Kobert on carbon monoxide poisoning,
70.
on cyanogen iodide, 222.
on deaths from lupin seeds, 479.
on the colour of blood in HCN
poisoning, 214.
effect of “schnaps,” 92.
effects of “phallin,” 429.
effects of sphacelic acid
and cornutin on ani-
mals, 465.
poison of spiders, 490.
symptoms of poisoning
by barium salts, 713.
toxalbumin of castor-oil
seeds, 478.
,, and Küssner on the physiological
action of oxalic acid, 539, 540.
,, and Küssner's experiments on
animals with oxalic acid, 536.
Kobert's classification of poisons, 24.
,, cornutin, 458.
5 3 definition of poison, 23.
,, test for HCN, 217.
Köhler on the action of ergot, 464.
Koller's prussic acid, 203.
Kombe, 447.
Koochla tree, 326.
Koppe, Dr., poisoned by digitoxin, 438.
5 x Separation of muscarine, 428.
Koppe's experiments on digitoxin, 435.
Koppeschaar's method of estimating car-
bolic acid, 192.
Kovallamarin, 449.
Kowalewsky on the combination of
albumin with uranium, 710.
Kraatzer on German sausage poisoning,
532.
Kraft. See Siebert.
Krait (Bungarus caeruleus), 503.
Kratter, Dr., on excretion of strychnine,
345.
Krocker, Physiological action of nicotine,
281.
Kromholz, A case of poisoning by the
common morelle, 431.
Kruger on arsenious acid, 547.
Kufferath on the electrolysis of copper
salts, 651.
48
754
INDEX.
Küsa-úsū, 377.
Küssner, Effects of sodic oxalate on
animals, 536, 539, 540.
Küster on a case of carbolic acid poison-
ing, 183.
,, on sensitiveness of animals to
carbolic acid, 183.
LABURNUM. See Cytisine.
3 5 seeds, Treatment in poison-
ing by, (App.) 727.
Ladenburg on alkaloids in belladonna
and datura plants, 378.
Ladenburg's hyoscine, 395.
2 3 preparation of coniine, 266.
Lajoux method of separating alkaloids,
257.
Lallemand, Perrin, and Duroy on alcohol
in the brain, 146.
Lamy on the effects of thallium salts,
707.
Lamson, Henry, the poisoner, 374.
Lancereaux on chronic poisoning by
copper, 649.
Landsberg on the excretion of morphine,
Lang, R. W., and Carson, C. M., on the
solubility of antimony sulphide, 612.
Langaard, A., on the poison of Illicium
religiosum, 470.
Langsdorf, Dr., on the effects of Amanita
muscaria, 427.
Lanthopine, 286.
Lassar, O., Observations on nitric acid
vapour, 110.
Lathyrus cicera, 480.
2 3 clymenum, 480.
3 5 sativus, 480.
Laudanine, 286, 324.
3 2 nitrate, Fatal dose for rabbits,
351.
Laudanum, 290.
Treatment in poisoning by,
(App.) 727.
Laudanidine, 286, 324.
Laudanosine, 286, 324.
Lauder, Formula for corydaline, 360.
Laurocerasin, 205.
Law on salts which facilitate separation
of arsenic, 581.
,, H. D., Electrolytic cathodes for
separation of arsenic, 594.
Laws relating to poisons, 20–22.
Lead, 616–637.
,, acetate, 617, 618.
,, and opium pills, 290.
,, as a poison, 620.
,, basic acetate, 633.
,, carbonate, 618.
2 3 Dose of, 634.
,, Chloride of, 617.
,, chromate, 625, 701.
Case of poisoning by,
704,
3 5
2 5 5 J
Lead, Chronic poisoning by, 625.
,, Deaths from, 620.
,, Detection and estimation of, 635.
,, Effects of, on animals, 622.
3 3 2 3 3 3 man, 623.
5 5 ,, nervous system, 623.
2. Pºlytic method of separating,
,, Elimination of, 633.
, , encephalopathy, 626.
,, Fatal dose of, 633.
,, glazes, 621.
,, in American overland cloth, 621.
,, in foods, 621.
,, in glass, 621.
,, iodide, 618.
,, Localisation of, 634.
5 5 3 y in the brain, 627.
, , nitrate, 619.
,, oxides, 616.
,, Peroxide test for, 635.
,, Pharmaceutical preparations of,
618.
,, Physiological action of, 632.
,, pigments, 619.
,, plaster, 618.
,, poisoning among white lead em-
ployés, 620.
from water, 629.
Influence on pregnancy,
625
Post-mortem
ances in, 632.
Statistics relative to,
620.
3 y Treatment of, 634.
,, pyrolignite, 619.
,, Salts of, Treatment in poisoning
by, (App.) 722.
,, Sulphate, 617.
,, sulphite, 617.
Lebert and Wyss on the urine in phos-
phorus poisoning, 234.
Ledoyen's disinfecting fluid, 619.
Lees, Isolation of gynocardin, 204.
Lefort on the excretion of morphine,
3.13.
Legrip on the localisation of lead, 634.
Lehmann on hydric sulphide poisoning,
79.
3 5 on hydrochloric acid in gastric
juice, 99,
2 3 on poisoning by chlorine, 77.
2 3 on the excretion of sulphuric
acid, 95.
3 J. on the quantity of laurocerasin
in the service tree, 205.
Ilehmann's experiments on the solubility
of copper, 638, 639.
5 3 experiments on the toxic
effects of copper, 645.
Leiblinger on a case of mercurial
poisoning through the skin, 672.
Lemaistre on poisoning by digitalin, 435.
appear-
INDEX.
755
Lemaurier's odontalgic essence, 292.
Ligº on Reinsch's test for arsenic,
84.
Liquor ammoniae, 117.
,, ammonii arsenitis, 552.
,, arsenicalis, 552.
,, arsenii et hydrargyri iodidi, 653.
,, matri carbolici, 176.
,, plumbi subacetatis, 618.
,, potassae, 122.
,, potassae effervescens, 123.
,, soda, 123.
Lloyd, J. W., on the
morphine salts, 297.
Lloyd's test for morphine, 300.
solubility of
Lemberger, Penetration of carbon mon- |
oxide gas into the body, 75.
L’Emery, Nicolas, 14.
Lentin on poisoning by sabadilla powder,
407.
Leo and Uffelmann's distinction between
acids and acid salts, 106.
Lersch on the effect of digitalis on man,
437. -
Lesfranc on the fatal dose of barium salts,
713.
Lesser on the action of hydrochloric acid
on skin, 102.
,, on the corrosive action of sulphuric
acid, 88.
,, on the pathological changes caused
by oxalic acid, 541.
Letheby, Dr., A case of nitro-benzene
poisoning, 194.
Leucin in phosphorus poisoning, 245.
Levenstein on strychnine in chloral
poisoning, 106.
Lewes' silver cream, 619.
Lewin on the toxic dose of copper, 647.
,, on jaundice in phosphorus
poisoning, 230.
Lewy on the effects of lead poisoning,
627.
Leyden, Fatty liver after phosphorus
poisoning, 238.
Leyden, E., and Munn, P., Urine in
sulphuric acid poisoning, 95.
L’Hote, Poisonous effects of potassic
chlorate, 131.
Liebert's cosmétique infaillible, 618.
Liebig and Wohler on the hydrolysis of
amygdalin, 204.
Liebreck on the blood in phosphorus
poisoning, 235.
Liebreich on the poisonous effects of
chloral, 164. -
Liersch's (L. W.) experiments with
turpentine, 140.
Lieth on the composition of nux vomica,
330.
Life-tests, 45–48.
Ling, A. R., and Rendle, T., on the
purification of hydrochloric acid, 581.
Linné on a case of poisoning by mezereon,
456.
Linossier, G., on the distribution of
barium in the body, 714.
Linstow, Dr., on a case of poisoning by
chromate of lead, 704,
705.
3 3 on the effects of Santonin,
455.
Liouville on the poisonous effects of
curare, 419.
ſi ,, on the post-mortem appearances
|---as in silver nitrate poisoning,
--~~~ 601. W918 - §
Lipowitz's test for phosphorus, 245,
j'i' ºv
Lobel, L., on the minimum dose of
phosphorus, 229.
Locke on the physiological action of
oxalic acid, 539.
Locusta, 6.
Locust tree, 481.
Loen on post-mortem appearances after
lead poisoning, 632.
Loew's theory as to poisons, 39.
Loewy on poisoning by mercuric chloride,
676.
Lolliot on the effects of arsenic on a dog,
560.
Lombard, H. C., A case of sulphuric
acid poisoning, 84.
Lotusin, 204.
Lowe, Charles, on the assay of crude
carbolic acid, 191.
Lubinsky on the detection of bismuth,
654.
Ludwig on the localisation of arsenic in
the body, 586.
Ludwig and de Wry on antiarin, 445.
Ludwig's method of separating mercury,
682.
Luff, Method of extracting the veratrum
alkaloids, 401.
,, properties of jervine, 404.
,, properties of rubi-jervine, 405.
Lupinine, 479.
Lupinidine, 263.
Lupins, 479.
Lupinus luteus, 272.
Lutidine as an antidote for strychnine,
342.
Lycosa tarantula, 490.
Lytta aspera, 492.
M“ADAM on the detection of strychnine,
345.
M“Conkey v. Reg., A case of aconite
poisoning, 370.
Macdougall's disinfecting powder, 176.
Mach on chronic poisoning by copper,
649.
Maclagan, Dr., and Rutter, J. T., on
arsenic eaters, 561.
MacMunn on blood in dinitro-benzen
poisoning, 201.
756
INDEX,
Macniven, E. O., on a case of poisoning
by bichromate of potash, 703.
Macphail's cases of carbolic acid poison-
ing, 180.
Macredy on a case of strychnine-laudanum
duplex poisoning, 336.
Madagascar ordeal poison, 449.
Magelhaes, Test for cytisine, 399.
Magendie on the action of hydrocyanic
acid on a dog, 210.
3 5 on the effects of phosphorus,
229.
Male Fern, 481.
Malmignette (Lathrodectes tredecim-
guttatus), 490.
Malpurgo's test for nitro-benzene, 198.
Mandelic nitrile, 223.
Mandelin's reagent for alkaloids, 251.
Manganja, 447.
Manjot, Dr., on symptoms of chloral
poisoning, 166.
Mannheim, Poisoning by cocaine, 358,359.
Mannkopf and Schultzen on excretion of
sulphates, 95.
2 3 on a sequel of sulphuric acid
poisoning, 89.
3 3 on urine in sulphuric acid
poisoning, 95.
Manouvriez, Dr., Case of potassic chlorate
poisoning, 132.
Marchand, F., Experiments on animals
with potassic chlorate, 130.
Markens, W., Purification of solanine,
396.
Marking-inks, 659.
Marmé-Borchers, Physiological action of
taxine, 416.
Marmé, W., isolates taxine, 416.
x 5 on potass - bismuth iodide
as a precipitant, 448.
2 3 on the effect of cytisine on
animals, 400.
5 3 on the effects of thallium
- salts, 707.
Marmé's experiments with cadmium on
animals, 615.
2 3 reagent for alkaloids, 251.
Marsh and Marsh-Berzelius test for
arsenic, 580–584.
Martin, Experiments on opium smoke,
311.
3 5 on a case of chronic poisoning
by ether, 150.
Martineau on the subacute form of
arsenic poisoning, 566.
Mascarel on phosphorus poisoning, 237.
Maschka on a case of acute poisoning by
copper sulphate, 647, 648.
,, on a case of poisoning by
morphine, 307.
,, on a case of poisoning by Nerium
oleander, 449.
3 y on phosphorus poisoning, 241.
,, on the effects of “phallin,” 429.
Maschka's case of alcoholic poisoning,
} % case of bitter almonds poison-
ing, 220. -
3 5 case showing caution neces-
sary in judging sulphuric
acid spots, 87.
Mason, W. P., on a doubtful case of
arsenic poisoning, 588.
Matches, 226.
Matzkewitsch on the distribution of
zinc in the body, 692.
Maybrick case, 569.
Mayer, Poisonous effects of oxalic com-
pounds, 545.
Mayer, J. L.,
morphine, 300.
Mayer's reagent for alkaloids, 264.
Mays on the physiological action of
brucine, 350.
Meadow saffron, 421.
Meconic acid, 286, 324.
3 5 Physiological
325.
5 3 Separation of, 325.
Meconidine, 286.
Mecomine, 324.
Medicus, L., and Kober, on the detection
of ergot, 460.
Meihuizin on the action of digitalin on
frog's heart, 443.
3 2 on the physiological action of
morphine, 305.
Meili on poisonous effects of phenol and
cresols, 179.
Meillere, G., on the localisation of lead,
634.
Melanthin, 450. -
Melitta venenosa, 488.
Melsens on the detection of nicotine,
282.
Menard on the blood in phosphorus
poisoning, 235.
Mendius’ reaction for producing cada-
verine, 517.
Menegazzi, P. G., on recovery of carbolic
acid, 190.
Menispermine, 465.
Merck on codeine in opium, 317.
,, on hyoscine, 395.
on pseudo-hyoscyamine isolated
by, 396.
on the solubility of Strychnine,
327. *
Mercurial lotion, 664, 665.
ointment, 663–665.
3 y suppositories, 663.
3 3 tremor, 673.
Merculic chloride, 664, 675.
cyanide, 667, 681.
ethyl chloride, 664.
methide, 674.
3 * potass-iodide, 249, 686.
5 * salts, Tests for, 681.
on Lloyd’s test for
action of,
3 3
9 3
5 y
3 3
} %
9 3
INDEX.
757
Mercuric salts, Volumetric estimation of,
- 685.
33 sulphide, 667.
Mercurous acetate, 664.
3 3 chloride, 662.
2 3 salts, 681.
Tests for, 681.
Volumetric estimation
of, 686.
Mercury, 662–686.
2 3 Absorption of, by the skin, 672.
2 3 and chalk, 663.
5 5 and quinine, 667.
5 3 cyanide, 221, 667, 677.
9 y Tests for, 680.
3 5 Deaths from, 669.
,, . Detection of, in organic sub-
stances, 681, 683.
5 3 Elimination of, 679.
2 3 Estimation of, 685.
5 5 Green iodide of, 666.
3 5 in the arts, 667.
33 5 3
2 3 2 3
33 in veterinary medicine, 669.
3 3 linimént, 663.
2 3 Localisation of, 679.
3 3 Medicinal and fatal dose of salts
of, 669.
3 * Medicinal preparations of, 662.
5 5. Museum preparations illustra-
tive of cases of poisoning by,
678.
2 3 nitrate, 666, 667.
3 × . 3 y Pathological changes in
cases of poisoning by,
676, 679.
5 5 2 3 Poisonous action of,
676.
,, oleate, 665.
,, Patent and quack medicines
containing, 668.
3 J. perchloride, 664, 675.
33 plaster, 663.
3 3 poisoning, Statistics of, 669,675.
,, Post-mortem appearances in
cases of poisoning by, 677.
... } } Potassic iodide reagent, 249.
,, Red iodide of, 665.
} 3 ,, oxide of, 666.
,, Separation of, 683.
,, subchloride, Ointment of, 665.
3 × 3 y Pill of, 665.
3 3 sulphate, 666.
,, sulphide, 662, 666.
9 J y 2 Identification of, 682.
,, sulpho-cyanide, 668.
2 3 Tests for, 680.
,, Treatment of poisoning by, 677,
(App.) 729.
,, vapour, Effects of, 670–673.
Meric, A case of chronic chloroform
poisoning, 159.
Metaldehyde, 170.
Metals, Detection of, 55.
Metantimonic acid, 601.
Metaphenylenediamine, 519.
Methaemoglobin, 60, 61.
Methene dichloride, 170.
Methocodeine, 305.
Methoxyl groups, Determination of, 263.
Methylamine, 513.
Methyl-aniline violet test for mineral
acid, 105.
,, brucine, 34.
,, chloride, 170.
Methylconiine, 263, 269.
Methyl cyanide, 222.
Methylguanidine, 521.
Methylmorphimethine, 299.
Methyl morphol, 299.
,, phenol. See Cresol.
,, Strychnine, 34.
,, urethane, 37.
Methylene dicytisine, 399.
Meyer, Elimination of methyl groups,
264.
,, on ergot epidemics, 461.
,, on narcotics, 37.
on the action of Strychnine on
blood pressure, 341.
Meyer, Dr. Carl, poisoned by aconitine ;
Post-mortem appearances, 376.
Meyer, H., on the constitution of can-
tharidin, 492. -
Meyer and Steinfeld on the toxic effects
of bismuth, 653.
Mezereum, The Daphne, 456.
Michet, M. Ch., Experiments on fish, 42.
Micro-millimetre, 65.
Milne-Edwards on the action of morphine
on the Felidae, 304.
Mineral blue, 555.
Mirto, D., Experiments on CO, 75.
Mitscherlich's discovery of nitro-benzene,
193
} % process for the detection
of phosphorus, 241.
Mohler, E., Test for benzoic acid, 365.
Mohr, The estimation of arsenic, 698.
Moissan, H., on the composition of
‘‘chandoo” smoke, 311.
Monacetin, 37.
Monkshood or wolfsbane, 360.
Morelle, The common, 431.
Morgagni on poisoning by hellebore root,
446.
Morgan on mortality from chloroform
vapour, 156.
Morphia. See Morphine.
Morphine, 250, 264, 265, 266, 286.
} } acetate, 297.
3 3 Action on animals, 303.
3 y 33 man, 306–309.
3 3 Constitution of, 298.
y 3 derivatives, Physiological ac-
tion of, 305.
3 y Dose of 294.
2 3 Excretion of, 313.
2 3 hydrochlorate, 297.
7.58
INDEX,
Morphine lozenges, 291.
} } meconate, 297.
2 3 Melting and subliming tem-
peratures, 260.
3 3 Physiological action of, 304.
} } poisoning, Treatment in, 312.
3 3 Post-mortem appearances after
poisoning by, 312.
3 y Properties of 296.
} } salts, Solubility of, 298.
} } Separation of, from animal
tissues, etc., 313, 314.
,, . Spectrum of colour reactions,
58.
9 x sulphuric acid, 305.
3 y suppositories, 291.
33 tartrates, 297.
3 3 Tests for, 300–303.
3 * Treatment in poisoning by,
(App.) 727.
Morphol, 299.
Morpholine, 299.
Mosso, Isolation of Clo His N, 528,
Mountain or mineral green, 644.
Mucor phymocetes, 5.
Muir, Patterson, on the estimation of
bismuth, 656.
Mulder on codeine in opium, 317.
Mulliken on preparation of dinitro-
benzoate, 147.
Multiple antidote, 733.
Munk and Leyden on the liver in phos-
phorus poisoning, 238.
Munk and Sippell on the effects of crypto
pine, 323.
Munn, P., on the urine in sulphuric acid
poisoning, 95.
Muraena helena, 487.
Murrell, Physiological effects of gelse-
mine, 354.
Muscarine, 266, 426, 430, 522.
3 * Detection of, 429.
3 y Effects on man, 428.
5 y Properties of, 428.
Mushrooms, Treatment in poisoning by,
(App.) 728.
Mussels, Poisoning by, 488, 526.
Mydaleine, 520.
Mydatoxine, 526.
Mydriasis, Toxic, 48.
Mylabris cichorei, Cantharidin in, 492.
2 3 punctum, 2 3 492.
,, pustulata, 2 3 492.
Myosis, Toxic, 48.
Mytilotoxine, 527.
NAGELvoort, J. B., Tests for physostig-
mine, 410.
Naphtha, Coal-tar, 136, 138.
2 3 Mineral, 135, 136.
3 3 Petroleum, 135, 136.
,, Shale, 136.
Naphthylamines as poisons, 34.
Narceine, Effects of, 320.
, , Melting and subliming tem-
peratures, 261.
,, Properties and constitution of,
3.19.
2 3 Tests for, 320.
Narcotics, 36, 37.
3 5 Minor, 170.
Narcotine, 250, 264, 265, 266, 286.
5 3 Constitution of, 316,
5 3 Effects of, 317.
9 3 Melting and subliming tem-
peratures, 261.
3 3 Properties of, 315.
} } Spectrum of colour reactions,
58.
y y Tests for, 316.
Nasse, O., on the blood in phosphorus
poisoning, 235.
3 2 on the physiological action of
nicotine, 282.
Nativelle's digitalin, 435.
Nemaesia coementaria, 489.
Nerianthin, 448.
Neriin, 448.
Nerium odorum, 440.
,, oleander, Poisoning by, 440, 449.
Nernst balance, 684.
Neumann on blood, 66.
,, on the distribution of barium
in the body, 714.
Neuridine, 515.
Neurine, 41.
Neuwieder green,644.
Nevin's (Dr.) experiments on animals
with tartar emetic, 606, 609, 610.
Newcastle white, 619.
Nicander of Colophon, 3.
Nickel. See Cobalt.
Nicloux and Gautier, Detection of CO, 76.
Nicoteine, 263.
Nicotelline, 263.
Nicotianum tabacum, N.
N. persica, 272.
Nicotine, 250, 263, 264, 265, 266, 272–
283.
Antidote to, 283.
rustica, and
3 3 distinguished from coniine,
276.
2 3 Effects on animals, 277.
} } 5 § man, 278.
Estimation of, in tobacco, 273.
7 5 Excretion of, 281.
7 5 Fatal dose of, 282.
2 3 Physiological action of, 281.
5 y Post-mortem appearances after
poisoning by, 282.
y 7 Properties and constitution of,
275,
2 3 Separation of, from organic,
matters, 282.
3 3 Tests for, 276.
3 3 Treatment in poisoning by,
(App.) 728.
INDEX.
7.59
Nicotinine, 263.
Nikitin on the action of ergot, 464.
,, on the fatal dose of sclerotic
acid, 461.
Nitrate of potash. See Potassic nitrate.
Nitre. See Potassic nitrate.
Nitric acid, 108–116.
9 3 Action of, on vegetation,
110.
2 3 Detection and estimation
of, 115.
2 3 Direct separation from
organic matter, 115.
3 3 Effects of liquid, 111.
3 3 Fatal dose of, 109.
Local action of 112.
2 3 poisoning, Museum speci-
mens of, 113, 114.
3 3 Post-mortem appearances
after poisoning by, 113.
j 3 Properties of, 108.
3 3 Statistics of poisoning by,
109.
5 3 Symptoms of poisoning by,
112.
Use of, in the arts, 109.
3 3 vapour, Poisonous action of,
110.
Nitro-benzene, 193–198.
5 3 Detection of, 197.
3 3 Fatal dose of, 196.
2 3 Oil of bitter almonds dis-
tinguished from, 198.
3 2 Pathological appearances
in poisoning by, 197.
2 3 Physiological action of,
197.
2 3 Properties of, 193.
5 § Separation from organic
matters, 197.
5 5 Symptoms of poisoning by,
193–196.
3 3 Treatment in poisoning
by, (App.) 729.
Nitrous oxide gas, Treatment in poison-
ing by, (App.) 729.
Nottingham cases of food poisoning, 530.
- 3 3 white, 619.
Novy, F. G., Toxines of hog cholera, 528.
Noyes, W. A., on the detection of
strychnine, 345.
Nunneley on the detection of strychnine,
345.
Nunneley’s experiments with HCN on
dogs, 212.
Nurses' drops, 292.
Nussbaum on mortality from chloroform
vapour, 156.
Nux vomica, 326. -
2 3 Analysis of 330.
5 y Aqueous extract of, 329.
3 3 Pharmaceutical preparations
of 329.
! 3 Spiritous extract of 329.
Nux vomica, Statistics of poisoning by,
, tincture (B.P.), 380.
OBOLONSKI on the separation of colchi-
cine, 425.
OEmanthe crocata. See Water hemlock.
Ogier's method for destroying organic
matter, 53.
Ogier, J., and Herscher, Biological test
for blood, 66.
Ogston, F., Test for chloral hydrate,
169
Oidtmann on the localisation of lead,
634.
Oil of bitter almonds, Estimation of HCN
in, 220.
3 3 5 5 Poisoning by, 220.
Oils, Essential, 139.
Oldham cases of food poisoning, 530.
Oleander digitalin. See Neriin.
Oleandrin, 448.
Oliver, T., on hydric sulphide poison-
ing, 79.
Onage, 447.
Onsum on the effects of barium salts on
animals, 712.
,, on the physiological action of
oxalic acid, 539.
Opalina ranarum, 43.
Ophiotoxin, 499.
Opianic acid, 316.
Opianine, 286.
Opianyl, 324.
Opium group of alkaloids, 285–325.
Action on animals, 303.
2 3 2 3 man, 306–309.
,, Action of solvents on, 287.
,, Ammoniated tincture of, 290.
,, and lead pills, 290.
,, Aromatic powder of chalk and,
290.
, , Assay of, 287.
,, Composition of, 285.
,, Compound powder of, 290.
,, Confection of, 291,
, , Detection of, 295.
,, Dose of, 294.
,, eating, 310.
,, Extract of, 291.
,, Fatal dose of 295.
,, Liniment of, 291.
,, lozenges, 291.
,, Medicinal and other preparations
of, 290.
,, The ointment of galls and,
291.
,, Patent and non-officinal prepara-
tions of, 292. *
,, poisoning, Diagnosis of, 304.
,, Poisoning of children by, 294.
,, poisoning, Post-mortem appear-
ances after, 312.
Statistics of, 293.
3 3 33
76O
INDEX.
Opium poisoning, Treatment in, 312, 727.
Tincture of 290.
,, wine, 291.
Opistoglypha, 498.
Orange red, 619.
Ordeal bean, 409.
Ore's (M.) injection of chloral hydrate,
164.
Orfila on a case of arsenic poisoning with-
out symptoms, 563.
poisoning by acid oxa-
late of potash, 538.
poisoning by tartar
emetic, 607.
poisoning by verdigris,
648.
2 3
on arsenic in bones, 588.
on perforation of stomach due to
potassic nitrate, 130.
on poisoning by water hemlock,
474.
on the destruction of organic
matter, 585.
effects of barium salts on
animals, 712.
elimination of antimony,
610.
imbibition of arsenic
after death, 590.
inflammatory effects of
arsenic, 575.
post-mortem appearances
In arsenic poisoning,
573.
separation of iron from
organic matter, 700.
time after death nicotine
may be detected, 282.
experiments on animals with
lead, 622.
experiments on animals with
oxalic acid, 536.
5 3 experiments on ether, 150.
Organic matter, destruction of, 52, 585.
drying of, 51.
2 3 5 3
Orfila's
5 5
} }
Orpiment, 551.
Osenbrüggen's case of nitric acid poison-
ing, 111.
Otori, J., on the amines, 510.
Otto on a coniine-like alkaloid, 272.
Oubain, 418.
Overend and Hofman on the action of
curare, 420.
Overton, Researches on narcotics, 36.
Oxalate of line, 534.
Oxalic acid, 533–544.
3 J. Effects of, on animals, 535.
2 3 3 5 leeches, 537.
y 5 } % man, 537.
2 3 Estimation of, 544.
3 y Fatal dose of, 535.
5 y in the form of vapour, 537.
9 Pathological changes pro-
duced by, 540.
Oxalic acid, Physiological action of, 539.
9 3 Properties of, 533, 534.
2 3 Separation of, 541.
3 3 Statistics of poisoning by,
535.
3 3 Treatment of poisoning by,
(App.) 729,
- } 3 Uses in the arts of, 535.
Oxalmethyline, 545.
Oxalpropyline, 545.
Oxyhaemoglobin, 60, 61.
Oxymandelic acid, 241.
Oxynarcotine, 286.
PAGE, Dr. D., on poisoning by anti-
monial lozenges, 606.
Pagel's process for destroying organic
matter, 54.
Palm, R., Separation of picrotoxin, 468.
Palmer, William, the poisoner, 333.
Papaveramine, 286.
Papaverine, 264, 266, 286.
3 5 Effects of, 321,
3 y Melting and subliming tem-
peratures, 261.
5 3 Properties and constitution
of, 321.
2 3 Spectrum of colour reactions
58.
Papaver somniferum, 285.
Paradigitaletin, 434.
Paraldehyde, 170.
Paramenispermine, 465.
Paraphenylenediamine, 519.
Paregoric, 290.
Parillin, 450.
Paraffin oil, 134.
Partition coefficients of narcotics, 37.
Chemical deter-
mination of, 38.
Physiological deter-
mination of, 38.
2 3 } }
y 3 2 3
l’attison’s white, 619.
Paul, M., on the hereditary effects of
lead poisoning, 629.
Paul of Ægina on the effects of lead on
the nervous system, 626.
º on the effects of thallium salts,
07.
Pauly, Epinephrin, 505.
Payne and Chevallier on the action of
organic fluids on zinc, 688.
Pedler on the poison of the cobra, 499.
Pehkschen's formula for jervine and
pseudo-jervine, 404.
Pelikan on the effects of saponin, 451.
,, on the poisonous action of mer-
curic cyanide, 222.
Pelletier and Cahours on the solubility
of strychnine, 327. -
3 y and Caventou on the solubility
of brucine, 349.
?? and Thiboumery discover
pseudomorphine, 323.
INDEX.
761
Pennavaria on a case of poisoning by eel
blood, 489.
Pentamethylenediamine. See Cadaverine.
Pental, 170.
Pentane, 170.
Peptotoxine, 524.
Pereirine, 353.
Perls on the lungs in phosphorus poison-
ing, 240.
Perrin, Alcohol in the brain, 146.
Personne's method of estimating mercury,
685. .
Pesci and Stroppa on the urine in phos-
phorus poisoning, 246.
Petrol, 135.
Petroleum, 135.
2 3 ether, 135, 136.
5 2 Poisonous effects of, 136.
y 3 Separation of, 137.
3 y spirit, 135, 136.
Petromyzon fluviatilis, 489.
Pottenkofer on cantharides in blood, 496.
5 3 on the solubility of mor-
phine, 296, 297.
solubility of strych-
nine, 327.
Pfaff's prussic acid, 203.
Pfeiffer's (E.) experiments on animals
with oxalic acid, 537.
Phallin, 429.
Phaseo-lunatin, 204.
Phenic acid. See Carbolic acid.
Phenol. See Carbolic acid.
Phenylaminoaceto nitrile, 223.
Phenylenediamine, 40. t
Phenylhydrazine, 40.
Phenylic alcohol. See Carbolic acid.
Phenyl sulphate of potash, Separation of,
from urine, 191.
5 5 3 3 Tests for, 191.
Phenyl sulphuric acid, 184.
Phipson, Active principles of Agaricus
ruber, 430.
Phisalix and G. Bertrand on bufonin,
3 3 5 3
,, . and G. Bertrand on the poison
of the common viper, 504.
Phloroglucin, 34.
Phosphine, 225, 235.
Phosphomolybdic acid reagent, Prepara-
. tion of, 249.
Colour reaction
with alkaloids,
250.
$ 3 3 5
Phosphorated oil, 226.
Phosphorus, 5, 224–274.
3 3 Antidote for poisoning by,
235, 729,
9 3 Chronic poisoning by, 234.
3 3 Detection of 241.
3 y Estimation of, 246.
} } Fatal dose of, 229.
matches and vermin-paste,
226.
Phosphorus, Medical preparations of, 226.
2 3 poisoning, The blood in,
23
2 3 3 3 Difference be-
tween yellow
atrophy and
fatty liver, 241.
Effects of, 229,
232.
Sequelae to, 232.
Urine in, 245.
When symptoms
commence, 232.
2 3 Post - mortem appearances
after poisoning by, 237–
241.
$ 2 Properties of, 224.
2 3 Statistics of poisoning by,
228.
5 y Time after which it may be
recognised in dead bodies,
247.
3 y Time of death after taking,
232.
2 3 Treatment in poisoning by,
(App.) 729.
3 3 Urine in poisoning by, 234,
245.
3 y vapour, Poisoning by, 232.
Phospho-tungstic acid reagent, 251.
Phosphuretted hydrogen, 225.
Photogen, 136.
Physostigma faba, 409.
Physostigmine, 409–413.
2 3 Effects on animals, 411
3 3 3 3 man, 412.
3 y Fatal dose of, 413.
Pharmaceutical prepara-
tions of, 411.
2 3 Physiological action of,
412.
> Poisoning by, 412.
3 y Post-mortem appearances
* after, 412.
} 3 Properties of, 409.
3 3 Separation of, from
organic matter, 412.
5 Spectrum of colour re-
- actions, 58.
3 x Tests for, 410.
35 Treatment in poisoning
by, (App.) 722.
Picric acid and Picrates, 470.
9 3 Effects of, 470.
5 y Tests for, 471.
Picrotin, 466, 467.
Picrotoxin, 465–469.
y 3 Effects on animals, 467.
9 3 y 2 man, 468.
y 5 Fatal dose of, 467.
3 3 Melting and subliming
temperatures, 262.
2 3 Physiological action, 468.
3 * Properties of, 466.
762
INDEX.
Picrotoxin, Separation of, from organic
matter, 468.
3 5 Treatment in poisoning by,
(App.) 730.
Picrotoxinin, 466,467.
Pigs’ tongues, Poisoning by, 530.
Pilocarpine, Melting and subliming
temperatures, 262.
3 3 Treatment in poisoning by,
(App.) 730.
Pilula asiatica, 553.
,, hydrargyri subchloridi composita,
603.
,, plumbi cum opio, 618.
Pinewood test for carbolic acid, 187.
Piotrowski, G., on carbon monoxide in
blood, 63.
Piperidoaceto nitrile, 223.
Piperine, 250, 266.
Pºi on the fatal dose of barium salts,
13.
Piturie, 283.
Platinic chloride reagent, 249.
Plenk on poisoning by sabadilla powder,
407
Plowright on a death from eating Agari-
cus phalloides, 430.
5 J Oxalic acid and oxalates in
fungi, 533.
Plugge on the action of aconitine on
reptiles, 367.
Plumstead murder case, 631.
Pohl on the poison of Synanceia brachio,
487.
Poison, Definition of, 20, 22, 23.
,, French law relating to, 22.
,, General method of search for,
48–56.
,, German statute relating to, 21.
,, lore, 1–13.
Poisons, Classification of, 23–29.
,, Statistics relating to, 29–32.
Polygallic acid, 450.
Pomeroy, A case of poisoning by chloro-
form, 155, 156.
Pommerais, Conty de la, 444, 445.
Popoirci’s (H.) method of estimating
nicotine in tobacco, 273.
Poppies, Syrup of, 292.
Pork, Poisoning by, 529, 530.
Porta, J. Baptista, 10.
Porte, Effects of ferric chloride on
animals, 697.
Portsmouth cases of food poisoning,
530.
Posner, Effects of chromium compounds
on animals, 702.
Potash (potassa caustica), 122.
,, Carbonate of, 123.
,, Pharmaceutical
122.
,, Properties, 122.
Potassic bichromate, 701.
Use of, in arts, 702.
preparations,
3 3 2 3
Potassic chlorate, 130.
Detection and estima-
tion of, 132.
Effects on man, 131.
Elimination of, 132.
Experiments on ani-
mals with, 120.
Poisonous properties of,
130
9 3 Uses of, 130.
,, chromate, 701.
,, cyanide. See Hydrocyamic acid.
,, ferro-cyanide, 221.
, nitrate, 128, 129.
} } ,, Post-mortem appear-
ances after poisoning
by, 130.
2 3 ,, Statistics of poisoning
by, 129.
1 y ,, Treatment in poisoning
by, 728.
,, phenyl-Sulphate, Separation from
urine, 191.
5 y Tests for, 191.
,, sulphate, 128.
,, . Sulphocyanide, 222.
,, tartrate, Elimination of, 128.
Hydro-, 128.
y 2 ,, Poisonous action of, 128.
,, Xanthogenate, 174.
,, -zinc iodide reagent, 251.
Potassium salts, Neutral, 128–134.
Pot-curare, 418.
Pouchet, Elimination of antimony, 610.
Poudre épilatoire, 711.
“Poudres de succession,” 12.
Poullson, Poisoning by male fern, 481.
Powell’s balsam of aniseed, 292.
Power and Cambier, Active principle of
locust tree, 481.
Power, F. B., and Lees, F. H., on a prussic
acid yielding glucoside, 204.
Praag, L. v., Action of aconitine on fish,
367.
3 3 Action of aconitine on
birds, 369.
Preyer on the action of hydrocyanic acid
on a rabbit, 210, 211.
,, separates curare alkaloids, 419.
Prichard, Mrs., poisoned by antimony,
607.
Priestley, Preparation of hydrochloric
acid, 97.
} } and Boussingault, Experiments
on the influence of mercurial
vapour on plants, 670.
Prochorow, Poisoning by Petromyzon
fluviatilis, 489.
Propylamine, 513.
Protocuridine, 418.
Proteroglypha, 498.
Protocurine, 418.
Protocurarine, 418.
Protopine, 286.
* 3 ! 3
INDEX.
763
Protoveratridine, 402, 404.
Prout, Hydrochloric acid in gastric
juice, 99.
Prussic acid, 202. See Hydrocyanic
acid.
5 7 Treatment in poisoning
by, (App.) 730.
Pseudaconitine, 362, 363.
Pseudaconitines, 362, 363.
Pseudaconhydrine, 269.
Pseudo-hyoscyamine, 377, 396.
Pseudo-jervine, 402, 404.
Pseudomorphine, 286, 298, 323.
Ptomaines. See Animal toacimes.
Putrescine, 518.
Puff adder (Vipera arietans), 504.
Pyrethrum rosea as an insecticide, 45.
Pyro-catechin, Separation of, from urine,
184.
Pyrogallol, 34.
Pyrrol, 40.
QUEBRACHINE, 353.
} } Spectrum of colour re-
actions, 58.
Quebracho blanco, 353.
Quillaja Sapotoxin, 450.
Quillajic acid, 450.
Quinidine, 265.
Quinine, 250, 265, 266.
,, Spectrum of colour reactions,
58.
RABUTEAU on the poisonous properties
of amyl alcohol, 148.
Radecki on the effects of cantharides,
493.
Rajpoots as takers of opium, 311.
Rattlesnakes, 503.
Raubenheimer, J. A., Case of phenol
poisoning, 180.
Rayner, Henry, Effects of lead on the
nervous system, 626.
Realgar, 551.
Red lead, 619,
Reece, Dr., on the imbibition of arsenic
after death, 590.
Reg. v. Massey and Ferraud, 477.
Reg. v. Moore, 677.
Reichard's (C.) test for morphine, 301.
Reiche, Effects of sulphuric acid on
kidney, 91.
Reid, Dr., Cases of carbon monoxide
poisoning, 69, 73.
Reinsch's test for arsenic, 584.
Rendle, Detection of arsenic, 581.
Resorcin, 36.
,, dimethyl, 36.
Retford cases of food poisoning, 530.
Rettgers, J. W., on arsenic mirrors, 583.
Reynold's gout specific, 423.
Rhigoleme, 135.
Ribau on coriamyrtin, 409.
Richardson on blood, 65.
Richardson, Sir B. W., on bichromate
disease, 702.
3 3 2 3 on methene
dichloride,
170.
3 3 5 5 on mortality
from chloro-
form vapour,
156.
action of
amyl nitrite,
149.
2 3 5 3 on dose of
chloral, 165.
effects of
turpentine,
140.
on the poison-
ous proper-
ties of amyl
alcohol, 148.
Richardson's (Sir B. W.) experiment
with strychnine, 341.
Richet, M., on the toxic action of
strychnine, 337.
Richet's experiments with strychnine,
341.
Richter on the detection of strychnine,
345.
Riegler's reagent for blood, 60, 61.
Riemer on the post-mortem appearances
in silver nitrate poisoning, 660.
Riess, O. L., Distinction between phos-
phorus poisoning effects and atrophy
of liver, 241.
Riner's prussic acid, 203.
Ringer, S., on the action of aconitine,
5 3 3 y Oll
2 3 5 3 OIl
375.
2 3 and H. Saintsbury on neutral
alkali salts, 128.
5 y and Murrell on physiological
action of gelsemine, 354.
Rinman's green, 688, 693.
Ritter on the blood in
poisoning, 235.
Roberts’ test for morphine, 300.
Robertson, A., and Wynne, A. J., on
cases of poisoning by eating Phaseolus
lunatus, 213.
Robertson, Dr., on the effects of lead on
the sight, 627.
Robinia pseudo-acacia, 481.
Robiquet's prussic acid, 203.
Roburite factories, Poisoning in, 199.
Roger on the effect of copper leguminate,
645.
Rogers (Leonard) on the poison of sea-
snake, 498.
Röhrig on the effects of oil of savin, 475.
,, on the excretion of milk dimin-
ished by chloral, 163, 164.
,, on the physiological action of
picrotoxin, 468.
Roman knowledge of poisons, 2.
phosphorus
764
INDEX.
Romellaere on the blood in phosphorus
poisoning, 235.
Roos, Separation of cadaverine, 516.
Rose on the effects of Santonin, 454.
,, on the estimation of arsenic, 597.
Rosenstein's experiments on animals with
lead, 622.
Rosenthal and Krocker on action of
nicotine on the brain, 281.
Ross, Dr., on the poisonous effects of
dimitro-benzol, 199.
Rossbach, N. J., on Opalina ranarum, 44.
5 3 on the action of ergot,
464.
2 3 on the effects of colchi-
cine, 423.
Rouget, on the effects of silver nitrate on
animals, 659. -
Roussin, Eſſects of sulphate of zinc as a
poison, 690.
Roussin's crystals, 276.
2 3 test for purity of chloroform,
152.
Ruberine, 430.
Rubi-jervine, 402, 405.
Rusma, 551. -
Russell’s viper (Duboia russellii), 504.
Rutter, Dr. J. T., on arsenic eating, 561.
SABADILLINE, 401.
5 y Spectrum of colour reac-
tions, 58.
Sabadine, 401.
5 x Spectrum of colour reactions,
58.
Sabina communis, 475.
Saint Ignatius' bean, Extract of, 329.
Saintsbury, Toxic effects of the neutral
salts of the alkalics, 128.
Salamander, The poison of the, 483.
3 3 The water, Poison of, 484.
Salerné, C., on the action of ergot, 464.
Salet, M., detection of phosphorus by
spectroscope, 243.
Salicin, Melting and subliming tempera-
tures, 262.
Salicylic acid, 36.
3 3 methyl, 36.
Salkowsky on the lessening of the alka-
loids of the blood, 88.
liver in phosphorus
poisoning, 240.
post-mortem appear-
ances in antimony
poisoning, 610.
separation of poison of
mussels, 526.
Salmon, Tinned, Poisoning by, 530.
Salzberger isolates protoveratridine, 404.
} } on rubijervine, 405.
7 3 on the melting-point of rubi-
jervine, 405.
Salzberger's (G.) protoveratrine, 402.
3 3 33
2 3 2 3
3 y 7 5
Sal volatile, 118.
Samandaridin sulphate, 484.
Samandrin, 483.
35 sulphate, 483.
Samuel, S., Observations on local action
of ammonia, 124.
Sanarelli, G., on the poison of the
Scorpiom, 486.
Sand, H. J., and Hackford, J. E., The
estimation of arsenic, 594.
Sanderson, Dr. Burdon, on the action of
gelsemine on respiration, 355.
Sanguimarin, Spectrum of colour re-
actions, 58.
Sansom on deaths under chloroform
vapour, 159.
Santonin, 453-455.
5 y Effects on animals, 454.
3 3 5 5 man, 454.
2 3 Fatal dose of, 454.
2 3 Poisoning by, 453. -
2 3 Post-mortem appearances after
poisoning by, 455.
3 3 Properties of, 453.
5 3 Separation of, from organic
matter, 455.
Sapindus-Sapotoxin, 450.
Saponin, 450–453.
2 3 Effects of, 451, 452.
} } Identification of, 453.
2 3 Melting and subliming tempera
tures, 262.
,, Properties of, 450.
,, Separation of, 452.
Saponaria officinalis, 450.
Saprime, 522.
Saporubin, 450, 451.
Sarsaparilla-Saponin, 450.
Sarsa-Saponin, 450.
Sausages, Poisoning by, 530.
Sautesson, The poison of the Heloderma,
486.
Savin, Oil of, 475.
3 3 ,, Post-mortem appearances
after poisoning by, 476.
Separation and identifica-
tion of, 476.
} % Tºwn on poisoning by, (App.)
31.
Scattergood on the toxic eſſects of silver
nitrate on man, 660.
Schaaf’s cases of camphor poisoning, 142.
Schacht's method of assaying opium, 288.
Schauenstein on a case of atropine poison-
ing, 385.
} } on a case of strychnine-
laudanum duplex poison-
ing, 336.
3 3 on a case of suicide by
chloroform, 157. w
2 3 on poisoning by hellebore
447.
3 y on strychnine in the urine,
334.
3 J 2 3
INDEX.
765
Schauenstein on the statistics of strych-
nine poisoning, 332.
y 5 on undissolved strychnine
in the stomach, 342.
Schaufféle on the action of organic fluids
on zinc, 688.
Scheele killed by prussic acid, 207.
Scheele's green, 555.
5 § prussic acid, 203.
Scheibler's process for separating alka-
loids, 256.
3 * reagent for alkaloids, 251.
Scherer's test for phosphorus, 245.
Schindelmeiser, J., on the solubility of
morphine, 297.
Schindler on codeine in opium, 317.
Schlimpert on the solubility of morphine,
297.
2 3 on the solubility of strych-
nine, 327.
Schmidt, Hydrochloric acid in gastric
juice, 99.
92 on hyoscine, 395.
Schmidtmann on poisoning by mussels,
526.
Schmiedeberg on aniline poisoning, 284.
2 3 on digitalin, 435.
5 5 on the poisonous action of
chloroform, 154.
3 y on the poisonousglucosides,
445.
3 × on the active principles of
oleander leaves, 448.
3 3 on the physiological action
of atropine, 389.
2 3 and Harnack on muscarine,
428.
J 3 and Koppe isolate muscar-
ine, 428.
Schmiedeberg's digitonin, 432.
3 3 method of estimating
chloroform, 161.
Schönbein on the action of prussic acid
on the blood, 209.
2 3 on the oxidation of arsenical
stains, 583.
Schönbein’s test for HCN, 216, 217.
Schraeder's prussic acid, 203.
Schraube, O., Statistics of phosphorus
poisoning, 228.
Schroff on the post-mortem appearances
after poisoning by colchicine,
425.
,, on poisoning by colchicine, 424.
Schroff's antidote for physostigmine,
412.
Schuchardt, Effects of phosphorus on the
blood, 235.
Schuler on the action of Strychnine,
338.
Schultzen, Secretion of sulphuric acid,
95.
Schultzen, O., and O. L. Riess, on fatty
liver in phosphorus poisoning, 241.
Schultzen, O., and O. L. Riess, on the
urine in phosphorus poisoning, 234.
Schulz, Penetrability of carbon mon-
oxide, 75.
3 5 and Praag, Action of aconitine
on fish, 367.
Schulz (H.) and Mayer's experiments on
the oxalic group of poisons, 545.
Schulz, W. von, on saporubin, 451.
Schulze's reagent for alkaloids, 251.
Schumacher and W. Juny's method of
detecting mercury, 684.
Schumm, O., on the detection of mercury,
683.
Schutte, W., on the alkaloids in the
belladonna plant, 378.
Schweinfurt green, 555.
Scillain or scillitin, 448.
Scillotoxin, 440.
Sclererythrin, 459.
Sclerocrystallin, 459.
Scleroidin, 459.
Scleromucin, 457.
Sclerotic acid, 458.
Sclerotium clavus, 456.
Scolosuboff on the localisation of arsenic
in the body, 586.
Scopola carmolica, 391.
Scopolamine, 378, 395.
Scorpio europaeus, 486.
Scorpion, The poison of the, 486.
Sea-snakes (Hydrophinae), 498.
Sea-hare, 3.
Secalin-toxin, 458.
Sedgwick on the symptoms of poisoning
by cytisine, 400.
5 3 on the effects of cantharides,
495.
Seeliger, Toxicity of copper oleates,
639. -
Seibert and Kraft's spectroscope, 57.
Seidel on the action of hydrocyanic acid
On a man, 211.
,, on the effects of mercurial vapour,
671.
,, on post-mortem appearances after
alcoholic poisoning, 145.
Selmi on the urine in phosphorus poison-
ing, 246.
Selmi’s process for separating alkaloids,
253.
Senegin, 450.
Siebold, Destruction of organic matter,
JZ.
Siebold's test for morphine, 302.
Siem, Paul, on the action of alum salts
on animals, 708.
Sieveking on the effects of Santonin,
455.
Silico-tungstic acid as a reagent for
alkaloids, 250.
Silver, 657–662.
,, Chronic poisoning by salts of, 660.
,, chloride, 657.
766
INDEX,
Silver cyanide, 222, 661.
,, Detection of, 661.
,, Doses of salts of, 659.
,, Use of, in the arts, 658.
,, nitrate, 658, 661.
Deaths from, 660.
Effects of, on man and
animals, 659, 660.
3 × 3 3 Tests for, 661.
,, oxide, 658.
,, Post-mortem appearances in cases
of poisoning by salts of, 660.
,, Separation of, 661.
,, sulphide, 657.
Sippell, Toxicity of cryptopine, 323.
Sjokvist’s method of estimating HCl in
stomach, 107. -
Smith, Angus, on chlorides in plants,
108.
Smith, F. J., on a case of aniline poison-
ing, 285.
Smith, R., on a case of poisoning by
petroleum, 137.
Smith, T. and H., discover cryptopine,
323.
2 3 2 3
$ 2 2 3
Jn the change of ferric
hydrate to oxy-
hydrate, 577.
Smith, Dr. Watson, on a case of poison-
ing by chromate of lead, 704.
Smoler, O., on the .urine in sulphuric
acid poisoning, 95.
. Snakes, Bite of, Treatment in poisoning
by, (App.) 731.
,, Poisonous, 498–504.
Snell, Simeon, on the poisonous effects of
dinitro-benzol, 199.
Snow, Dr., on a case of poisoning by lead
carbonate, 622.
Soap-pill, The compound, 291.
Soda, Caustic, 123.
Soda carbonas, 123.
3 ) 2 3 exsiccata, 123.
Sodic cyanide, 221.
,, mitrate, 129.
Sodium bicarbonate, 123.
,, hydrate, 123.
,, nitro-prusside, 223.
,, salts, Neutral, 127–134.
Sokoloff, N., on separation of HCN from
organic matter, 218, 219.
Solanaceae, Alkaloids of, 377.
Solanine, 250, 396, 398.
2 3 Melting and subliming tempera-
tures, 261.
3 y Poisoning by, 398.
3 2 Properties of 397.
3 3 5 5
5 x Separation of, from organic
matter, 398.
5 3 Spectrum of colour reactions, 58.
5 5 Tests for, 397.
Treatment in poisoning by,
(App.) 731.
Solanidine, 397.
Solanum dulcamara, 396.
5 y nigrum, 396.
y 5 tuberosum, 396.
Somoform, 170.
Somnenschein on a case of nicotine
poisoning, 279.
5 5 on a case of poisoning by
hyoscyamine, 395.
3 y on poisoning by ferro-
cyanide, 221.
2 3 on the detection of
phosphorus, 242.
} } on detection of phos-
phorus long after death,
247.
3 2 on the estimation of phos-
phorus, 246.
5 3 on the imbibition of
arsenic after death, 587.
Sophora tomentosa and speciosa, 398.
sººn on the bitter taste of brucine,
49.
Sparteine, 263, 264, 284.
Spartium scoparium, 284.
Spectroscope as an aid to the identifica-
tion of poisons, 56.
Spectroscopic appearances of blood, 60.
Spectrum of phosphorus, 244.
Speichert, Case of arsenic poisoning, 573.
Spermoedia clavus, 456.
Sphacelic acid, 465.
Sphacelo toxin, 458.
Spiders and insects, Poisonous, 489–497.
Spiritus ammoniae aromaticus and foeti-
dus, 117.
Städeler’s fuchsine test for alcohol in
chloroform, 152.
Stadelmann on ingestion of oxybutyric
acid, 88.
Stadelmann's experiments on animals
with arsine, 549.
Stadthagen and Brieger on the isolation
of animal toxines, 510.
Stannius on the influence of digitalis on
the heart, 440.
Starling, E. H., and Hopkins, F. G., on
the urine in phosphorus poisoning, 234.
Stas separates nicotine in the Fougnies
case, 278.
Stas-Otto process for separating alka-
loids, 252.
Statira, Poisoning of, 6.
Steinfeld, Toxic effects of bismuth, 653.
Stevenson, T., on the antimony found in
the Chapman case, 609.
2 3 on carbon monoxide in
blood, 63.
on dangerous dose of
nitro-benzene, 196.
} } on poisoning by water
gas, 72.
3 ) on the post-mortem ap-
pearances after poison-
ing by lead, 632.
INDEX.
767
Stevenson, T., and Dupré, Separation of
aconitine, 376.
Stevenson, Dr. T., and Dr. Fagge, Action
of digitalin on frog's heart, 442.
Stibine, 614.
Stillmark on the toxalbumin of castor-
oil seeds, 478.
Stockmann and Dott on the physiological
action of morphine, 305.
Stolnikow, 36.
Stramonium extract, 380.
Treatment in poisoning by,
(App.) 731.
Straussmann and Schulz, Experiments
on CO, 75.
Strophantin, 440, 447. *
3 2 Treatment in poisoning by,
(App.) 731.
Strophanthus hispidus, 447.
Stroppa on phosphine in the urine,
246
2 3
Strychnos castelnaca, 418.
2 3 colubrina, 326.
2 3 ignatius, 326.
2 3 nux vomica, 326.
92 tieuté, 326.
5 3 toxifera, 418.
Struve on the detection of HCN long
after death, 220.
Stuart's (Anderson) experiments on
nickel and cobalt salts, 693.
Substituting poisons, Loew’s, 41.
Succus conii, 270.
Sugar of lead, 617, 633.
Suicide by poison, 2.
Sulphaemoglobin, 61, 62.
Sulphates in sulphuric acid poisoning,
96.
Sulphides of metals, Identification of,
612.
Sulpho group, 41.
Sulphonal, 37, 171.
Sulphones, 171.
Separation and identification,
172.
Sulphuretted hydrogen.
sulphide.
Sulphuric acid, 81–97. ;
Aromatic, 82.
Blood in poisoning by,
96.
Chronic poisoning by, 92.
Detection and estimation
of, 93–97.
Excretion of, 94,
Fatal dose of, 85.
Local action of, 85.
Museum specimens of
pharynx, gullet, etc.
after poisoning by, 92.
Nordhausen, 82.
Poisoning by, 83.
Post-mortem appearances
after poisoning by, 90.
Properties, 81.
Purification from arsenic,
582.
Spots of, on
matter, 86, 87.
Statistics of poisoning by,
82.
Symptoms of poisoning
by, 87–89.
Treatment of poisoning
by, 89.
3 3 anhydride, 82.
Sulphur trioxide, 82.
Superbin, 440.
Suppositoria plumbi composita, 618.
Surucucu (Lachesis muta), 503.
Susotoxine, 528.
Swieten on the non-fatal dose of sugar
of lead, 633.
Synanceia brachio, 487.
Syringin, 450.
2 3
Strychnine, 250, 264, 265, 266.
acetate, 328.
Action of, on animals, 337.
3 3 man, 338.
3 2 chromate, 328.
2 3 Diagnosis of poisoning by,
340.
3 5 double salts, 329.
Elimination of, 344.
3 5 Fatal dose of, 334.
3 y in atropine, Test for, 383.
in brucine, Detection of, 331.
3 5 iodide, 329.
Melting and subliming tem-
- peratures, 261.
• 3 nitrate, 328.
,, Fatal dose for
rabbits, 351.
$ 3 not destroyed by putre-
faction, 345.
5 : Pharmaceutical preparations
containing, 329. ---
Physiological action of, 340.
; : 32 test for, 347.
Post - mortem appearances
after poisoning by, 341.
Properties of, 326.
2 3
3 *
3 *
$ 3 Quantitative estimation of,
348.
2 3 Separation of, from organic
matter, 342.
,, . Spectrum of colour reactions,
58.
3 3 Statistics of poisoning by,
332.
$ 3 sulphate, 328.
2 > sulpho-cyanide, 329.
5 y sºme of poisoning by,
8.
5 3. Tests for, 345.
22 trichloride, 329.
3 J. Treatment in poisoning by,
342, (App.) 731.
See Hydric
organic
768
INDEX.
TAHARA, G., on tetrodon poison, 487.
Takahashi, D., and G. Inoko, on tetrodon
poison, 487.
Tamus communis, 481.
Tanghinia venenifera, 440.
Tanqueril on the effects of lead poison-
ing, 625, 626.
Tanret, C., on the active principles of
ergot, 457.
Tar acids, 174–193, 449.
Tarantula, 490.
Tardieu on phosphorus poisoning, 237.
,, on the action of digitalis on
man, 436.
effects of cantharides,
495.
effects of phosphorus,
229.
nervous form of arsenic
poisoning, 568.
,, and Roussin on a case of poison-
ing by zinc, 690.
Tardieu's case of prussic acid poisoning,
207. -
Tartar emetic, 601.
Antidotes for, 610, 720.
Effects of, on animals, 605.
2 3 on man, 606.
2 3 ,, Estimation of, 601.
5 5 ,, Treatment in poisoning
by, (App.) 720.
,, Salt of, 123.
Tartarated antimony. See
emetic.
Tartarate of potash and antimony. See
Taºtaºr emetic.
Tartaric acid, Treatment in poisoning by,
(App.) 732.
Tartra on gas formation in nitric acid
poisoning, 112, 113.
Tartra’s treatise on nitric acid poisoning,
111.
Taube on ergot epidemics, 461.
Taxine, 416, 417.
Effects on animals, 416.
3 3 3 3 man, 417.
Poisoning by, 416.
Post-mortem appearances after
poisoning by, 417.
,, Properties of, 416.
Taylor, A. S., A case of alcohol poison-
2 3 5 *
3 y 5 5
3 3 3 3
y 5 5 5
$ 3 5 y
5 y 3 3
Tartar
5 3
5 y
3 y
ing, 144.
y 5 A case of ammonia poison-
ing, 120.
3 3 A case of antimony
chloride poisoning, 611.
A case of arsenic poison-
ing, 563.
A case of carbonate of
potash poisoning, 125.
case of chloroform
poisoning, 155.
A case of coniine poison-
ing, 271.
3 3 A
Taylor, A. S., A case of hydric sulphide
poisoning, 79.
5 y A case of hydrochloric
acid poisoning, 103.
3 y A case of mercuric chloride
poisoning, 675, 676.
5 3 A case of morphine
poisoning, 309.
5 3 A case of naphtha poison-
ing, 138.
5 5 A case of nicotine poison-
ing, 279.
$ 2 A case of nitro-benzene
poisoning, 194.
3 2 A case of oxalic acid
poisoning, 539.
3 3 A case of petroleum
poisoning, 137.
9 3 A case of phosphorus
poisoning, 237.
} } A case of prussic acid
poisoning, 213.
3 y A case of tartar emetic
poisoning, 606.
2 3 A case of taxine poison-
ing, 417.
3 5 Cases of turpentine poison-
ing, 140.
3 y Cases of white precipitate
poisoning, 677.
5 2. on chronic poisoning by
copper, 648.
y 5 on chronic lead poisoning,
529.
2 3 on the action of chloro-
form, 154.
} } on the effects of digitalis
On man, 437.
2 3 on the effects of oil of
Savin, 475.
x 5 on the fatal dose of
cantharides, 493.
2 3 on the fatal dose of
colohicine, 423.
3 y on the fatal dose of oxalic
acid, 535.
5 y on the fatal dose of prussic
acid, 208.
2 3 on the fatal dose of
Strychnine, 336.
2 3 on the minimum lethal
dose of sulphuric acid,
85.
3 y on the post-mortem ap-
pearances after aconi-
time poisoning, 376.
3 3 on the post-mortem ap-
pearances after alcoholic
poisoning, 145.
3 y on the solubility of
arsenious acid, 547.
3 y Poisoning by nitric acid
vapour, 111.
Teichmann's crystals, 63.
INDEX.
769
Teilleux, The active principles of Lathyrus
sativus, 480.
Terebenthene, 139.
. Terpenes, 139.
Teschemacher and Smith's method of
assaying opium, 287.
Tetanic acid test for morphine, 301.
Tetanine, 525.
Tetanotoxine, 525.
Tetanus, Poisons connected with, 525.
Tetramethylenediamine. See Putrescine.
Tetra-methyl-diamino-phenyl-methane
test for lead, 635.
Tetrodon, 487.
Tetrodonic acid, 487.
Tetrodonin, 487.
Tetronal, 171.
,, 37.
Thaeter, K., Separation of helleborin, º
446.
Thallium, 707.
3 3 Separation of, 707.
Thallium salts, Effects of, 707.
Thebaine, 264, 266, 286.
Effects of, 322.
Melting and subliming tem-
peratures, 261.
Properties of, 322.
Tests for, 322.
nitrate, Fatal dose for rabbits,
351.
Theine, 250, 266.
Melting and subliming tempera-
tures, 262.
Theobromine, 40, 41, 250, 266.
3 3 Subliming temperature,
262.
Theraphosa avicularia, 489.
2 3 blondii, 490.
3 3 javanensis, 490.
Thevatia neriifolia, 440, 447.
2 3 iccotli, 440.
Thevetin, 447.
Thiboumery, Properties of
morphine, 323.
Thompson, W., on copper in a water, 641.
on the solubility of
copper in oil, 638.
Thompson's experiments on animals with
oxalic acid, 536.
3 3 hair destroyer, 711.
Thorn apple, 379.
Thorne, L. T., and Jeffers, E. H., on the
purification of hydrochloric acid, 582.
Thorne's (L.T.) method of purifying zinc,
580.
Thorpe, T. E., on carbon monoxide from
bunsen burner, 69.
3 y
pseudo-
7 5
3 3 Estimation of CO, 76.
3 3 Lead in lead glaze, 622.
3 3 Method of estimating
arsenic, 592.
Thudichum on the elimination of lead,
633.
Thudichum on examination of urine in
carbolic acid poisoning,
191.
on the excretion of alcohol,
146.
on the excretion of sulphuric
acid, 95.
on the urine after taking
carbolic acid, 185.
Thuillier on the cause of ergot epidemics,
461.
Tidy, C. M., on a case of poisoning by
barium nitrate, 714.
5 5 on the composition of
arsenical violet powder,
562.
5 § Reaction with old blood-
stain, 64.
Tillner, E., on the detection of HCN long
after death, 220.
Tinctura veratri viridis, 406.
Tissot on ergot epidemics, 461.
Toad, The poisons of, 484.
Tobacco. See Nicotine.
Tobacco leaves, Composition of, 273, 274.
,, smoke, Composition of, 280.
, , poisoning, 279.
Toffana, 11.
Tollens, Karl, on fatal dose of tar acids,
179
Tolmatscheff on the poisonous action of
mercuric cyanide, 222.
Toluylenediamine, 40.
Tolylaminoaceto nitriles, 223.
Toulmouche, M., Poisoning by water
hemlock, 473.
Toxic action and chemical composition,
32–42.
Traube on the influence of digitalis on
the heart, 440.
Treatment in cases of poisoning, (App.)
717–733.
Treupel, Relation between toxicity and
condition of molecule, 35.
Triacetin, 37.
Trichlormorphine, 305.
Triethylamine, 513.
Triethylenediamine, 511.
Trigonocephalus contortus, 503.
Trimeresurus, 503.
Trimethylamine, 513.
Trimethyloxyammonium hydrochloride,
523.
Trional, 37, 171.
Triton cristatus, 484.
Tritopine, 286, 324.
Trochisci sodae bicarbonatis, 124.
Tropa-cocaine, 356.
Tropaeolin test for mineral acid, 105.
a-Truxilline, 356.
8-Truxillime, 356.
Tschirch on chronic poisoning by copper,
Oll copper oleate, 639.
2 3
49
77o
INDEX.
Tschirch on phyllocyanate of copper, 642.
,, on the toxic dose of copper, 646.
Tube-curare, 418.
Tubo-curarine, 418.
Tungstic acid test for morphine, 301.
Tunstall on a case of chronic alkali pois-
oning, 126.
Turbith, 666.
Turner's yellow, 619.
Turpentine, Elimination of, 140.
3 y Oil of, 139.
2 3 Poisonous effects of, 140.
3 3 Treatment in poisoning by,
(App.) 732.
Tutin, 469.
Typhotoxine, 529.
Tyrosin in phosphorus poisoning, 245.
Tyrotoxicon, 527.
UDRANSKY, L. W., and Baumann, B., on
the isolation of animal toxines, 510.
Uffelmann method of distinguishing be-
tween the acidity due to free and to
combined acids, 106.
Ulex europaeus, 398.
Ullmann on the elimination of mercury,
679.
Unguentum antimonii tartarati, 602.
plumbi acetatis, 618.
carbonatis, 618.
• 3 ,, iodidi, 618.
5 y veratrinae, 406.
Upas tree (Antiaris toxicaria), 445.
Uppmain's (J.) experiments on animals
with oxalic acid, 536.
Uranium, 710.
3 3 Detection and estimation of,
710.
Urechitoxin, 440, 449.
Urecthin, 440, 449.
Urine, Examination of, for sulphuric
acid, 94.
,, in phosphorus poisoning, 245.
Urobutylchloral acid, 168.
Urochloral acid, 168.
} }
x 3 3 3
WACUUM APPARATUS, 50.
Valentin, The poison of the scorpion, 486.
Valette's (Dr.) cases of arsenic poisoning,
551.
Wallance on the symptoms of poisoning
by cytisine, 400.
Van Kobell's test for bismuth, 655.
Wanadic acid test for morphine, 301.
Vapor conii, 270.
Vaughan on tyrotoxicon, 527.
Wauquelin's prussic acid, 203.
Was, F., on the composition of tobacco
smoke, 277.
Veal pie, Poisoning by, 530.
Wee on the extraction of physostigmine,
409.
,, on the fatal dose of physostigmine,
413.
Venetian poisoners, 9.
Venturoli on separation of HCN from
organic matters, 219.
Weratralbine, 402, 405.
Weratridine, 401, 402, 403. -
Weratrine, 250, 264, 265, 266, 401, 402.
j 3 Commercial effects on animals,
407
5 3 Effects on man, 407.
2 3 Fatal dose of, 407.
3 × Pharmaceutical
of, 406.
5 * Properties of, 406.
5 5 Separation from
matters, 408.
> 2 Spectrum of colour reactions,
preparations
organic
3 y Symptoms of poisoning by,
408
2 3 Tests for, 406.
3 3 Treatment in poisoning by,
(App.) 733.
Weratroidine, 402,405.
2 3 Spectrum of colour re-
actions, 58.
Weratrum—Used by Romans, 4.
5 3 alba, 401.
3 3 Sabadilla, 401.
2 3 viride, 401.
3 y Old knowledge of, 4.
Weratrums, The alkaloids of the, 401–409.
Verdigris, 644.
Vermin killers, 332.
Vermin paste, 226.
Veronal, 172.
Veryken on
matter, 52.
Vidali's test for chloroform, 161.
3 2 5 3 morphine, 301.
Vienna paste, 123.
Wietor, L., Action of sulphuric acid on
living animal tissues, 85.
Wigla on the mental effects of chloroform,
159.
Williers, H., and Favolle, M., Test for
hydrochloric acid, 105.
Williers' method for destroying organic
matter, 53.
Vinum antimoniale, 602.
Vinylamine, 41.
Violet powders, Composition of, 562.
Viper, The poison of the common, 504.
Viperidae, 498, 503.
Viperinae (vipers), 498.
Viperin, 504. -
Virchow on the post-mortem appearances
after phosphorus poisoning, 238.
Vitali, D., on arsenic in the urine, 577.
3 J. on the separation of digitoxin,
434. -
Vitali’s test for atropine, 382.
,, method of detecting cyanide of
mercury, 681.
Vivisection Act, 45.
destruction of organic
INDEX. 771
Vogel on the excretion of sulphuric acid,
95
Voisin and Liouville's experiments with
curare, 419.
Woit on the elimination of mercury, 679.
,, , , excretion of morphine, 313.
Volatile matter, Separation of, 49.
Von Furth, Epinephrin, 505.
Vossler, Fatal dose of picrotoxin, 467.
Wrewen, Distinction between hyoscya-
mine and atropine, 383.
Vulpino, The poison of the water sala-
mander, 484.
WACHHOLZ and Lemberger, Experi-
ments on CO, 75.
Wall, Dr. A. T., on the effects of cobra
poison on man, 501.
Waller, E., on the estimation of carbolic
acid, 191,
Walz’s digitaletin, 433.
Wanklyn on the estimation of carbon
monoxide, 76.
Ward's red pill, 604.
Warner on the fatal dose of strychnine,
335, 336.
Wartmann, Physiological
aconitine, 375.
Water gas, 68, 72.
Water hemlock, 473.
3 3 Post-mortem appearances
after poisoning by,
474.
Watt, J., on the effect of barium salts on
animals, 711. *
Weehuizen's (F.) test for HCN, 217.
Weil and Meihuizen, Action of digitalin
on frog's heart, 443.
Weiske's experiments with sulphuric
acid, 92.
Welbeck epidemic of food poisoning,
530.
Weldon process for preparing bleaching
powder, 77.
Wenzel’s ergotinine, 457.
3 3 echoline, 457.
Wernick on the action of ergot, 464.
Weyl, Isolation of tetanine, 525.
Whatley, J. C., on effects of sulphonal,
171,
Whitchurch cases of food poisoning, 530.
White lead, 619.
White oil, a limiment for horses, 117.
White, Prof., on the poisonous effects of
dinitro-benzol, 199.
White precipitate, 665, 677.
White vitriol, 687.
Whitelock, Dr., on poisoning by carbolic
acid lotion, 180.
Wigner, G. W., and Harland, R. H., on
the composition of commercial car-
bonate of lead, 618.
Williams' apparatus, 45.
effects of
Wilson, Margaret, The case of Reg. v.,
424.
Wilson, W. H., on the poison of the
scorpion, 486.
Wine, Lead poisoning from, 622.
Wissel on the composition of nux vomica,
330.
Witkowsky, Physiological
physostigmine, 411.
Wittmann, Purification of solamine, 397.
Wittstein on the solubility of strychnine,
327.
Wittstock on the separation of colchicine,
426.
Woehler and Siebold, on the destruction
of organic matter, 52.
Wöhler on amygdalin, 204.
,, on the elimination of potassic
chlorate, 132.
Wolckenhaar on an alkaloid like nico-
time, 283.
Wolffenstein on the scopolamines, 396.
Wollaston, Dr. C., Observations on ergot
poisoning, 462.
wºrhampton cases of food poisoning,
30.
Wood on the estimation of arsenic, 597.
Woodland on the amount of opium in
laudanum, 290.
Wormley on the solubility of strychnine,
327.
Woudreton, Confession of, 8.
Wright, A., and A. P. Luff, on the extrac
tion of veratrum alkaloids,
401.
$ 2 and A. P. Luff, onjervine and
pseudo-jervine, 404.
5 3. and A. P. Luff, on rubi-
jervine, 405.
Wright, W. H., on the poisonous effects
of katipo bite, 491.
Wumnenauer, Karl, on the electrolytic
estimation of bismuth, 657.
Wunderlich, C. A., on the appearance of
* intestine after nitric acid poisoning,
112.
Wynne, A. J., Cases of poisoning by
hydrocyanic acid, 213.
Wyss, Oscar, A case of sulphuric acid
poisoning, 90.
3 y on the liver in phosphorus
poisoning, 240.
3 3 on the urine in phosphorus
poisoning, 234.
3 J. on the urine in sulphuric
acid poisoning, 95.
effects of
XANTHALINE, 286.
Xanthine, 39, 40, 80.
Xanthogenic acid, 174.
YEW (Taxus baccata), 416.
Yung, M. E., on cephalopoda, 44.
772
INDEX,
ZALACKAS' (C.) antidote to nicotine, 283.
Zangrilli on tarantula poison, 490.
Zeisel on the constitution of colchicine,
422.
*; S., and Wittman, J., on solanine,
9
Zeisel's method for methoxyl groups,
263.
Ziegenbein, H., Experiments with digi-
toxin, 433.
Zinc, 686–693.
,, carbonate, 687.
,, chloride, 687, 690.
,, chromate, 688.
,, Detection of, in organic matter, 692.
,, Effects of, on animals, 689.
man, 689.
... Fatal dose of 689.
Zinc fever, 689.
,, green, 688.
,, in the arts, 688.
,, lactate, 688.
,, Museum specimens,
effects of, 691, 692.
,, oxide, 687.
,, sulphate, 687, 690.
,, sulphide, 687.
,, Pharmaceutical preparations
687.
,, Post-mortem appearances in pois-
oning by, 691.
,, purification from arsenic, 580.
,, Treatment in poisoning by, (App.)
733.
Zweifler on sulphates in newly - born
infants, 96.
illustrating
of,
ÜNJV. Or MickleAN,
JUL 21 1914
PRINTED BY NIEILL AND CO., LTD., EDINBURGH.

！，-- ~
|
3 9015 08:12226
|
|
2
<C
©
I
C
>
ll -
O
ūō
CC
Ll]
>
2
D
§<.
**…* {
... ~~~~
¿
« %. . ?
|
...--..."
a *.5:--
***
{..
§:
” . y^iț¢&
sº-ſ*:）*?
§§§） {
）;
}
*-ſłº ſº • .y
·&&
ș**
• ,º'，-。
};¿C$$$}\,\%|-ſae！
*: < .
± √° ‚Ä
&#}&{;;·№<№wºſº).ſº
¿º§§§· -→-→§§§§§· }- <sºŒ-~·
x· |-→Ç* ，- --'.' &&.¿?\\~# ¿ $¢,§ →;:----* * *，…，-
|-！ -ž， * .*---* …“_№_%·ſſs！！！ （…-3., - №- ~。 ... ~&x
******'）:',; -º. Șºſ: ¿::：:-: ſº, ººk*: ~~~.-ļģºſ* … ×::::：：:::
！**>:' …,.，:--... • • • •·*** ģ,ī£}}¿_%）·§-ſº
-* · · · ·łº§<！--¿?
*** ** ***
*

ſae
§;§§
§§
§
§:ſsä，
¿
§§
§§
¿