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H A N D B O O K
OF
MO DE R N C H E MIS T R Y
INO R GANIC AND ORGANIC.
for the use of students.
in
& ſº
* e
RY ſº • * * * *
* & He
* 6. :
tº §
* i.
CHARLES MEYMOTT TIDY, M.B., F.C.S.,
Professor of Chemistry & of Medical Jurisprudence & Public Health at the London Hospital;
Medical Officer of Health for Islington;
Late Deputy Medical Officer of Health & Public Analyst for the City of London :
Master of Surgery, &c., &c., &c.
L O N D O N :
J. & A. CHURCHILL, NEW BURLINGTON STREET.
sºmeº

1878.
LONDON :
PRINTED BY WERTHEIMER, LEA AND Co.,
C1RCUS PLACE.
r-
>
s
§
i
;
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s
:
TO
HENRY CLIFTON SORBY, F.R.S.,
President of the Geological Society, &c., &c.
48, QUEEN ANNE STREET,
CAVENDISH SQUARE, W.
April, 1878.
MY DEAR MR. So RBY,
Our long friendship would of itself be sufficient reason for
my desiring to dedicate this work to you.
The high position you have attained in the scientific world adds,
however, a deep sense of pride to my feeling of pleasure in seeing
your name upon its opening page. Most truly do I wish that those
who study its contents may find some slight reflection of that re-
markable accuracy of thought and work, of which all that you
have done and written affords so brilliant an example.
Believe me,
My dear Mr. So RBY,
Ever sincerely yours,
C, MEYMOTT TIDY.
2936.24
PREFA CE.
WHEN an author writes a new book on a subject upon which
so many good books have been already written, he is expected
to give some reason for doing so.
I venture, therefore, to plead my apology for the publication of
these outlines of Chemistry. Within three months of graduat-
ing—in other words, when “fresh from the schools”—I was ap-
pointed Joint Lecturer on Chemistry with the late Dr. Letheby,
at the London Hospital. Consequently, my first lecture-notes
were prepared when familiar by practical experience with the
wants of a student. Year by year, these notes have been added
to, and, to some extent, re-written; nevertheless, except in a few
instances, I have strictly adhered to the general plan I first
adopted. I submit these lecture-notes to the profession as the
joint experience of a student and a teacher.
In the first section of this work, I have considered the chem-
istry of the non-metals; in the second, the chemistry of the
metals; and, in the third, the chemistry of organic bodies.
Before proceeding to details, I have in each case general-
ized largely on the subject matter of the section. Thus, as in-
troductory to the science of chemistry generally, and before
describing the metalloids, I have discussed at some length the
subject of chemical affinity. In a similar manner, I have general-
ized on the metals and on the chemistry of organic bodies, before
proceeding to the consideration of the several elements or com-
pounds comprehended under the sections. Nothing to my mind
is more important than for teachers and students to grasp the
notion that the lecture-room is not the same as the study—in
other words, that the lecture will not take the place of the book,
vi PREFACE.
any more than the book can take the place of the lecture. Each
has its own special work in education. Thus it appears to me
that in the lecture-room the work of the teacher is best fulfilled
by sketching accurately, yet broadly, the general outlines of the
whole subject, intensifying them where necessary by illustration
and experiment (in fact, so to speak, covering the canvas), leav-
ing the student, in the quiet book-work of the study, to fill in
the minute details for himself. With this view of the different
functions of lectures and books, I have always adopted in the
lecture theatre the system of broad generalization, such as I have
briefly shadowed forth in the remarks introductory to the several
sections. I hope these may prove of general use as an introduc-
tion to the detailed work that follows, but they are mainly
intended as a guide to my own pupils at lecture.
Thus much for introductory generalization.
As regards the details, my aim has been to be methodical. I
have therefore considered each element, and, as far as possible,
each compound, under the several heads of (1.) History, (2)
Natural History, (3) Preparation, (4.) Properties, (a.) Sensible,
(3) Physical, and (y.) Chemical ; (5.) Uses in Medicine and in
the Arts and Manufactures, and (6.) Tests.
In dealing with the metalloids I have commenced with
oxygen and finished with hydrogen, discussing under each
element the compounds it forms with the elements previously
considered in detail. Thus, for example, under hydrogen (the
last of the metalloids), I have described all the compounds that
it forms with the non-metals.
From page 437 to page 462 will be found the tables I am in
the habit of employing in my practical chemistry class. Before
considering the course to be adopted in the separation of the
several groups, I have always insisted on the necessity of an
accurate knowledge, not only of the reactions of each member of
the group, but more particularly of the relationship between the
reactions of the several members of the group with the same
reagent. This I have attempted to set forth in a series of Tables.
In respect of order (regarding classification as simply a question
of convenience), I prefer beginning my practical course of lectures
with the alkaline metals and working backwards.
PREFACE. vii
The reactions of the rarer metals are not included in the
analytical tables, but they will be found in the body of the work
under their several headings.
Bearing in mind the requirements of students preparing for
examinations, I have described the reactions of organic bodies at
the end of the several chapters devoted to their study. Thus
the reactions of cyanogen compounds will be found on page 522;
of the alcohols (together with the starches and sugars) on page
589; of the organic acids on page 626; and of the alkaloids on
page 674.
As regards notation, although I recognise great advantages
in that suggested by Dr. Frankland, I am by no means prepared
to abandon the old formulae. Under these circumstances I have,
in the inorganic portion of the work, stated equations in both
molecular and constitutional formulae.
In the case of each metal I have drawn up a table of its most
important compounds, their formulae, and such tabulated in-
formation respecting them as I thought would prove useful to
the student.
My first object in this book is that it should serve as a manual
for students. As a medical man and a professor in a medical
school, I have always made a special point in my lectures of
noting the bearing of chemical science on medicine. This will
account to the general student of chemistry for my dealing
with certain subjects in a greater detail than is usual in similar
works.
Further, bearing in mind the special knowledge required of
medical officers of health in dealing with nuisances arising from
various trade operations, I have given the outlines (limited of
course to the strictly scientific details) of most manufacturing
processes, and of the chemical reactions involved in the same.
To cure a nuisance is more scientific than to annihilate a manu-
factory, and to suggest the cure we must accurately understand
the case.
To the lecture-notes of Dr. Frankland and to the manuals of
Chemistry of Odling, Williamson, Roscoe, Bloxam, Thorpe, Miller,
and Fownes, and particularly to the excellent manual on Organic
Chemistry by Dr. Armstrong, I desire to express my obligations,
viii . - PREFACE.
I should wish to add that, although I have spared no pains to
render this Handbook as complete and as accurate as possible,
nevertheless I trust that some allowance will be made for un-
avoidable errors arising from the circumstance that it has been
written amidst the constant interruptions of professional work.
Not unfrequently indeed has it had for a time to be laid aside
altogether, thereby rendering continuity of thought and uni-
formity of treatment a matter of some difficulty.
48, QUEEN ANNE STREET,
CAVENDISH SQUARE.
April, 1878.
() () NT ENTS,
CELAPTER I.
CHEMICAL AFFINITY: Definition—Conditions necessary for its exertion—Phe-
nomena—The circumstances influencing its action—The means of estimat-
ing the energy of the force
CHAPTER II.
Nomenclature—Chemical Symbols and Formulae — Combining Proportions—
Atoms—Molecules—Atomic and Molecular Combination—Compound Radi-
cals—Volume—Standard Pressure and Temperature—Relative Weight—
The Crith—Relation between Atomic Weights and Specific Gravity—Re-
lation between Atomic Weight and Specific Heat—Atomicity and Quanti-
valence—Chemical Formulae—Substitution—Isomerism—Isomorphism—
Allotropism—The Metric System
SECTION I.--THE METALLOIDS.
CHAPTER III.
Oxygen : Synonyms—History—Natural History — Preparation—Properties.
OzoNE: History—Natural History — Preparation — Properties—Tests —
Quantitative Determination—Uses of Oxygen—Respiration--Combustion. .
CHAPTER IV.
The Halogens or Haloid Elements : FLUORINE. CHLoRINE : Compounds of
Chlorine and Oxygen – Hypochlorous anhydride — Hypochlorous acid—
Chlorous anhydride—Chlorous acid—Chloric peroxide—Chloric acid—Per-
chloric acid. BROMINE : Compounds of Bromine with Oxygen and Chlo-
rine. IoDINE : Compounds of Iodine and Oxygen–Iodic acid—Periodic
acid—Compounds of Iodine and Chlorine—Generalization on the Halogens
CHAPTER W.
NITRogeN: Atmospheric Air—Its Constituents—Compounds of Nitrogen and
Oxygen--Nitrous oxide—Hyponitrous acid—Nitric oxide–Nitrous anhy-
dride–Nitrous acid—Nitric peroxide—Nitric anhydride—Nitric acid—Com-
pounds of Nitrogen and the Haloids—Compounds of Nitrogen with Oxygen
and the Haloids
PAGE
X CONTENTS.
CHAPTER WI.
PHosphorus: Compounds of Phosphorus and Oxygen–Suboxide of Phosphorus
—Hypophosphorous acid—Phosphorous anhydride—Phosphorous acid—
Phosphoric anhydride–Metaphosphoric acid—Pyrophosphoric acid—Ortho-
phosphoric acid—Compounds of Phosphorus and the Haloids—Phosphorous
chloride – Phosphoric chloride – Phosphoric oxy-trichloride— Phosphoric
Sulpho-trichloride—The Iodides of Phosphorus–Phospham—Action of Am-
monia on Phosphorus compounds • * . . . . * * - - g
CHAPTER WII.
SULPHUR: Compounds of Sulphur with Oxygen and Hydroxyl—Sulphurous
anhydride and acid—Sulphuric anhydride and acid—Hyposulphurous acid—
Thiosulphuric acid—Dithionic acid—Trithionic acid—Tetrathionic acid—
Pentathionic acid—Compounds of Sulphur and Chlorine—Compounds of
Sulphur, Oxygen, and the Haloids—Compounds of Sulphur and Phospho-
rus. SELENIUM : Compounds of Selenium and Oxygen. TELLURIUM :
Compounds of Tellurium and Oxygen .
CEIAPTER VIII.
CARBON : Compounds of Carbon and Oxygen–Compounds of Carbon and the
Haloids—Compounds of Carbon with Oxygen and the Haloids—Compounds
of Carbon and Sulphur. Boron : Boracic acid –Compounds of Boron with
Nitrogen, the Haloids, and Sulphur. SILICON: Compounds of Silicon with
Oxygen, the Haloids, Nitrogen, and Sulphur . *
CHAPTER IX.
HYDRogEN: Compounds of Hydrogen and Oxygen—Water—Compounds of
Hydrogen with the Haloids, with Nitrogen, with Phosphorus, with Sulphur
and Selenium—Compounds with Carbon, viz., Methane, Ethylene and
Acetylene—Flame—Compound of Hydrogen and Silicon
SECTION II.—THE METALS.
CEIAPTER X.
GENERAL REMARKs on THE METALs : Derivation and Definition of a Metal—
Order of Discovery—Natural History—Physical and Sensible Properties—
Chemical Properties—The Oxides—Classification of the Metals º
CHAPTER XI,
ALLoys AND SALTs: Alloys—Changes in property effected by Alloying-Acids—
Bases—Salts. Haloid Salts—Chlorides, Bromides, Iodides, Fluorides,
Sulphides, Selenides, Phosphides, Carbides, Borides, Silicides. Ory-salts,
Sulphates, Selenates, Chromates, Manganates, Tungstates, Molybdates,
Tellurates, Hyposulphates, Thiosulphates, Sulphites, Hyposulphates,
Nitrates, Nitrites, Hyponitrites, Chlorates, Bromates, Iodates, Perchlorates,
Periodates, Chlorites, Hypochlorites, Phosphates, Hypophosphites, Phos-
phites, Arsenates, Antimonates, Arsenites, Carbonates, Silicates, Borates.
Double Salts
PAGE
122
143
J 66
191
236
CONTENTS.
CHAPTER XII.
Group VI. : The Alkaline Metals : PotAssIUM-SoDIUM-LITHIUM-CAESIUM-
RUBIDIUM-AMMONIUM .
CHAPTER XIII.
Group V. : The Metals of the Alkaline Earths : BARIUM and its Compounds—
STRONTIUM and its Compounds—CALCIUM and its Compounds—MAGNESIUM
and its Compounds
CHAPTER XIV.
The Metals of Group IV. : MANGANESE and its Compounds—ZINC and its Com-
pounds — CoEALT and its Compounds —NICKEL and its Compounds —
URANIUM and its Compounds—INDIUM and its Compounds ..
CEIAPTER XW.
Group III. : The Metals of the Earths : ALUMINIUM-GLUCINUM-YTTRIUM-
ERBIUM–CERIUM-LANTHANUM-DIDYMIUM-THORINUM –ZIRCONIUM.
IRON and its Compounds—CHROMIUM and its Cornpounds
CHAPTER XVI.
The Metals of Group II. : A.— Metals whose Sulphides are Insoluble in the Alkaline
Sulphides. CoPPER and its Compounds–BISMUTH and its Compounds—
CADMIUM-Compounds with Oxygen, with the Haloids, and with Sulphur–
PALLADIUM and its Compounds—RHODIUM and its Compounds—OSMIUM
and its Compounds—RUTHENIUM and its Compounds.
B.—Metals whose Sulphides are Soluble in the Alkaline Sulphides. TIN
and its Compounds—ANTIMONY and its Compounds—ARSENIC and its Com-
pounds—GoLD and its Compounds–PLATINUM and its Compounds—Bases
produced by the action of Ammonia on the Chlorides of Platinum—MoLYB-
DENUM and its Compounds
CHAPTER XVII.
The Metals of Group I. : LEAD and its Compounds—SILVER and its Compounds—
MERCURY and its Compounds—THALLIUM and its Compounds—TUNGSTEN
and its Compounds - - s tº - - - - tº e - - - -
Supplement to the Metals. GALLIUM (omitted from p. 347)—IRIDIUM
(omitted from p. 409) . . - - tº tº - - tº e
CHAPTER XVIII.
Notes for Practical Analysis . .
SECTION III.—ORGANIC CHEMISTRY.
CHAPTER XIX.
Organic Compounds and Organised Bodies—Definition of Organic Chemistry—
ORGANIC ANALYSIs—Ultimate Analysis—Vapor Density—Method of deter-
mining Vapor Densities — Proximate Analysis Q tº
PAGE
288
314
339
364
4 10
434
437
463
xii CONTENTS.
CHAPTER XX.
The Natural and Artificial Changes of Organic Bodies : A.—Natural : FERMEN-
TATION.—Warieties—I. Alcoholic—II. Lactic–III. Butyric—IV. Mucous—
W. Acetous–Conditions necessary for Fermentation— Circumstances in-
fluencing Fermentation—Theories to account for it—Practical applications.
PUTREFACTION.—Disinfectants. EREMACAUSIs.
B.—Artifical : Action of Heat—Action of Acids—Action of Alkalies—
Action of Haloid Elements—Action of Nascent Oxygen and Hydrogen—
and of other Reagents—Action of Light and Electricity & ©
CHAPTER XXI.
CYANOGEN: Hydrocyanic Acid–Cyanides—Compounds of Cyanogen with the
Haloids and with Hydroxyl—Sulphocyanic Acid—Double Cyanogen Salts
—The Nitroprussides—Prussian Blue—Reactions of Cyanogen Compounds
CHAPTER XXII.
THE HYDROCARBONs: Series of Hydrocarbons : The Paraffins—Chloroform—
The Olefines—Acetylene—Turpenes—Benzenes—Naphthalene—Anthracene
—Formation of Alizarin.
Supplement : Paraffin and Petroleum—Turpentine—Wolatile Oils—
Camphors—Resins—Gum Resins—Oleo-Resins—Balsams—India Rubber—
Gutta Percha
CHAPTER XXIII.
THE ALcohols: Relation of the Alcohols to other Bodies—Series of Alcohols—
General preparation and properties of the members of the various Series—
Mercaptans.
Supplementary Chapter : Sugar—Glucosides—Starches—Gums—Reac-
tions of various Alcohols and allied Bodies - * - - - -
CEIAPTER XXIV.
THE ORGANIC ACIDs: Relationship to other bodies. Monobasic Acids: Acetic
—Acrylic—Sorbic—Benzoic—Cinnamic—Naphtoic. Dibasic Acids : Suc-
cinic – Fumaric — Phthalic. Tribasic Acids : Tricarballylic – Mesitic.
Reactions of the acids.
Supplementary Chapter : Fats and Oils—Soaps—Candles—The Tan-
nins—Ink—Tanning - e. - is - e. tº tº - *
CHAPTER XXV.
THE ETHERs: Oxy-Ethers—Ethers of Monohydric Alcohols—Preparation—
Ethers of Di- and Trihydric Alcohols. Sulpho-Ethers. Haloid Ethers
CHAPTER XXVI.
THE ALDEHYDEs (Alcohol Dehydrogenatum); Constitution—Preparation— Re-
actions—Aldehydes of the Acetic Series—Formic Aldehyde–Aldehydes of
the Acrylic and Benzoic Series—Other Aldehydes º tº b - -
FAGE.
483
508
5
5
7
638
CONTENTS.
xiii
CHAPTER XXVII.
THE KEToNEs: Constitution—General Preparation—Properties and Reactions
CEIAPTER XXVIII.
THE ALKALOIDs: The Natural Alkaloids, Vegetable and Animal—Constitution
of the Alkaloids—The Amines (Aniline)—Phosphines—Arsines–Stibines
—Bismuthines—Kakodyl—Organo-Boron and Organo-Silicon Compounds
—Organo-Metallic Compounds—Amides—Imides—Alkalamides—Nitriles—
Tests
CHAPTER XXIX.
CoLoRING MATTERs: Natural History—General Preparation and Properties—
Yellows—Reds—Blues—Browns—Blacks.
Supplementary Chapter : Dyeing and Calico Printing . .
CHAPTER XXX.
VEGETABLE CHEMISTRY : Tissues of Vegetable—Cellulin—Vegetable Parchment
—Gun Cotton—Woody and Corky Tissue—The Life of a Plant
CHAPTER XXXI.
ANIMAL CHEMISTRY : Albuminoids.-I. Animal Solids—II. Nutrient Fluids—
III. Digestion, and the Fluids concerned in it—IV. Excrementitious Pro-
ducts
646
648
683
688
APPENDIX.
IIQUEFACTION OF Oxy GEN, etc.
MENDELEEFF's LAW of PERIODICITY
TABLEs . . - - * to - - * * & © e - tº e a $ 726–736
* -
723
723
TABLE OF THE ELEMENTS,
NoTE.—1. The page after the Elements refers to the page in the book where the Element is described.
2. The Metalloids are printed in Black type, and the Metals in Roman type.
3 : tº
Specific | Specific f Mel Boil 15 # =
-- * Relative Gravity of Gravity o elting oiling .5; ; e
Element, Symbol. Atºmic Atomicity. Weight | Gas %. Solids † Point. Point. | .3 - B Discoverer and
Weight. gº tº © o 3 3.5 Date of Discovery.
b H = 1. Vapor Liquids F. F. F 3 -º
Air = 1. Water = 1. 3 & .#
C cº- *
r—t O 2*
Aluminium (p. 339) . . . . Al 27.5 IV. 2.6 842 - 0 Wöhler, 1828.
Antimony (Stibium) (p. 388) Sb 122- 0 III., W. 6-7 806 - 0 Basil Walentine.
Arsenicum (p. 394) . . . . As 75' 0 III., W. 150 10' 6 5'90 Wolatilizes 329:13. Brandt, 1733.
before fusing
at 356.
Barium (p. 314) , . Ba. 137-0 II. 4 - 0 Below.redheat Davy, 1808.
Bismuth (p. 372). , Bi 210-0 III., W. 9.83 507-2
Boron (p. 183) . . B 11 - 0 III. 2.68 Davy, 1807.
Bromine (p. 83) Br 80 - 0 I. 80 - 0 5-54 3. 187 —4 145.4 Balard, 1826.
Cadmium (p. 376) Col 112'0 II. 56' 0 3-94 8 : 604 442 1580 | 122-33 Stromeyer, 1818.
Caesium (p. 309) . . Cs 133-0 I. Bunsen and Kirch-
hoff, 1860.
Calcium (p. 317) .. Ca 40' 0 II. 1:578 Red heat. Davy, 1808.
Carbon (p. 166). . C 12' 0 (II.) IV. 3- 5 Pre-historic.
Cerium (p. 346) .. Ce 92.0 II.
Chlorine (p. 70) Cl 35' 5 I. 35' 5 2.47 1 : 33 76.3 Scheele, 1774.
Chromium (p. 357) . . Cr 52-5 (II., Iv.) WI. 7:01 Vauquelin, 1797.
Cobalt (p. 333) . . . . . . Co 58-8 II. (Iv.) WI. 8-95 Brandt, 1733.
Copper (Cuprum) (p. 364) . . Cu (33.5 II. 8-96 1996 - 0 Pre-historic.
Didymium (p. 347) .. Di 96.0 II.
Erbium (p. 346) . . E 112.6 II.
Fluorine (p. 69) F 19-0 I. 1-318 (?) 40.87 (?) Davy, 1808. -
Gallium (p. 434) . . . . . . . . Ga 69 - 9 IV. 6'935 86-27 Boisbaudran, 1875,
Glucinum (Beryllium) (p. 346) .. G. 9.5 II. | 2. I
Gold (Aurum) (p. 400) tº º Au 196-7 (I.) III. 19-4 219.2-0 Pre-historic.
Hydrogen (p. 191) . , BI I - 0 I. 1-0 || 0-0693 2: 1496 || Cavendish, 1766.
Indium (p. 337) . . . . In 113-4 III. 7.4 Reich and Richter,
1863.
Iodine (p.86) . . . . I 127-0 I. 127.0 8:716 4:947 225' 0 347.0 270:32 Courtois, 1812.
Iridium (p. 435) . . . . Ir 198-0 | II., IV., VI. i 21 - 15 Smithson Tennant.
Iron (Ferrum) (p. 347) Fe 56.0 II., IV. (VI.) 7.79 Pre-historic,

Lanthanum (p. 347) . . .
Lead (Plumbum) (p. 410) . .
Lithium (p. 308) . . . .
Magnesium (p. 322)
Manganese (p. 326) . . . . . .
Mercury (Hydrargyrum) (p. 421)
Molybdenum (p. 408) . . . . . .
Nickel (p. 335)
Niobium tº # * *
Nitrogen (p. 93)
Osmium (p. 380) ..
Oxygen (p. 54) . .
Palladium (p. 377) . .
Phosphorus (p. 122)
Platinum (p. 403) g is is a
Potassium (Kalium) (p. 289)
Rhodium (p. 379). .
Rubidium (p. 30.9)
Ruthenium (p. 381) . .
Selenium (p. 162) . .
Silicon (p. 185). . . .
Silver (Argentum) (p. 416)
Sodium (Natrum) (p. 297) . .
Strontium (p. 316) . . &
Sulphur (p. 143)
* &
s ſº
Tantalum . . . .
Tellurium (p. 164)
Thallium (p. 430)
is ſº
tº ſº
Thorinum (or Thorium) (p. 347)
Tin (Stannum) (p. 383) . . . .
Titanium (p. 361) . . . .
Tungsten (Wolfram) (p. 432)
ljranium (p. 336). . . . . .
Wanadium . . . .
Yttrium (p. 346) ..
Zinc (p. 330)
Zirconium (p. 347)
2
.
2
.
h
º
31 - 0
1974
39 . ()
104 - 3
85 - 4
104.4
79.5
28' 5
108-0
23-0
87.6
32-0
J 82.0
128.0
204 - 0
231 - 5
118'' ()
60° 0
184 - 0
240° 0
51 3
61.7
65. ()
89.5
II. (Iv.)
I.
II.
II., IV. (VI.)
II.
II., IW., WI.
II., IV., VI.
V
I., Iii., v.
II., IV., VI.
II
II, iv.
III., W.
(II.), IV.
I.
III., WI.
I.
II., IV., VI.
II., IV., WI.
IV.
I.
I.
II.
II., IV., VI.
IV.
II., IV., VI.
III.
• ?
II., IV.
II., IV.
II., IV.
IV., VI.
II., IV., VI.
V.
II.
II.
IV.
100'0
7
9
5
32.5
0-9713
1 - 1056
4 - 290
2-222
at 1040° C.
9. ()
11:445
0. 59.3
1 743
6'85
13:56
8-9
617-0
356. ()
Red heat.
37.9
773-0
Infusible.
6.75- 0
554
Low red
heat.
Below
white
heat.
1,904
216'09
30. 137
34-27
133: 23
176' 08
68.76
279:0
Mosander, 1841,
Pre-historic.
Davy.
Davy, 1808.
Gahn, 1780.
Pre-historic.
Cronstedt, 1751.
Chapta), 1789.
Tennant, 1803.
Priestley, 1774.
Wollaston, 1803
IBrandt, 1669.
Wood, 1741.
Davy, 1807.
Wollaston, 1803.
Bunsen and Kirch-
hoff, 1860.
Claus, 1846.
Berzelius, 1817.
Davy, 1807.
Pre-historic.
Davy, 1807.
Davy, 1808.
Pre-historic.
Müller, 1782.
Crookes, 1861.
Berzelius, 1829.
Pre-historic.
Gregor, 1891.
Rlaproth.
In 13th Century.
A.
HANDBOOK OF MODERN CHEMISTRY,
CHAPTER I.
CFIEMICAL AFFINITY.
Definition—Conditions necessary for its exertion—Phenomena—The circumstances
influencing its action—The means of estimating the energy of the force,
AFFINITY may be defined as ‘a force of attraction acting between two
or more dissimilar particles brought together at an inappreciable distance,
whereby a new compound is formed, having properties different from
those of its constituents.” Thus, if we effect a chemical combination
between Iodine (a black, poisonous substance) and Potassium (a silvery
white metal) we obtain a compound (Potassic Iodide) which bears no
resemblance sensibly, chemically, physically, or physiologically to
either of its constituent elements. This change of property is the
special characteristic of Chemism or Chemical Affinity. In gravita-
tion we have attraction between similar or dissinnilar molecules, at an
appreciable distance; in cohesion, attraction between similar molecules
at an inappreciable distance; in adhesion, attraction between dis-
similar molecules at an inappreciable distance; but in none of these
attractive forces have we any change in the matter on which the
force is exerted.
The chemical force has been designated by different names: Berg-
man called it “Elective Gravitation ;” Azais “Molecular Gravitation;”
Newton “Chemical Attraction or Action ;” others “Heterogeneous
Affinity;” whilst Stahl invented the name “Chemical Affinity” or
simply “Affinity,” with the idea that bodies that combined chemically
had some common resemblance. (“Like consorts with like.”—Hip-
pocrates.) In employing the term Affinity as a name for the force,
we do not accept the grounds upon which it was originally adopte l;
for, chemically, like does not consort with like, but, par excellence,
with unlike; bodies the most opposite, as, for example, acids and
alkalies, being invariably the most disposed to combine.
l}
2 PIANDBOOK OF MOIDERN CHEMISTRY.
I. The Conditions necessary for the Exertion of Affinity.
(a.) There must be two or more dissimilar particles.—There can be no
chemical union between iron and iron, or between sulphur and
sulphur, but iron and sulphur are capable of chemical combination.
Further, the more completely the substances are chemically unlike,
the more intense usually is the play of affinity. The constituents of
most chemical compounds, when subjected to an electric current, pass
to opposite poles—those attracted to the positive pole of the battery
being termed electro-negative elements, and those attracted to the negative
pole, electro-positive elements. Two positive or two negative elements
may, and under some circumstances do, combine, but the chemical
phenomena resulting from such combinations are usually so slight,
that at times it is difficult to say whether such compounds are not
purely molecular or mechanical.
In affinity, moreover, we note a certain elective power. If, e.g.,
hydrochloric acid be poured on lime and alumina, upon both of
which it is capable of acting, we find that the acid acts by preference
on the lime (“Elective Affinity” of Bergman).
(3.) The particles concerned must be brought into absolute contact.—This
may be effected by various agencies, such as heat, Solution, or me-
chanical action.
II.-The Phenomena of Affinity.
All the phenomena of affinity are indicative of change. In a
mechanical mixture the constituents are not changed, and consequently
the nature of the compound is a mixture of the natures of the con-
stituents. In a chemical micture the properties of the compound may
bear no resemblance whatsoever to the properties of the constituents
of which it is composed. Thus we notice, as the results of affinity,
changes in the sensible, the physiological, the physical, and the chemical
properties of bodies.
(A.) CHANGES IN THE SENSIBLE PROPERTIES.
(a.) Color. This may be—
(1.) Produced; (Example) Solutions of potassic iodide and
plumbic acetate (both of which are colorless)
produce, when mixed, the yellow plumbic
iodide.
(2.) Altered; (Example) The action of an acid on litmus, or of
an alkali on turmeric.
(3.) Destroyed; (Example) Action of chlorine on indigo.
THE PHENOMENA OF AFFINITY 3
(6.) Odor. This may be—
(1.) Produced; (Example) Sulphuretted hydrogen, a compound
of sulphur and hydrogen.
(2.) Altered; (Example) Nitro-benzene formed by the action
of nitric acid on benzene.
(3.) Destroyed; (Example) Action of chlorine on Sulphuretted
hydrogen.
(y.) Taste : This may be—
(1.) Produced; (Example) Nitrogen and hydrogen form
ammonia.
(2.) Altered; (Example) Chlorine and sodium form common
salt.
(3) Destroyed; (Example) Baric oxide and sulphuric acid
form the tasteless baric sulphate.
(B.) CHANGES IN THE PHYSIOLOGICAL PROPERTIES.
(a.) IIarmless bodies become active—
Example (1.) Strychnia, a deadly poison, is formed by the
combination of the harmless bodies, carbon,
hydrogen, oxygen and nitrogen.
(2.) Sulphuric acid, a corrosive poison, is formed
by the combination of the inert bodies,
sulphur, hydrogen, and oxygen.
(3.) Active bodies become inert.—This is the principle of antidotes;
sulphuric acid is a poison, but if this be combined with calcic hydrate,
the inert body calcic sulphate is formed.
(C.) CHANGES IN THE PHYSICAL PROPERTIES.
(a.) Aggregation—
(1.) Solids become liquids; (Example) Sulphur and carbon form
carbonic disulphide CS2.
(2.) Solids become gases ; (Example) Gunpowder when heated
produces a gas.
(3.) Tiquids become solids; (Example) Solid carbon is set free
by the action of sulphuric acid on strong syrup.
(4.) Liquids become gases; (Example) Effervescence.
(5.) Gases become solids; (Example) Ammonia gas and hydro-
chloric acid gas form solid ammonic chloride.
(6.) Gases become liquids; (Example) Hydrogen and oxygen
form water, OH.g.
(6.) Density.—The density of bodies is usually increased by affinity.
If I volume of alcohol (Sp. Gr. 0-796) be mixed with 1 volume of
water (Sp. Gr. 1-0) a liquid is produced having a Sp. Gr. of 0-917,
whereas the mean Sp. Gr, would be 0.898.
4 - FIANIDROOR OF MODERN CHEMISTRY.
Various other properties are also changed along with density, such
as the hardness of a body, its sonorousness, etc.
(y.) Changes in the thermotic properties of bodies.
(i.) Temperature.—Heat is usually if not always produced as the
result of affinity. The heat evolved may be very slight, as when an
alkaline sulphate is added to baric nitrate; whilst it may result in com-
bustion, where the evolution of light and intense heat are accompany-
ing phenomena. Cases where cold apparently results from chemical
combination are exceptional, and are always more or less accompanied
by the phenomena of fluidity, the heat required to effect the change
of the solid to a liquid being in excess of the heat produced.
(ii.) Fusibility.—With few exceptions the chemical compound is
more fusible than the mean fusibility of the constituents.
(1.) Fusibility increased.—A mixture of 1 part of lead, 1 of tin, and
2 of bismuth, melts at 167° F. (75° C.), whereas the mean melting
point of the constituents would be 512°F. (267°C.).
(2.) Fusibility diminished.—Such cases are rare. The metallic sul-
phides supply us, however, with illustrations.
(iii.) Volatility.—This may be increased or diminished ;-
(1.) Volatility increased.—When carbon (a non-volatile body) is
combined with sulphur, which is volatile at 600° F (316° C.), car-
bonic disulphide (CSz) is formed, which is a liquid that has never
been frozen, is volatile at ordinary temperatures, and boils at 111° F.
(44° C.).
(2.) Volatility diminished.—Water boils at 212° F (100° C.). In
some chemical compounds, however, it is absolutely non-volatile.
So again the electrical states and the crystalline forms of bodies are
altered by the action of affinity.
III.—Circumstances Influencing Chemical Affinity.
Inasmuch as affinity depends on molecular attraction, it follows
that whatever tends, on the one hand, to bring the particles together,
or, on the other hand, to separate them, must influence the action of
the force; in the former case aiding, and in the latter case pre-
venting it.
1. GRAVITATION MODIFIES CHEMICAL ACTION.
Gravity affects affinity by the disposition of the heavier particles to
sink, and of the lighter particles to rise to the surface.
2. CoHESION MoDIFIES CHEMICAL ACTION.
Affinity being a molecular force, it follows that it will be favoured
by any means that lessen cohesion, such as mechanical division
(powdering), heat (fluidity), or solution. Cohesion may for a time
overrule affinity, affinity coming into play immediately the cohesion
is broken down. The action of cohesion in influencing the force
may be either exerted upon the constituents or upon the resultant.
CIRCUMSTANCES INFLUENCING CHEMICAL AFFINITY. 5
(a.) Cohesion of the Constituents.—A lump of lead is very slowly
acted upon when exposed to the air, but if it be in a finely powdered
state (pyrophoric) it instantly ignites. If finely powdered antimony be
introduced into chlorine it takes fire, but this intense chemical action
does not occur when a lump of the metal is placed in the gas.
(3) Cohesion of the Resultant.—When sulphuric acid is added to a
baric nitrate solution, baric sulphate is precipitated. The sulphuric
acid thus removes the barium out of the sphere of chemical action,
by reason of the superior cohesion of the resultant. This action is
often attributed to what is called superior affinity, but there are diffi.
culties in admitting this as an explanation in such cases, owing to the
capricious action of the force. For example, if acetic acid be added
to a solution of potassic carbonate in water, carbonic anhydride escapes,
and potassic acetate is formed; but if carbonic anhydride be passed
through a solution of potassic acetate in spirit, acetic acid is set free
and potassic carbonate is formed, which, being insoluble in the spirit,
is precipitated.
We may here consider—
(A.) The action of acids on salts in Solution.
(a.) If an acid be added to a solution of a salt, such acid being of
nearly equal chemical power to the acid of the salt, and with the base
of which salt it can unite to form a soluble compound, the probability
is that the base will be divided between the two acids, equally or un-
equally, both acids being also present in solution in the free state.
Example: Sulphuric acid + potassic nitrate = potassic sulphate + potassic nitrate +
sulphuric acid + nitric acid.
(b.) If an acid be added to a solution of a salt, such acid being of
much greater chemical activity than the acid of the salt, but with the
base of which salt it can unite to form a soluble compound, the strong
acid will then appropriate the whole of the base, and set free the
whole of the acid originally combined with the salt.
Example: Sulphuric acid + sodic biborate = sodic sulphate + boric acid.
(c.) If an acid be added to a solution of a salt, aqueous or other-
Wise, it being immaterial whether the acid so added be of greater or
of less chemical power than the acid present in the salt, but with the
base of which salt it is capable of forming a precipitate insoluble in
the menstruum in which the salt is dissolved; the acid added will
appropriate the whole of the base, and set free the original acid.
lºxamples (l) Sulphuric acid + baric nitrate = baric sulphate + nitric acid.
(2) IIydrocyanic acid + argentic nitrate = argentic cyanide + nitric acid.
* }
(3) Tartaric acid + argentic sulphate = argentic tartrate + sulphuric acid.
(d.) If to a solution of a salt, the acid of which is insoluble in the
menstruum in which the salt is dissolved, an acid be added which
forms with the base of the salt a soluble salt, the acid added will then
6 HANDBOOK OF MODERN CHEMISTRY.
combine with the whole of the base, whilst the acid previously in
combination with it will be precipitated. -
Example: Nitric acid + potassic tungstate = potassic nitrate + tungstic acid.
(B.) The action of bases on salts in solution.
(a.) If to a solution of a salt, the base of which is soluble, another
base be added which is also soluble and capable of forming a soluble
salt with the acid of the original salt, the acid will then be divided
between the two bases in proportion to its affinity for each.
Example: Potassic hydrate + sodic nitrate = sodic nitrate + potassic nitrate +
sodic hydrate + potassic hydrate.
Note further that in some cases a portion of the base may be pre-
cipitated, owing to its somewhat imperfect solubility.
Example: Potassic hydrate + baric nitrate = potassic nitrate + baric nitrate +
potassic hydrate + baric hydrate (a portion of which will be precipitated).
(b.) If to a solution of a salt, the base of which salt is entirely in-
soluble, a base be added which forms a soluble salt with the acid of
the original salt, then the base of the original salt will be precipitated,
and the whole of the acid set free will combine with the new base
added.
Example: Ammonia + ferric sulphate = ferric oxide + ammonic sulphate.
This rule has its exceptions; ammonia will not throw down the
base of mercuric cyanide, although it is insoluble.
(c.) If to a solution of a salt a base be added, which with the acid
of the salt forms an insoluble compound, all the acid of the original
salt will be precipitated with the newly added base, the other base if
soluble remaining in Solution.
Example: Baric hydrate + potassic sulphate = baric sulphate + potassic hydrate.
(d.) If to a solution of a salt, the base of which is insoluble, a base
be added which forms an insoluble compound with the acid of the
original salt, both bases, as well as the acid previously in contact with
the one base, will be precipitated from the solution.
Example: Baric hydrate + argentic sulphate = baric sulphate + argentic hydrate.
(C.) Action of salts on salts in Solution.
(a.) If a soluble salt be added to a soluble salt, both salts, by a
mutual interchange of acids and bases also forming soluble salts, a
solution of four salts in unknown proportions will probably result.
Example: Potassic sulphate + sodic nitrate = potassic sulphate + potassic
nitrate + sodic sulphate + sodic nitrate.
(b.) If a soluble salt be added to a soluble salt, both salts by a
mutual interchange of acids and bases forming an insoluble or
sparingly soluble salt, decomposition will result, and the compound
that is least soluble will be precipitated.
Example: Argentic nitrate + sodic chloride = argentic chloride + Sodic nitrate
(the argentic chloride being precipitated).
CIRCUMSTANCES INFLUENCING CHEMICAL AFFINITY. 7
3. ELASTICITY MODIFIES CHEMICAL ACTION.
Elasticity (that is, the absence of cohesion) bears a close re-
lationship in its action upon affinity to cohesion (that is, the
absence of elasticity). Both are capable of effecting the re-
moval of bodies from compounds; cohesion, by reason of the
insolubility of certain bodies, and elasticity by reason of the
volatility of others. But, although the action of the two forces are
thus analogous, they are often opposite. If, for example, we add
ammonia to a solution of magnesic sulphate, magnesia is precipitated,
and ammonic sulphate remains dissolved. This precipitation of mag-
nesia is the action of cohesion. But if dry ammonic sulphate and dry
magnesia are heated together, ammonia is expelled and magnesic
sulphate is formed. This evolution of ammonia is the action of
elasticity. It is the spring of repulsion between the particles, or, in
other words, the distance maintained between the particles (elasticity)
which prevents hydrogen and oxygen combining, but when this repul-
sion or distance is overcome by some such power as pressure, heat, or
the action of spongy platinum, combination immediately results. Thus
elasticity is made use of by the chemist for the purpose both of
breaking up old compounds and of producing new ones. Acids,
bases, and salts are all more or less affected by its action;–Thus
(a.) Acids.—If an acid be added to a salt containing an acid capable
either of assuming a gaseous form at ordinary temperatures, or of
being converted into vapour at a temperature below that required to
volatilise the acid added to displace it, the acid in the salt will be
driven off and a new compound formed, consisting of the base of the
original salt with the new acid. For example, if we add to a carbonate
any acid except hydrocyanic or hydrosulphuric acid, the carbonic
anhydride of the salt is immediately evolved, owing to its elasticity.
Thus—
Potassic carbonate + sulphuric acid = potassic sulphate + carbonic anhydride.
Again : Sulphuric acid displaces nitric, hydrochloric, acetic, formie,
butyric, and other volatile acids from their salts during distillation.
Further, it is to be noted that whatever tends to increase the
elasticity of a body, such as heat, will also favour or modify chemical
action. This circumstance explains certain contradictory phenomena,
whereby salts of strong acids are decomposed by the action of weak
acids. For example—sulphuric acid has a strong affinity, and
boracic acid a weak affinity for bases. If sulphuric acid be added to
a solution of sodic borate, boracic acid is set free, and sodic sulphate
is formed. But if sodic sulphate and boracic acid be fused together,
sulphuric acid is volatilised (elasticity) and sodic borate is formed.
The same is also true of the action of silicic and phosphoric anhy-
drides on the sulphates. Or, again, if oxalic acid be boiled with a
solution of a chloride, hydrochloric acid will be expelled from the
8 HANDDOOK OF MODERN CHEMISTRY.
solution. Thus it will be noted that a feeble acid may drive off a
strong acid, provided that the stronger acid be the more volatile of
the two.
(3) Bases.—If a salt of a volatile base be heated with a fixed base,
the fixed base displaces the volatile base. For example: If an am-
monic salt be heated with calcic or potassic hydrate, a salt of the new
base is produced, and ammonia gas evolved. Here, again, contra-
dictory phenomena may be noted. For if ammonia be added to an
aluminic sulphate solution, alumina is precipitated and ammonic
sulphate formed; but if dry alumina and dry ammonic sulphate be
heated together, ammonia is evolved and aluminic sulphate formed.
(y) Salts.-Reactions of a similar nature occur in the case of
Salts. If a solution of ammonic carbonate be added to a solution of
calcic chloride, calcic carbonate is precipitated and ammonic chloride
remains in solution ; whilst, on the contrary, if dry ammonic chloride
and dry calcic carbonate be heated together, ammonic carbonate is
evolved and calcic chloride remains.
The power of elasticity on affinity is curiously influenced by certain
mechanical processes whereby the components of the body under-
going change are removed from the sphere of action. For example—
If ferric oxide be heated in a current of hydrogen, the iron is reduced,
the little steam formed being carried away by the ea:cess of hydrogen :
whilst if metallic iron be heated in a current of steam, the water is
decomposed, ferric oxide is formed, and the hydrogen liberated is
Carried away by the ea:cess of steam.
Further chemical action may be retarded if the escape of bodies
be prevented by mechanical means. For example, if an acid be
poured on calcic carbonate in a flask provided with a stopcock, the
stopcock being open, carbonic anhydride escapes, owing to its elas-
ticity, and a new lime salt with the acid is formed ; but the escape of
the acid, and the consequent formation of the new salt will be im-
peded if the stopcock is closed, the action again proceeding when it
is reopened,
Again, if calcic carbonate (as in a lime kiln), be heated exposed to
the air, all the carbonic acid is driven off, and quick lime (CaO)
remains. But if calcic carbonate be heated in a closed tube, so that
the escape of the carbonic anhydride is prevented, it may be fused
without decomposition resulting.
4. ADITESION MoDIFIES CHEMICAL ACTION.
Just as cohesion opposes, so adhesion invariably assists affinity.
Nor is this other than would be expected, when we remember the
close relationship subsisting between affinity and adhesion, it being
often difficult to mark the exact line dividing them. The powerful
influence of solution (i. e. adhesion of liquids and solids or liquids
and gases), in aiding affinity has been already referred to. As an
CIRCUMSTANCES INIFLUENCING CELEMICAL AFFINITY. 9
example—baric nitrate is soluble in water as well as in dilute nitric
acid, but is insoluble in concentrated nitric acid. If strong nitric acid
be poured on baric carbonate, no action results; but if water be
added to the mixture, carbonic anhydride is evolved, and baric nitrate
remains in solution. The chemical action in this case did not
occur until circumstances favoured solution. So also an alcoholic
solution of an acid (as tartaric acid) will not decompose a carbonate
(as potassic carbonate), unless the resulting salt is soluble in alcohol.
If dry sulphuretted hydrogen be mixed with dry sulphurous anhy-
dride they will not act, whilst decomposition is immediate if moisture
be present.
(a.) Adhesion of gases to solids (surface action).-If a piece of porous
charcoal be introduced into ammonia gas standing over mercury, the
charcoal, by reason of the force of adhesion between itself and the
gas, condenses the gas in its pores. The action of spongy platinum
in effecting the combination of mixed hydrogen and oxygen gases,
and the ease with which a piece of platinum foil may be kept red hot
by allowing a jet of coal gas to play upon it, are further illustrations
of the power of adhesion in aiding affinity. In this latter case we
may regard the elastic force of the gases as the cause preventing their
union. The platinum, however, by effecting a condensation of the
gases upon its surface, brings them within the range of each other's
chemical attraction (Faraday). This being so, it will be understood
that the larger the surface exposed, the greater the condensation.
Hence the more intense action of platinum when finely divided, as in
the state of platinum black. In this power of adhesion, moreover,
we have the means of effecting chemical combinations otherwise
unprocurable. For example, spongy platinum will coerce the formation
of water and nitric acid from ammonia and air—a reaction impossible
to effect by heat alone,—whilst ammonia may be formed from the
oxides of nitrogen and hydrogen in a similar manner. Sulphurous
anhydride may be oxidised by the action of spongy platinum, to
sulphuric anhydride—a process which has been suggested as a means
of preparing sulphuric acid. Nor is this action peculiar to platinum ;
in an inferior degree gold, silver, palladium, iridium and other metals
having no strong affinity for oxygen, (for otherwise the surface of
such metals would soon become oxidized), act similarly. This action
is modified and often entirely stopped by the presence of minute
quantities of certain vapours and gases, such as, e.g., carbonic oxide,
vapour of carbonic disulphide, phosphoretted hydrogen, sulphuretted
hydrogen, etc.
(3.) Action of nascent matter.—If hydrogen be generated in the
presence of arsenious acid, it combines with the arsenic to form
arseniuretted hydrogen. But its power of combining with the arsenic
is limited to the instant of its being set free, for, if the hydrogen,
immediately after being generated, be conveyed through a solution
10 HANDBOOK OF MODERN CHEMISTRY.
of arsenious acid, no such combination will be found to result. Again,
if a stream of hydrogen be passed through a mixture of argentic
chloride and water, no action on the silver salt will be apparent ;
but if the hydrogen be generated in the presence of argentic chloride,
the silver will be instantly reduced.
Again, in the colour tests for morphia, strychnia, or aniline, it is
essential that the oxygen be generated in the presence of these
bodies. This is commonly effected by the action of sulphuric acid on
some salt, such as potassic bichromate, or by the oxygen liberated at
the positive pole of the battery. But by whatever means we set free
the oxygen, the gas must be nascent, that is, the bodies upon which
it is to act must be present at the moment of its birth.
We may suppose in such cases that the gases are for a moment
under coercion, or in other words, that the elasticity of the gases has
not yet come into play. In such a condition, chemical combinations
may be easily effected.
5. INFLUENCE OF MASS OR QUANTITY ON AFFINITY.
It will be remarked, that if one body unites with another body in
several proportions, the compound which possesses the smallest
number of elements is generally the most difficult to decompose. For
example, if plumbic dioxide (PbO2) be heated, it becomes plumbic
oxide (PbO), but a continuance of the same heat will not decompose
the plumbic oxide.
We have now to examine this subject from another point of
view.
If we add an equivalent of sulphuric acid to a solution of potassic
nitrate, we have said that a mixture of potassic sulphate and potassic
nitrate will be formed, together with free acids. Suppose we add,
however, a great eaccess of sulphuric acid, the question is, Will this
excess influence the relative quantities of the two salts formed 2 This
subject was first investigated by Berthollet, who deduced the law
“ that in elective attraction the power eacerted is not in the ratio of the affinity
simply, but in the ratio compounded of the force of affinity and the quantity of
the agent.” That is, in other words, that quantity may be made to com-
pensate for a weaker chemical action. Gladstone has further inves-
tigated this subject, employing the change of color brought about
by affinity (as by the action of potassic sulphocyanide on ferric salts)
as a means of determining the extent of the decomposition. The fact
was demonstrated that if a quantity of potassic sulphocyanide be
mixed with ferric nitrate, the quantity of sulphocyanogen of the
former being exactly equivalent to the iron of the latter, the whole of
the iron was not withdrawn as ferric sulphocyanide; but that if a
second equivalent of potassic sulphocyanide be added, more ferric
sulphocyanide was formed, and so on with a third and a fourth
equivalent, up to 375 equivalents, although, judging by the color,
CIRCUMSTANCES INFLUENCING CHEMICAL AFFINITY. 11
the effect of every addition became less and less. Gladstone concludes
that mutual interchange takes place in determinate proportions, inde-
pendent of the combination of the compounds, but dependent on the
mutual strength of their affinities and on the proportions of each con-
stituent present.
The effects of quantity in the combinations of gases, have also
been investigated by Bunsen and Debus. Mixtures of hydrogen,
oxygen, and carbonic oxide, in various proportions, the hydrogen
and carbonic oxide being always in excess, were fired, and the relative
proportions of water and carbonic anhydride formed, estimated. These
were found to be dependent on the preponderation of the carbonic
oxide, in accordance with an ascertained law. Harcourt and Essen
have further investigated this influence of quantity, and agree in
the general conclusion that chemical affinity is affected by quantity
Ol' DOla SS.
6. MECHANICAL FORCE MAY MODIFY CHEMICAL ACTION.
Pressure, percussion, friction, agitation, and indeed all forms of
mechanical action influence the chemical force, both by disturbing and
by favoring its manifestation. A solution of tartaric acid added to a
solution of potassic chloride needs to be well stirred in order to
secure the complete formation of the potassic tartrate. This, as well
as numerous other cases where the stirring-rod is so constantly in
requisition in the laboratory, illustrates the influence of mechanical
action on affinity.
On the other hand, mechanical action may destroy the force. A
touch, e.g., disturbs the equilibrium of the particles of iodide of ni-
trogen. The fulminating compounds need simply a blow to break
them up. This is indeed the history of explosions generally.
7. CoNTACT DECOMPOSITION.—FERMENTS.–CATALYSIs.
Certain bodies exert on other bodies by their mere contact (i.e.,
by the action of presence) a power whereby the decomposition of the
body is effected, and new compounds are formed. The substance which
excites this action (i.e., the ferment) neither gives anything to the
compound on which it acts, or takes anything away from it.
Illustrations of contact decomposition may be noted in the following
C8,SèS : -
(1.) Hydric peroxide (H.O.) is a powerful oxidizing agent. If,
however, finely divided metallic gold, silver, or platinum be added to
the liquid it will suffer decomposition, although the metal itself will
undergo no change. Further, if instead of employing metallic gold or
silver, auric or argentic oxide be placed in the liquid, not only will
the hydric peroxide be decomposed, but the metallic oxide itself will
suffer decomposition and the metal be reduced.
(2) Again, potassic chlorate is decomposed at 698°F (370° C.),
12 IIANDIBOOR OF MODERN CEIEMISTRY. . .
and liberates oxygen. If, however, the potassic chlorate be mixed
with manganic peroxide or with cupric oxide and heated, the oxygen
will be given off at a temperature of from 446° to 500° F (230° to
360° C.), although the manganic peroxide itself undergoes no change.
(3) Nitric acid converts starch into oxalic acid (H, C, O.), but in
the presence of a manganese salt, carbonic anhydride is formed.
(4.) Sugar, under the influence of yeast, breaks up into alcohol and
carbonic anhydride, the yeast neither giving anything to, nor taking
anything from, the Sugar.
(5.) Starch in the presence of diastase is converted into sugar, a
change which takes place in every germinating seed.
(6.) Amygdaline in the presence of synaptase (an albuminoid prin-
ciple present in the pulp of the seed) breaks up into hydrocyanic acid,
oil of bitter almonds, sugar, and formic acid.
These three last illustrations are regarded as cases of fermentation.
The bodies capable of effecting the changes (ferments) in no way,
however, contribute to the new products, although they themselves
undergo specific changes during the process.
The theories to account for these phenomena will be discussed
under fermentation. Berzelius imagined them due to a new force,
which he designated Catalysis. Catalysis means fermentation, and
the explanation of Berzelius is little else than “that fermentation is
fermentation.” Liebig imagined that they might be explained by
supposing that the motion in the atoms of one body were communi-
cated to the atoms of another body, thereby setting up similar
changes, just as one body on fire is able to set on fire other
bodies. Very frequently, however, the body that starts the fer-
mentation, and the body that ferments, undergo vastly different
changes. In such cases as 1, 2, and 3 given above, to which the
term “concurring attractions” has been given, the catalytic body may,
and possibly does, play a part, but what part is not exactly known.
In case 1 Brodie has shown that there is a direct relationship between
the quantity of the metallic oxide reduced and the hydric peroxide
decomposed, and he supposes that the particles of the same element
may attract one another, the atoms being in different electrical states.
Liebig considered that various diseases, such as the Exanthems,
were due to the contact of germinal matter (acting as a ferment) with
substances in the blood capable of undergoing fermentation. The
materials in the blood capable of being thus split up being exhausted,
the disease could not, as he explained, again recur. -
At present we class these phenomena together, awaiting further
investigation, regarding the doctrine of Catalysis as a convenient fiction.
8. INFLUENCE OF HEAT AND COLD ON AIFFINITY.
The chemical force acts only within a given range of temperature,
the limits differing with different bodies. A red-hot glass rod, e.g.,
CIRCUMSTANCES INFLUENCING CHEMICAL AFFINITY. 13
will effect the combination of oxygen and hydrogen, whilst a white heat
is necessary to decompose the compound so formed, into oxygen and
hydrogen (Phil. Trans., 1847). Mercury, when exposed to the action
of oxygen at 698°F. (370°C.) forms mercuric oxide (HgC), whilst
mercuric oxide at a higher temperature is again resolved into mercury
and oxygen. Baric oxide (BaO) at a red heat becomes baric peroxide
(BaO2), but at a white heat baric peroxide is resolved into oxygen and
baric oxide (BaO). Thus it is clear that a high temperature may
undo the work done at a lower temperature.
(a.) Heat may promote affinity.—It does so by overcoming the force of
cohesion. Thus an extreme cold, as, for example, the cold produced
by a bath of ether and sodic carbonic anhydride(–104.8°F., or—76°C.)
will prevent the combination of iodine and phosphorus, or of chlorine
and phosphorus, or of chlorine and finely powdered antimony, but
these bodies will severally combine on exposing them to ordinary
temperatures. At common temperatures, again, sulphur will not
combine with carbon, whilst at a high temperature the union of these
bodies may be easily effected.
(3.) Heat may destroy affinity.—It does so by effecting a separation
of the ultimate particles of the body. Probably, indeed, all substances
would be decomposed if we could apply sufficient heat. Ammonia
may be decomposed by heat. At a red heat C, H, is decomposed into
carbon and C.H., whilst this latter at a higher temperature may be
further decomposed into hydrogen and carbon.
To the partial decomposition of some bodies at a high temperature
Deville has given the name “dissociation.” Thus, if steam and
carbonic anhydride be passed through a red-hot porcelain tube, the
gases left after the un-decomposed carbonic anhydride has been
absorbed by potash will be found to be an explosive mixture of
oxygen, hydrogen, and carbonic oxide, the hydrogen of the steam at
the moment of its liberation from the oxygen, reducing a portion of
the carbonic anhydride. Even the partial reduction of carbonic
anhydride itself into carbonic oxide and oxygen may be effected by
passing it through a porcelain tube heated to 2372° F. (1300° C.)
Again, carbonic oxide may be partially resolved into carbon and
carbonic anhydride by passing it through a heated porcelain tube, in
the axis of which is placed a small and hollow brass tube kept cool by
a constant current of water within, and upon which the carbon will be
deposited. In a similar manner sulphurous anhydride may be partially
resolved into sulphuric anhydride and sulphur.
(y). Heat modifies chemical action.—In other words, the nature of the
products may be influenced by the temperature. Thus, carbonic
anhydride and water are formed by the combustion of ether in air,
and carbonic anhydride and nitrogen by the combustion of cyanogen.
But if a platinum wire be allowed to glow in a mixture of air and
ether, aldehyde and acetic acid will be formed, whilst if the glowing
14 HANDBOOK OF MODERN CHEMISTRY.
platinum wire be placed in a mixture of cyanogen and oxygen, nitric
Oxide, and not nitrogen, will be produced.
9. INFLUENCE OF LIGHT ON AFFINITY.
Light both promotes and destroys chemical action.
(a.) Light promotes chemical action.—Thus, chlorine and hydrogen will
not combine in the dark, but in direct sunlight they combine with
explosion. Chlorine and carbonic oxide under the influence of light
combine to form phosgene, or light-formed gas.
(3) Light destroys chemical compounds.-Thus, photography depends
on the power of light to decompose argentic chloride. Sun-light again
decomposes nitric acid, oxygen being evolved, the nitrous acid formed
communicating a yellow tint to the acid.
10. INFLUENCE OF ELECTRICITY ON CHEMICAL ACTION.
(a.) Electricity promotes chemical combination.—Dilute sulphuric acid
has no action on the amalgamated zinc of a battery until a current is
set up by bringing the poles together.
(6.) Electricity both alters and destroys chemical combinations.—Thus
Davy decomposed the alkalies by electricity, and in this manner
obtained the alkaline metals. When the galvanic current is passed
through water it is split up into its constituent gases.
11. INFLUENCE OF WITAL FoRCE ON CHEMICAL ACTION.
This influence is manifest in every living organism from the pro-
duction of a simple cell to the highest manifestations of life. Elements
are re-arranged under the influence of life to form the constituents of
the organism, and out of a single fluid all the elements of growth and
nutrition are elaborated, whilst the various secretions (mucous, bile,
urine, milk, etc.), have their compositions determined by the agency of
the vital force.
Thus it would seem that all forms of force influence affinity. The
influence depends on their power respectively either to draw particles
nearer together, thus promoting affinity, or to separate them, thus
retarding or preventing it.
IV-Degree, Force, or Energy of Affinity.
There is a great inequality in the action of affinity. The want of
energy between oxygen and fluorine, and the intensity of energy
between oxygen and potassium, is an illustration. The more opposite
the bodies on which affinity is brought to bear, the more intense is
its energy. If an iron rod be placed in a copper salt, the copper is
thrown down on the iron, manifestly because the acid has a greater
affinity for the iron than it has for the copper. Bergman termed the
force of affinity an elective force, but he entirely overlooked the modi-
fying influences of cohesion and elasticity. Berthollet, who pointed
DEGREE, FORCE, OR ENERGY OF AFFINITY. 15
out these modifying influences, insisted that these were the forces that
determined chemical decompositions.
Can we estimate, then, the amount of affinity between different
bodies? Not absolutely, but, to a certain extent, relatively. Several
methods have been proposed.
(1) AEFINITY MEASURED BY REFERENCE To THE SPECIFIC GRAVITY
OF BODIES (Laplace and others).
Acetic acid (Sp. Gr. 1063) poured on carbonates turns out carbonic acid.
Hydrochloric acid (Sp. Gr. 1247) , , acetates , , acetic acid.
Nitric acid (Sp. Gr. 1421) ,, chlorides 3 ) hydrochloric acid.
Sulphuric acid (Sp. Gr. 1-60) ,, nitrates 3 * Initric acid.
Thus it would seem that the greater the specific gravity of the acid,
the more intense is its chemical action. But when we examine the
alkalies we shall find that their energy of action, as shown by their
specific gravity, is almost in an inverse order. Thus:–
Baryta... ſº º º - - - s & & ... 5'456
Magnesia tº e - © tº º e - © ... 3-60
Lime ... * - - tº tº º & © tº • * tº 3 * 180
Potash... tº 4 º' e - © & e 9 & © tº 2. 20
Soda ... e tº º & B e. © - e. ... 2' 13
Ammonia solution ... -> 0-90
Thus it is manifest that specific gravity affords no test of the relative
power of the force.
(2.) AFFINITY MEASURED BY THE FORCE OF ADHESION
(Guyton Morveau).
Guyton Morveau, who first suggested adhesion as a test of the
energy of affinity, acted under the impression that adhesion was the
first stage of affinity. He employed equal-sized discs of different
metals suspended from one end of a scale beam, and estimated the
weight necessary to separate them respectively from a layer of mer-
cury. These weights he regarded as the measure of their affinity.
AFFINITY MEASURED BY ADHESION (Guyton Morveau).
Gold adheres to Mercury with a force of 446 grains.
Silver 3 y 3) 2.9 429 33
Tin 25 } } * > 4.18 3 J.
Lead } } } } 33 397 ,,
Bismuth , > y 3 y 37.2 25
Platinuum , y 3 - 3 y 282 y?
Zinc 5 y 35 2 3 204 52
Copper , 7 y 3 y 142 35
Antimony, 5 * 3 * 126 5 y
Iron 9 3 }} 33 115 }}
Cobalt } } 3 y 33 S 3 y
Achard followed out the same principle in greater detail, by using
other solids and fluids. Gay Lussac estimated the force required to
16 HANDBOOIC OF MODERN CTIEMISTRY.
separate a circular glass disc (4-6 in. diameter) from the following
fluids, and found it as follows:–
From water ... (Sp. Gr. 1'000)—814.7 grains.
,, turpentine (Sp. Gr, 0.869)—523-6 53
,, alcohol (Sp. Gr. 0.819)—474.4 35
But there were manifest objections to this as a test of affinity : —
(1.) It was not a measure of affinity at all, but of adhesion.
(2.) It was more often a measure of cohesion than of adhesion, a
layer of mercury being separated from mercury, or water from
Water, etc.
(3.) The results obtained as the energy of adhesion were often
found to be exactly the opposite to the energy of affinity.
3. AFFINITY MEASURED BY THE AMOUNT OF FORCE REQUIRED TO
EFFECT THE DECOMPOSITION OF A CoMPOUND.
(a.) This decomposition may be effected by the agency of heat (Fourcroy,
Tavoisier, etc.).-A very slight heat, for example, is sufficient to
destroy the combination of oxygen with certain metals, such as gold
or silver, whilst no heat will effect the decomposition of other metallic
oxides. Thus it is evident that the force between oxygen and calcium,
for example, is very much greater than that between oxygen and gold.
An attempt was made to express this amount in figures; as e.g.
in the case of the sulphides, by noting the temperatures at which
they are decomposed, and deducting therefrom the temperature
at which sulphur itself is volatilized. Thus, sulphur volatilizes
at 836° F., whilst sulphide of iron (FeS2) is decomposed at 1500°F.
Therefore 1500 — 836 = 674, the amount of the force between
sulphur and iron relatively. Sulphide of gold (AusS) is decom-
posed at 842° F. 842 – 836 = 6. Therefore, supposing the power
of affinity holding the sulphur to the gold to be 6, in the case
of iron it is 664; that is, nearly 111 times greater in iron than in gold.
Thompson recommends a reverse method of estimating the force, viz.,
by a reduction of temperature. Certain saline solutions part with their
salts in the act of freezing, and they do this at various temperatures.
Hence, by observing the temperature at which the saturated solution
freezes, and remembering that the greater the affinity the lower the
temperature, he considered we might be able to form some estimate of
its relative force.
(3) The decomposition may also be effected by the agency of a superior
affinity.—Mayow in 1674, Geoffrey in 1718, and Bergman in 1775,
attempted to estimate the force by what they called single elective
affinity; that is, where one substance takes away another to the exclu-
sion of a third. Thus, ammonia turns out magnesia from magnesic
sulphate; soda, ammonia from ammonic sulphate; potash, soda from
sodic sulphate; strontia, potash from potassic sulphate ; and baryta,
strontia from strontic sulphate. These experiments led Geoffrey to
DEGREE, FORCE, OR ENERGY OF AFFINITY. 17
invent tables of attraction, as they were called, such as the fol-
lowing:—
TABLE OF ATTRACTION (Geoffry).
Sulphuric Acid. Potash.
Baryta. Sulphuric acid.
Strontia. Nitric acid.
Potash. Muriatic acid.
Soda. Acetic acid.
Lime. Carbonic acid.
Ammonia.
Magnesia.
These views held their ground until 1803, when Berthollet pointed
out, as the result of a more rigid analysis of the question, the error
into which Geoffry and Bergman had fallen, in overlooking the
modifying effects of cohesion and elasticity. Further, he showed that
Bergman's tables were simply tables of the order of decomposition,
and not tables of the attractive force. Berthollet, however, fell into
the opposite error of denying the existence of a superior attractive
force at all, and of supposing that decompositions were always deter-
mined by cohesion and elasticity.
We should note, however, that Bergman was clearly aware of some
influence other than affinity, affecting chemical results. This is shown
by the fact, that in many cases he compiled two sets of tables, setting
forth the different effects resulting from the combination of bodies by
Solution, and by fusion.
Guyton Morveau, seeing that no dependence could be placed on the
measure of chemical action, as deduced from Geoffry and Bergman’s
tables of “single elective affinity,” attempted to estimate the force by
“double elective affinity,” that is, where four elements are employed in
the decomposition, the two of the one compound reciprocally acting
on the two of the other. But still the same modifying influences
were at work, and we may conclude with Berthollet that, whilst the
tables of affinity give us good ideas of the order of decomposition,
they are not, owing to the influence exerted by cohesion and by
elasticity, indications of the relative force of affinity.
4. AFFINITY MEASURED BY THE TIME OF COMBINATION.
It was suggested by Wenzel that the time required for one body to
dissolve another might serve as a measure of affinity.
Thus he immersed known weights of different metals in a weak
acid, and at the end of a given time, estimated the quantity of the
several metals dissolved. These quantities he supposed corresponded
to the ratio of their affinities.
Again, it will be noted that the energy of the combination will be
largely dependent upon the cohesion of the body, the temperature of
the liquid, and other circumstances.
C
5 y
18 HANDBOOK OF MODERN CHEMISTRY.
5. AFFINITY MEASURED BY COMBINING Proportions.
When Kirwan was engaged in his inquiries on the composition of
salts, he remarked that each salt possessed a different per-centage
amount of acid and base, and he supposed that these might serve as a
means of estimating the force of affinity. Tables were drawn up by
Rirwan as follows:–
TABLE No. 1.


|
100 Grains. Potash. Soda. Lime. Ammonia. | Magnesia. | Alumina.
Sulphuric acid . . 215 165 110 90 80 75
Nitric acid . . . . 215 1.65 96 87 75 65
Muriatic Acid . . 215 158 89 79 71 55
TABLE No. 2.
100 Grains. Sulphuric acid. Nitric acid. Muriatic acid.
Potash , , tº 9 46 - 5 46'5 46 - 5
Soda $ tº - tº 60-9 60-9 63' 4
Lime & s tº tº 91 - 0 104 - 1 112-0
Ammonia. . . tº II 1 - 1 115' 0 126'5
Magnesia . . * * 125-0 133' 3 14 1-0
Alumina . . is tº 133-3 153 : 6 181-8
ICirwan thus arrived at two general laws :
1. That the quantity of any base required to saturate a given quantity of
any acid, was DIRECTLY as the affinities.—Thus, potash had more affinity
for sulphuric acid than Soda, soda than lime, lime than ammonia, and
SO OIl.
2. That the quantity of any acid required to saturate any given quantity
of a base, was INVERSELY as the affinities.—Thus, sulphuric acid had more
affinity for potash than it had for soda, nitric acid less affinity for lime
than sulphuric acid, hydrochloric acid less than nitric acid, and so on.
Bergman, arguing on the same facts, expressed the law of affinity
differently: “The force of affinity, whether of acid or base, is in the ratio
of the quantities required to saturate.” But it was manifest that this was
not so, for the first table would show lime, for example, to have more
affinity for sulphuric acid than for nitric acid, whilst the second table
would indicate exactly the reverse.
Berthollet again, expressed what he deemed the law of affinity from
the same facts as follows: “ The force of affinity is INVERSELY as the
quantities required to Saturate.” .
Again, as Sir H. Davy showed, Berthollet's law involved a contra-
diction, inasmuch as the action between the constituents of a compound
must be mutual. “Sulphuric acid,” writes Sir H. Davy, “has as
much attraction for baryta as baryta for sulphuric acid. Now baryta
is the alkaline earth of which the largest amount is required to Saturate
DEGREE, FORCE, OR ENERGY OF AFFINITY. 19
sulphuric acid, therefore on Berthollet's views it has the weakest affinity
for that acid. But less sulphuric acid saturates baryta than any other
earthy or alkaline body, therefore, according to Berthollet, sulphuric
acid has a stronger affinity for baryta than for any other substance,
which is contradictory.”
Again, experiment proves Berthollet's law fallacious. From his
tables, such as the following, it would seem that ammonia had a
greater affinity for sulphuric acid than baryta, and carbonic acid a
greater affinity for baryta than sulphuric acid, which we know not to
be the case ;-
40 parts of Sulphuric acid require 77 parts of Baryta require for
for neutralization. neutralization.
292 Morphia. 165 Iodic acid.
162 Quinine. 118 Bromic acid.
77 Baryta. 76 Chloric acid.
52 Strontia. 54 Nitric acid.
48 Potash. 49 Sulphuric acid.
32 Soda. 37 Muriatic acid.
28 Lime. 36 Oxalic acid.
20 Magnesia. 22 Carbonic acid.
17 Ammonia.
Berthollet, however, was fully aware of the contradictory results of
the law and of experiment, but explained these contradictions by
reference to the effects of cohesion and elasticity.
It is certain, however, that combining proportions and power of
saturation, are in no respect a measure of relative affinity.
6. AFFINITY MEASURED BY THE ELECTRICAL CONDITION.
Thompson has drawn up a table of affinity, founded upon the order
of decomposition, as effected by electrical influence.
Becquerel points out that if a current of electricity of known
activity be passed through a mixed solution of the metals, it decom-
poses them in a given order. If a solution, for example, be made,
containing atomic proportions of argentic nitrate, cupric nitrate, and
plumbic nitrate, and a galvanic current be passed through the liquid,
the silver will be thrown down first, then the copper, and finally the
lead. Thus it would seem that the silver had the least affinity for
Oxygen, and lead the most. But if, instead of mixing these nitrates
in atomic proportions, a greater quantity than its equivalent of cupric
nitrate be added, there comes a time when both copper and silver
will be thrown down together, mass thereby overcoming resistance.
It is an important question yet to be decided, whether the order and
the rate of decomposition of a mixed solution of metallic salts in
atomic proportions, coincide with the results obtained by experi-
menting on solutions where the resistance is overcome by quantity.
Summarizing these facts we may note, first, that we have no means
of estimating the force of affinity absolutely; and secondly, but very
uncertain means of estimating it relatively.
20 HANDBOOK OF MODERN CHEMISTRY,
CHAPTER II.
Nomenclature—Chemical Symbols and Formulae—Combining Proportions—Atoms –
Molecules—Atomic and Molecular Combination—Compound Radicals—Volume—
Standard Pressure and Temperature—Relative Weight—The Crith–Relation
between Atomic Weights and Specific Gravity—Relation between Atomic Weights
and Specific Heats—Atomicity and Quantivalence—Chemical Formulae—Substi-
tution—Isomerism—Isomorphism—Allotropism—The Metric System.
Elements and Compounds,--By an element or simple body we
understand a substance which cannot be decomposed, and from which
nothing can be taken but the substance itself. Iron is an element;
you can extract nothing from iron but iron. The elements are divided
into two classes—metals and non-metals, or metalloids. This division,
however, is arbitrary.
By a compound body we understand one formed by the union of two
or more elementary bodies. Common salt is a compound body. It
may be formed by combining sodium and chlorine. From common
salt we can obtain sodium and chlorine. The first is the synthetical
proof, and the second the analytical proof, of its compound nature.
Names of Bodies.—The ancient names given to bodies were most
often fanciful. They were derived either (a) from their resemblance to
certain things (as, e.g., oil of vitriol, sugar of lead, butter of antimony
liver of sulphur, etc.); or (3) from some remarkable property of the body
(as, e.g., caustic alkali, corrosive sublimate, vital air, sal polychrest,
phosphorus, antimony, etc.), or (y), from the names of a person or
heathem divinity, (as e. g., Glauber's Salts, Tantalum, Niobium, etc.) or
(3) from the name of a place (as, e.g., Epsom salts, Cheltenham salts,
Columbium, etc.), or (e) from the name of a planetary body (as, e.g.,
Tellurium, Uranium, etc.)
A reformation in nomenclature was suggested, in 1781, by Guyton
Morveau, who proposed that the name should indicate somewhat the
properties and composition of the body, and should have its root in
the dead languages. In 1787, he obtained for this purpose the
assistance of the French Academy of Sciences, and Iavoisier, Ber-
thollet, and Fourcroy were appointed to join him in the work. To a
large extent their efforts were successful.
Many of the names of bodies now employed, express some special
characteristic. Thus chlorine (x\opóc, green) refers to the color of
the substance; bromine (8ptºpog, stench) to its odor, etc. Most of the
metals, although many of the common names are retained, are dis-
tinguished by the termination um. The haloid group terminate in
ine; some terminate in on, as carbon and boron; and some in gen
TERMINATIONS. 21
(yev, 40), as hydrogen (water-begetter), oxygen (acid-begetter), nitrogen
(nitro-begetter), etc.
In the case of compounds, the name is made to express the com-
ponents of the body, and, as far as possible, its constitution. Thus, the
name “sodic chloride ’’ expresses a compound of sodium and chlorine.
The term “ anhydride" signifies a binary compound containing
oxygen (an oxide), which, when combined with water, forms an acid :
for example—
SOs + H2O = H2SO4.
Sulphuric anhydride + Water = Sulphuric acid.
We may here consider the meaning of the various terminations and
prefixes used in chemical nomenclature.
I. TERMINATIONs. -
(1.) “ide" is applied to the negative constituent of a binary com-
pound (that is, a compound formed by the union of two elementary
bodies), the positive constituent being made to terminate in “ic.”
For example—
Potassium + Iodine form Potassic Iodide.
Lead -- Oxygen ,, Plumbic Oxide.
[NotE.—Sir H. Davy suggested that the terminations in these
cases should indicate property, “ide" being employed for acid, and
“ uret” for alkaline compounds.]
(2.) “ic ’’ and “ous.”—Two bodies may combine in different propor-
tions. Thus, tin and chlorine combine to form Sn Cl2 and Sn Cl4.
The termination ic is given to the positive constituent of the com-
pound (Sn) which contains the largest proportion of the negative con-
stituent (C1), and the termination ous to the positive constituent,
which contains the smallest proportion of the negative constituent.
For example—
Sn + Cl2 - SnCl2.
1 Tin + 2 Chlorine = Stannous chloride.
Sn + Cl, F. SnCl4.
1 Tin -- 4 Chlorine = Stannic chloride.
(Similarly Fe0 = ferrous oxide, Fe2O3 = ferric oxide; Hg,O =
mercurous oxide, Hg.0 = mercuric oxide; etc.)
These terminations “ic” and “ous,” moreover, are employed to
distinguish acids that are composed of the same elements, but in
different proportions. Thus, sulphur forms two acids by its combina-
tion with oxygen. The acid which contains the most oxygen is called
sulphuric acid, whilst that containing the least oxygen is called
Sulphurous acid.
Sulphurous acid (, Sulphuric acid.
Phosphorous acid | Contain less oxygen than Phosporic acid.
Nitrous acid Nitric acid.
22 HANDBOOK OF MODERN CHEMISTRY.
(3) “ite” and “ate.”—The termination “ite” implies that the salt
is a compound of a base and an acid terminating in “ous,” and the
termination “ate” that the salt is a compound of a base and an acid
terminating in “ic;” for example—
Sodic sulphite is a salt of Sulphurous acid.
Sodic sulphate 92 Sulphuric acid.
(4) “a” and “ia.”—The termination “a” is usually given to in-
organic alkalies,” such as soda, and “ia” to organic alkalies, such as
Strychnia. The rule is not absolute.
(5.) “ine” or “in” are used to denote a neutral alkaloid, such as
caffeine, piperin, etc.
(6) “yl” or “yle” is adopted in the case of many of the compound
radicals, such as methyle, propyl, etc. In these latter cases the rule
is by no means constant.
II. PREFIXES.
(1.) Bin, Ter, etc. (Latin); or Mon or Mono, Deut, etc. (Greek);
or Di, Tri, Tetra, etc., denote various proportions of constituents, and
the position of various compounds in a series; for example—
Carbonic monoxide (or oxide) signifies C + O.
Carbonic dioxide (or anhydride) , C + O2.
There is no rule as to the use of the Latin or the Greek forms.
(2.) “Per” denotes the highest compound in a series; for example,
a peroxide signifies that oxide which contains the largest quantity of
Oxygen in a series of oxides.
(3.) “Sesqui” denotes a compound where the relationship of the
elementary atoms is as 2 to 3; for example, sesquioxide of iron (really
ferric oxide) has the formula Fe2O3.
(4.) “Proto’’ (Tparoc, first) denotes the first of a series of com-
pounds; for example, the protoxide of iron Fe0 (also called ferrous
Oxide) contains the Smallest quantity of oxygen of any iron and oxygen
compound.
(5.) “Hypo ’’ (itro, under) denotes the position of a compound.
Thus, the acid containing less oxygen than Sulphurous acid, is called
hyposulphurous acid.
(6.) “Hyper’ (Wrºp, over) refers to the converse of the prefix
“hypo.” Thus, hypersulphurous acid (commonly called hyposulphuric
acid) denotes an acid containing more oxygen than sulphurous acid.
(7.) “Para’’ signifies equal; for example, paracyanogen implies a
body chemically equal to cyanogen.
(8.) “Meta’ signifies “near to.” Thus, metaphosphoric acid only
differs from orthophosphoric acid by 1 molecule of water.
(9.) “Sub’’ implies that the compound contains less of a constituent
than is indicated by the rest of the word.
(10.) “Sulph" or “Sulpho,” “Hydr" or “Hydro.”—The composi-
tion of acids formed by the combination of sulphur or hydrogen (without
CHEMICAL SYMBOLS AND FORMULAG. 23
ozygon) with other elements is expressed by the foregoing prefixes, the
terminals “ous” and “ie” being also employed, in the case of the
sulphur compounds, to indicate the proportions of sulphur relatively
present. In the case of hydrogen, such terminations are not needed,
inasmuch as only one acid is formed by the union of an element with
hydrogen.
Chemical Symbols and Formulae.
The alchymists adopted signs to represent bodies. Thus G) (sol)
represented gold, and ) (luna) silver, etc. Chemists now-a-days denote
the various elementary bodies by symbols, using either the first letter
of the Latin name, or, where several elements have the same initial
letter, the first letter conjoined with a smaller one. Thus, O = oxy-
gen; C = carbon; Ca = calcium; Cl=chlorine, etc.
Further, this symbol represents one equivalent or combining weight
of the element. Thus, the symbol O represents a similar bulk of
oxygen, that the symbol H represents of hydrogen, but a weight 16
times as great.
A compound is represented by the symbols of the several com-
ponents placed one after the other. Thus, HCl represents a com-
pound, formed of one atom of hydrogen and one of chlorine, or by 1
part by weight of hydrogen and 35.5 parts by weight of chlorine.
If we desire to express more than one atomic proportion, we place a
little figure above or below the symbol. Thus, H2O (or H2O) implies
that with every atom or 1 atomic part by weight of oxygen there is
conjoined 2 atoms or 2 atomic parts by weight of hydrogen.
If the figure be placed before the whole formula, it implies that all
the elements composing the group, i. e., either as far as a comma, or
some other sign following, or else included in brackets immediately
succeeding the number, are to be multiplied by the said number.
Thus, in the equation* Casp,0s +2(H2SO.) = 2(CaSO4) + H,CaF.O.s,
the 2 before the H2SO, and the 2 before the CaSO, implies that the
whole number is to be multiplied by 2; but there being a + after
the CaSO4, it follows that the H,CaF20s is not to be multiplied by the
2 preceding the CaSO4.
It is not, however, necessary to employ brackets unless a comma be
introduced into the formula; thus, in the equation—
Caa P20s --2H2SO4–20aSO4+H CaF20s
the multiplication of the H2SO, and of the CaSO, respectively by 2 is
just as much indicated, as if the formulae had been placed within
brackets. Thus, the formula 3Cu,2NO3 implies that the Cu only is
to be multiplied by 3, and not the 2NOs; whilst if the formula fol-
y
* A chemical “equation'
formulae.
It will be remarked that in chemical as in algebraical equations, the sign + signifies
addition (or admixture); the sign — subtraction, and the sign = equals (or yields, or
is converted into). -
signifies the expression of chemical reactions by chemical
24 HANDBOOK OF MODERN CHEMISTRY.
lowing the number be placed in brackets, thus, 3(Cu,2NO3), it then
implies that the whole number is to be multiplied by 3. Thus—
3Cu,2NOs would be equivalent to CusN2O6; but
3Cu2NO3 or
3(Cu,2NOs) } 2 3 ,, Cu3N6O18,
COMBINING PROPORTIONs—ATOMIG THEORY.
In 1774, Wenzel, a German chemist, published a work on “The
General Theory of Affinities.” This in reality, contained the germ
of the atomic theory. The great fact noted by Wenzel was, that
when two neutral salts, such as sodic sulphate, and plumbic acetate
were mixed together, an exchange of acids took place, but that, never-
theless, the resulting products were neutral, proving, as he remarked,
that the acid of the one salt was sufficient for the base of the other salt.
In 1792 Richter, a Prussian chemist, wrote a work on “Stochio-
metry, or the Mathematics of Chemical Elements” (arouxsiov, an
element, puerpéo, I measure). This was mainly directed to illustrating
the relative quantities of acid and base necessary for saturation.
He further constructed numerous tables, such as the following, as
the result of his enquiries* :—
- 1. Acids. 2. Bases.
Fluoric . . * @ e - . . 427 Alumina . . & e - - , , 525
Carbonic . . & © e e . . 577 Magnesia . . s tº * * . . 615
Sebacic . . w & tº º . . 706 Ammonia . . u º w 4 , , 672
Muriatic . . tº - tº 0 . . 712 Lime * * * * a tº . . 793
Oxalic a s * - tº g , , 755 Soda * - tº ºr * * . , 8.59
Phosphoric * - tº tº , , 979 Strontia . . * tº - - . . 1329
Formic . . tº a & sº , , 988 Potash * * e is & 4 , , 1605
Sulphuric . . tº - a tº , , 1000 |Barytes . . tº is 4 tº . , 2222
Succinic . . t & e tº . . 1209
Nitric & º * - s & , , 1405
Acetic tº e- a tº * & , , 1480
Citric & ºt * * * * , , 1683
Tartaric . . ſº g . . 1694
In 1800, whilst Dalton was analysing some compounds of hydrogen
and carbon, he remarked that the several quantities advanced in
multiple proportions. The same, moreover, he found to be true with
other compounds, such as those of carbon and oxygen, sulphur and
oxygen, etc. It therefore occurred to him “that matter was composed
of particles of definite weights, and that it combined in those weights.
This constituted Dalton's “Atomic Theory,” the fundamental pro-
positions of which were—
(1.) That matter is composed of indivisible and indestructible par-
ticles called atoms.
(2.) That the atoms in a mass do not touch, but are surrounded by
an atmosphere of heat.
* These tables are taken from Thompson, and represent the mutual combining
proportions of acid and base.
CHEMICAL SYMBOLS AND FORMUL.AE. 25
(3.) That they are endowed with attractive and repulsive forces.
(4.) That they have specific weights. -
Atoms (a, not, and Téuvo, I cut). —Here we refer entirely to the
atoms of elementary bodies and not to “compound radicals,” which
have been called “compound atoms.”
(1.) Every element consists of ultimate particles called “atoms.”
The chemical symbol of any element represents this atom. Thus, O
represents the atom or smallest indivisible particle of oxygen.
(2.) We have no actual knowledge either of the shape, or of the
absolute weight, or of the absolute volume of these atoms.
(3.) The atoms of any given substance are believed to be of identical
weight, under any and every condition. One atom of oxygen weighs
the same as every other atom of oxygen –
(4.) Nevertheless the atom of one body does not weigh the same as
the atom of every other body. An atom of oxygen weighs 16 times as
much as, and an atom of carbon 12 times as much as, an atom of
hydrogen. These comparison weights of the atoms, (hydrogen as the
lightest body known, being regarded as 1,) are called atomic weights.
Atomic weights, therefore are relative weights, but not absolute weights.
For example: When we say that mercury has an atomic weight of
200, we mean, that the atom of mercury would weigh 200 times as
much as the atom of hydrogen, but inasmuch as we cannot deter-
mine the absolute weight of the hydrogen atom, the number 200 does
not express the absolute weight of the mercury atom.
Accurately, we may define the atomic weight of an element, as “that
weight which would occupy in the state of gas the same volume as the unit
weight of hydrogen under the same temperature and pressure.”
If, however, we cannot obtain the element in a state of gas (as, e.g.,
in the case of carbon), the atomic weight is then deduced from other
considerations such as the specific heat of the body, etc.
By the term “combining proportion ” Sir H. Davy implied the smallest
proportion by weight (hydrogen being regarded as unity), in which
bodies combine with each other.
Molecule (Molecula, a little mass.)—These may be compound or
elementary.
(a.) Compound Molecules. A compound body is made up of two
or more elementary atoms. A molecule of any given compound is
“the smallest possible cluster of elementary atoms capable of existing as the
compound, and of having an independent chemical action.” Thus a mole-
cule of water (H2O) consists of 2 hydrogen atoms and 1 oxygen atom.
Therefore the water molecule consists of 3 atoms, inasmuch as nothing
less than an aggregate of 3 atoms can form water. Or again, a mole-
cule of ammonia (NH3), consists of 4 atoms, viz., 3 of hydrogen and 1
of nitrogen. It could not be ammonia if there were less than 4 atoms
present. A molecule, therefore, may be a cluster of any n&mber of atoms
jrom two upwards.
26 HANDBOOK OF MODERN CHEMISTRY.
The atomic weight of a molecule is the sum of the weights of the
several atoms of which it is composed. Thus 18 is the atomic weight
of a molecule of water (H2O=2+ 16). The molecular weight of a
hydrogen salt is always that weight which contains as many hydrogen
atoms as can be replaced by potassium, silver, etc. Thus C20, H2 is
the formula for a molecule of oxalic acid, and 90 is its molecular
weight. We do not regard CO2H as its formula, or 45 as its mole-
cular weight, because we are able, not only to replace both atoms of
hydrogen by potassium, forming the neutral potassic ozalate C.O.K.,
but to replace one hydrogen atom only by potassium, thereby forming
hydric potassic oſcalate C20, HK.
Conversely, we represent 63 as the molecular weight of HNO3, and
Inot 126 (viz., H2N2O6) because, whilst we have the salt KNO3 we know
of no such salt as HKN2O6.
(b.) Elementary molecules.—There are strong reasons for believing
that our knowledge of the reactions of elements pertains exclusively
to their molecular and not to their atomic condition, and that in all
decompositions and combinations the molecule of the element is con-
cerned, although only one of the atoms of the molecule may be at
work in effecting the change. Hence a free element, such as hydro-
gen, never appears to work singly, but in clusters, and we therefore,
in a molecular formula, double the simple or atomic formula. In a
bottle of hydrogen therefore, we shall do well to regard the gas, not
as made up of particles of EI | = 1, but as made up of atom-clusters
Of H | E[ ] =2; and the convenience of this diatomic symbolization,
|
as it is called, will appear further, when we note that, with very few
exceptions, compound bodies in their vaporous condition, occupy two
volumes. This leads us to define—
An atom of an elementary body as the smallest proportional weight
of that body capable of existing in chemical combination ; and
A molecule of an elementary body as the smallest proportional weight
capable of existing in a free or uncombined state.
By the phrase molecular weight, then, we imply “the weight of two
volumes of any substance, elementary or compound, compared with
the weight of two volumes of hydrogen.” Thus—
H.-2: Therefore the molecular weight of O2=32, of Cl2=71, of
EIC1–36'5. -
The symbol of a compound body represents a molecule of that body.
Dr. Frankland expresses this fact by stating that no element can
exist with any of its bonds unconnected, and that therefore the mole-
cules of all elements having an uneven number of bonds are generally
diatomic, but are always polyatomic. Thus—
Hydrogen (H.) H–H; Nitrogen (N3) N = N : Phosphorus (Pº) º
P–P
CEIEMICAL SYMBOLS AND FORMULAE. 27
In some cases (viz., mercury, zinc, and cadmium) we find an
element capable of existing as a monatomic molecule, its own bonds
satisfying each other. In such a case, however, its atomicity must be
even (artiad). Thus—
Mercury (Hg") —Hg—); Zinc (Zn") —Zn—; Cadmium (ca.) —cº-
but, on the other hand, such an element may be also polyatomic, as in
ozone, which is an allotropic form of oxygen where the molecule is
triatomic. Thus O2 (0=0) represents the ordinary diatomic mole-
O
cular form of oxygen, whilst O3 (*) represents the triatomic
molecule of ozone.
COMBINATION BY WEIGHT.
The laws of chemical combination as taught by Dalton are as
follows:—
I. That every definite chemical compound has a fived and invariable
composition; that is, a given compound always consists of the same elements
united in the same proportions.
Thus, hydrochloric acid (HCl) consists of 1 atom of hydrogen (H)
combined with 1 atom of chlorine (Cl). The weight of the hydrogen
atom being 1, and the chlorine atom 35°5, it follows that in every 36-5
grains, or pounds, or tons of hydrochloric acid, there is 1 grain, or
pound, or ton of hydrogen, and 35.5 grains, or pounds, or tons of
chlorine. Hydrochloric acid can be formed in no other proportion
than 1 part of hydrogen to 35°5 parts of chlorine.
II. If one substance combines with another in more than one proportion,
the Several proportions are always some multiple or sub-multiple of the lowest
of these proportions.
This is illustrated, for example, in the oxides of nitrogen :-
Atomic weight
Nitrogen. of Oxygen.
Nitrous oxide. . . . . . . . . . . , N.0 . . . . . . . . . . . . 28 to 16.
Nitric oxide . . . . . . . . . . . N202 . . . . . . . . . . . . 28 to 16 × 2 = 32.
Nitrous anhydride. . . . . . . . N209 . . . . . . . . . . . 28 to 16 × 3 = 48.
Nitric peroxide . . . . . . . . . . N20, . . . . . . . . . . . . 28 to 16 × 4 = 64.
Nitric anhydride . . . . . . . . N20s . . . . . . . . . . . . 28 to 16 × 5 = 80.
It will be seen how the various quantities of oxygen increase by
definite multiples of 16. It often happens, however, that a series may
be deficient, or that the proportions are less simple than in the
illustration given.
III. If the weights in which a series of bodies (B, C, D, E, etc.) com-
bine with another body (A) be determined, these weights or some multiple or
sub-multiple thereof, are also the weights with which B, C, D, and E com-
bine amongst themselves :— -
Example: 16 of oxygen will combine with 65 of zinc, and
16 × 2 = 32 of oxygen 3 * 32 of sulphur;
Therefore 65 of zinc } } 32 of sulphur.
28 IIANDBOOK OF MODERN CHEMISTRY.
IV. In a compound body, the combining weight of the compound is the
total combining weight of the components.
For example, the combining weight of sulphur is 32, and of oxygen
16. The combining weight of sulphuric anhydride (SO3), which is
Composed of 1 of sulphur and 3 of oxygen is, therefore, 80. -
These facts give accuracy to all chemical reactions. In the labora-
tory no materials are mixed at random ; bodies combine in exact
proportions, and form products of definite weights. It follows that,
“As the total molecular weight of the substance given is to the total molecular
weight of the substance required, so is the given weight to the required weight.”
That is, if we desire to obtain 500 grammes of carbonic anhydride
from sodic carbonate, knowing that every 106 parts of sodic carbonate
contain 44 parts of carbonic anhydride, the exact quantity of sodic
carbonate necessary to produce the 500 grammes may be estimated by
the equation—
44 : 106 : : 500 : ac.
Atomic and Molecular Combination.—H represents an atom of
hydrogen. He represents a molecule of hydrogen, or the smallest
portion of hydrogen capable of existing in the free state. Cl similarly
represents an atom, and Cl2 a molecule of chlorine. To express the
combination of these bodies in atomic formula we write it thus—
C1-i-H-HCl,
whilst to express their combination in molecular formula we write it
thus—
Cl2 + H2=2|HCl,
this latter implying the bringing together of two molecules, and a
mutual interchange occurring, whereby two molecules of a new body
are formed. Two molecules occasionally, though rarely, unite to form
One molecule, from the latent atomicity of an element becoming
active. Thus—
"C"O+ Cl2=CivOC]2 (phosgene gas),
where the latent atomicity of the carbon equal to 2 in the CO becomes
active in the COCl3, thereby making the active atomicity of the carbon
in the latter compound, double what it was in the former.
There is what Frankland calls a molecular union or combination, where
no change results in the active atomicities; as, for example, in the com-
bination of Salts with their water of crystallization. In such cases we
place a comma between the molecules. Thus, crystallized magnesic
sulphate is represented by Frankland as SOHo, Mgo",6OH2, which
implies that the 60Hz is molecularly combined with the salt. Such
combinations are, for the most part, unstable.
Compound Radicals, LA compound radical is “a group of two or
more atoms, which behaves in all respects as though it were an element.”
$uch compound groupings were supposed by Liebig to be peculiar
CHEMICAL SYMTBOLS AND FORMUILAE, 29
to bodies of organic origin, but their existence is now recognised
amongst inorganic substances.
Theoretically, the number of compound radicals must be endless;
practically, however, chemists only dignify those groupings as com-
pound radicals, that can be shown to enter into the composition of a
large number of compounds.
Respecting these compound radicals we must note that—
(1.) Every compound radical must contain a polyad element; that
is, an element requiring two or more hydrogen atoms, or their equiva-
lent, to saturate it. -
(2.) Compound radicals, like the elements, are of different atomici-
ties, the atomicity depending on the number of hydrogen or other
monad atoms required to satisfy them. Thus—
If you remove H from the fully saturated NH3 (ammonia), a
“residue.” or “compound radical” remains, which is no longer satu-
rated, called amidogen (NH2) of monad atomicity. Thus, amidogen
will combine with the monad element potassium, to form potass-amine
(NH.K.).
If you remove H2 from NPIs, a radical is left called imidogen (NH),
of dyad atomicity. Thus, imidogen will combine with two atoms of
the monad compound radical methyl (CH3) to form dimethyl-amine
NH(CHA).
(3.) The molecule of a monad, triad, or pentad compound radical,
like the atom of a monad, triad, or pentad element, cannot exist in a
free state, but when isolated combines with itself. Thus, H., repre-
sents a molecule of hydrogen, and (HO), a molecule of the monad
compound radical hydroxyl.
A few examples will render these facts clear, and illustrate their
application.
In nitric acid we have a body built up on the water type, containing
a monad compound radical NO, in the place of a hydrogen atom.
# O = H.0 [OH-]; so sº O = HNO, [NO.Ho.]
In sulphuric acid we have the dyad compound radical SO, having two
unsatisfied bonds (—O—S–0–), each bond being combined with
(Ho); thus—
HO
SO. | Hö or H.S.O. = [SO. Ho.]
In phosphoric acid we have the triad compound radical (PO) having
three unsatisfied bonds, phosphorus being a pentad, each bond being
combined with (Ho); thus—
TIO
PO (H0 = H, PO, [POHos.]
| Hö
In organic chemistry we have the well-marked compound mon-
atomic radical, cyanogen (CN or Cy). Like chlorine, which combines
30 HANDBOOK OF MODERN CITEMISTRY.
with hydrogen to form hydrochloric acid (HCl), it combines with
hydrogen to form hydrocyanic acid (HCy), two volumes, as in the
former case, combining without condensation.
Dr. Frankland recognizes in his notation the following compound
radicals : —
Molecular Semi-molecular Semi-molecular
formula. formula. symbols.
Hydroxyl ... ... (HO), ... ... HO ... ... Ho
Hydrosulphyl ... (HS), ... ... HS ... ... Hs
Ammonium ... ... (NH4)2 ... ... NH4... ... Am
Ammonoxyl... ... (NH40). ... NH4O ... Amo
Amidogen ... ... (NH2): ... ... NH4... ... Ad
Compounds of metals with oxygen, each oxygen atom being com-
bined with the metal by one bond only, the other or others being free
to combine with other elements, are also regarded as compound
radicals.
Semi-molecular
Molecular - ... l- > --> Graphic
formula. or combining formula.
symbols.
Potass-oxyl ... (KO), ... Ko ... —O—K
Zinc-oxyl ... (ZnO.) ... Zno" ... —O—Zn—O—
In adopting the abbreviated form for the compound radical (e.g., Ko,
Zno") the use of the little o merely expresses that it forms part of the
radical, but it does not express the atomic proportion in which the
oxygen is present, this being determined by the atomicity of the
element with which it is associated, and which, as in the case of the
elements, is marked by dashes.
Thus: Ko–KO ; Zno"—ZnO2.
Volume (volvo, I roll).—“A volume" in chemical language implies
the space occupied by a known weight of a gas at a given temperature
and pressure, compared with the space occupied by known weights of
other gases at a similar temperature and pressure.
Gay Lussac in 1809 proved that, as in compound bodies the ele-
mentary atoms combine in fixed weights (as shown by Dalton), so, in
gaseous compounds, the constituents combine in fixed volumes.
The symbols H, O, Cl represent atoms of hydrogen, oxygen, and
chlorine, having relative weights of 1, 16, and 35-5 respectively. If
we take 1 gramme of hydrogen we should find that at a certain tem-
perature and pressure the volume of the gas would measure 11:2 litres.
In order to obtain a volume of oxygen measuring 11.2 litres, or a
volume of chlorine measuring 11.2 litres at a similar temperature and
pressure, we should require in the former case 16 grammes, and in
the latter case 35.5 grammes. These weights are, it will be noticed,
the atomic weights of oxygen and chlorine. Hence, the symbols H, O,
and Cl represent different weights of the gases, but similar bulks.
| | to represent separate volumes of hydro-
--
Again, imagine this
gen, oxygen, and chlorine. If this volume of hydrogen weighed 1
CHEMICAL SYMEOILS AND FORMUL.AE. 31
grain, a similar volume of oxygen would weigh 16 grains, and of
chlorine would weigh 35.5 grains. Hence the symbols H, O, Cl represent
similar bulks of the several gases, but different weights.
These facts were first noted in 1811 by Amedeo Avogadro, and in
1814 by Ampère. They remarked that the effect of changes of tem-
perature and pressure on all gases was alike, and reasoning on the
constancy of the results they concluded “that equal volumes of all sub-
stances in a gaseous state contain under like conditions the same number of
molecules” (“Journal de Physique,” July, 1811). But, inasmuch as
equal volumes had different weights, it followed that the molecules of
different gases must also have different weights.
An illustration will make these facts clear :-
(a.) The volume-combination of hydrogen and chlorine to form
hydrochloric acid may be thus expressed,
| H | + |Cl | = | HiCl];
which implies that a given volume of hydrogen combines with a
similar volume of chlorine to form two volumes of hydrochloric acid.
(ſ3.) The combination of hydrogen and chlorine by weight is
expressed thus—
H+Cl–HCl;
which implies that 1 part by weight of hydrogen combines with 35-5
parts by weight of chlorine to form 36'5 parts by weight of hydro-
chloric acid.
(y.) If therefore the hydrogen volume has a weight of 1, the
chlorine volume must have a weight 35.5 times as great; inasmuch,
however, as both volumes contain the same number of molecules, it
follows that the weight of the chlorine molecule must be 35.5 times
that of the hydrogen molecule.
(6.) It is evident that the volume of any two gases making a com-
pound are to one another as the atoms of the elements forming the
Compounds. Thus—
1 atom of EI combines with 1 atom of Cl,
H + Cl = HCl; i.e. Ol'
| 1 vol. of FI combines with 1 vol. of Cl.
2 atoms of H combine with 1 atom of O,
He + O = H,0; i.e. Ol'
2 vols, of FI combine with 1 vol. of O.
(e.) To this law there are certain exceptions : —
(1.) In the case of Phosphorus and Arsenic, the number of volumes
must be halved, - .
Thus—
In P. H. | 3 vols. of H combine with , vol. of P vapour; or
* l 6 vols, of H combine with 1 vol. of P vapour.
In As FI | 3 vols. of H combine with # vol. of As vapour; or
* ! 6 vols, of H combine with 1 vol. of As vapour.
32 - HANIDBOOK OF MODERN CHEMISTRY.
(2.) In the case of Mercury, Zinc, and Cadmium, the number of
volumes must be doubled. -
Hence, the general facts may be stated as follows:–“The com-
bining volumes of all elementary gases are equal, excepting Phos-
phorus and Arsenic, which are one-half, and Zinc, Mercury, and
Cadmium, which are double those of the other elements in the
gaseous state.”
STANDARD PRESSURE AND TEMPERATURE.
In connection with our study of volume-combination, it is im–
portant to understand the method of correcting gases to standard
temperature and pressure, when the volume is estimated at irregular
temperatures and pressures.
The standard pressure is when the barometer stands at 30 inches or
760 millimetres (really 29-92 inches), and the standard temperature is
regarded as 0° Centigrade.
(1.)—Standard Pressure.—This implies “the pressure of a column
of mercury of 30 inches, or of 760 mm , at the temperature of 0° C.”
By the term “1 pressure " or “1 atmosphere * is implied the
weight of a 30-inch column of mercury, which the air (on an average)
is capable of supporting. Such a column is found to press with a
weight of 15 lbs. on the square inch. A pressure of 15 lbs. on the
square inch, therefore, constitutes what is called “l pressure” or “1
atmosphere; ” a pressure of 30 lbs. on the square inch constituting
“2 pressures” or “2 atmospheres,” etc.
The relationship of the volume of a gas to pressure, known as the
Law of Boyle and Marriotte (1662) is as follows:–“ The temperature
being constant, the volume of a gas varies inversely as the pressure;” that
is, the smaller the pressure, the greater the volume; the greater the
pressure, the smaller the volume.
A given quantity of any gas at 1 pressure = 1 volume.
} } 5 y 2 pressures = } volume.
7 5 3 y 4 pressures = } volume.
3 y 3 y # pressure = 2 volumes.
7 5 3 y # pressure = 4 volumes.
Or the facts may be stated thus : —
1 litre of gas at 30 in. B.P. (760 mm.), would occupy 2 litres at
15 in. B.P. (380 mm.), and 0.5 litre at 60 in. B.P. (1,520 mm.); or
100 cubic inches at 1 pressure would become 50 cubic inches under a
pressure of 2 atmospheres, and 200 cubic inches under a pressure of
half an atmosphere.
To correct a gas, therefore, from an irregular pressure to the
standard pressure, the simple rule is,
As the required pressure (i.e. 30 in. or 760 mm.) is to the given pres-
sure, so is the given bulk to the required bulk.
MOLECULAR COMIBINATION. 33
Examples—
(a) If a gas occupies 250 cubic in. at 29.2 in. B.P., what bulk will it occupy at
standard pressure ?
30 : 29-2 : : 250 : æ, Ans. 243.3 c. i.
(3.) If at 754 mm. a gas measures 1:25 litres, what will it measure at standard
temperature ?
760 : 754 : : 1:25 : ac. Ans. 1-240 litre.
(y.) What bulk will a gas occupy at 29 in. B.P. which measures 0-6 litre at 30 in. P
29 : 30 : : 0 6 : a. Ans. 0-62 litre.
(2.)—Standard Temperature.—The law of Charles states that
“ The volume of a given mass of gas, the pressure being constant, varies
directly as the absolute temperature.”
The standard of temperature is regarded as 0°C.
The law of Charles therefore declares, that gases, unlike solids
and liquids, expand by heat and contract by cold regularly for every
increase or decrease of temperature. What, then, is this regular in-
crease? Experiment proves that it is an increase of the 343 part of
the volume of the gas (or 0.00366), for every 1° C., or the +}o part
(or 0.00204) for every 1° Fah. ; Hence—
273 vols. at 0°C. become 274 vols. at 1° C.
273 5 y 3 * 275 ,, 2°C.
273 5 y ? » 373 , 100° C.
If, therefore, a gas measures a litre at 273°C., it will only measure
half a litre at 0°C., the pressure being constant.
To correct for temperature, the rule is, -
“As 273--- the given temperature (in Centigrade degrees) is to 273 +
the required temperature, so is the given bulk to the required bulk.”
Examples— 4.
(a.) A gas measures 1 litre at 273.0°C., what will it measure at 0°C. (standard
temperature)?
273 + 273 : 273 + 0 : : 1 : æ. Ans. a = 0-5 litre.
(3.) A gas measures 25 cubic in. at 20°C., what will it measure at the standard
temperature ?
273 + 20 : 273 + 0 : : 25 : ar. Ans. … = 23:29 c. i.
In stating, therefore, the volume of a gas, it must in all cases be
corrected, (1) to standard pressure (30 in, or 760 mm.), the bulk of the
gas varying, according to the law of Marriotte, “inversely as the pres–
sure; ” and (2) to standard temperature (0°C), the bulk of the gas
varying, according to the law of Charles, “directly as the tempera-
ture.”
MoDECULAR CoMBINATION. CoMBINATION BY WOLUME.
DOOTRINE OF TYPEs.
(1.) A molecule of hydrogen #} is represented thus |HEI (Hydro-.
gen Type). .
One of the H atoms of the molecule, may be replaced by one or
other of the haloid elements (Cl; Br, I, F), to form a hydracid; Thus—
I)
34 HANDTBOOK OF MODERN CEIEMISTRY.
|H| + |Cl | = |H:01 or 1 + 35.5 = 36.5.
1 vol. + 1 vol. = 2 vols.
Such acid may be represented as the combination of 2 volumes of
chlorine (1 molecule) with 2 volumes (1 molecule) of hydrogen, four
volumes of hydrochloric acid gas resulting.
|H| + |Cºol] = Hoi Hol
HCHHCI
Whenever 1 volume of one gas combines with 1 volume of a second gas,
no condensation results; that is, the bulk of the compound formed, is the
same as the bulk of the two gases, and the weight as the weight of the two
gases, from which it was produced. The fact, therefore, is that—
1 litre of chlorine + 1 litre of hydrogen = 2 litres of hydrochloric acid gas.
Or, in other words, a given bulk of hydrochloric acid gas is one-half
hydrogen and one-half chlorine. The same is also true of hydriodic
acid, hydrobromic acid, &c., which are also formed on the hydrogen type.
(2.) # } O represents a molecule of water (Water Type).
Whenever 2 volumes of one gas combine with 1 volume of another gas,
they suffer condensation to the eatent of 4; that is, the bulk of the compound
formed is only 3 that of the original gases from which it was produced,
nevertheless the weight of the two volumes so formed, is the total weight of
the three volumes that formed them. Thus—
|H|H| + |o | = | Hjo or 2 + 16 = 18.
2 vols. + 1 vol. - 2 vols.
This, again, constitutes a type of another group of compounds,
such as H2S, H2Se, etc.
H
(3.) H N represents a molecule of ammonia gas (Ammonia Type).
EI
Whenever 3 volumes of one gas combine with 1 volume of another gas,
they suffer condensation to the eatent of #; that is, the bulk of the com-
pound formed is only one-half that of the original gases from which it was
produced, nevertheless the weight of the two volumes so formed, is the total
weight of the four volumes that formed them. Thus—
|HiRi H| + |N| = |N H, or 3 + 14 = 17.
3 vols. + 1 vol. = 2 vols.
TH
(4.) # C represents a molecule of marsh gas (Marsh Gas Type).
PI
Whenever 4 volumes of one gas combine with 1 volume of another gas, they
UNIT OF WOLUME-THE CRITH, 35
suffer condensation to the extent of #; that is, the five volumes, after com-
bination, only measure 2 volumes, nevertheless the weight of the two volumes
so formed, is the total weight of the five volumes that formed them. Thus—
|H|H|H|H| + c = |c H, or 4 + 12 = 18.
4 vols. + 1 vol. = 2 vols.
It would thus appear that the molecules of compound bodies in the
gaseous state, occupy twice the volume of an atom of hydrogen gas;
all compounds, no matter what the number of atoms or volumes may
be of which they are composed, becoming condensed into 2 volumes.
Relative Weights of Compound and Elementary Gases.
By the Specific Gravity of a gas we imply its weight compared with
Gº)".
By the relative weight of a gas we imply its weight compared with
hydrogen.
(a.) In the case of the elementary gases, it is manifest that their
atomic weights must be also their relative weights. A given volume of
oxygen weighs 16 times as much as a similar volume of hydrogen;–
16, therefore is the relative weight of oxygen.
(3.) In the case of compound gases it must be remembered that after
the combination of their constituent elements, two volumes are formed.
Hence the relative weight of any compound gas is the sum of the
weights of the component elements divided by 2. For example, a
volume of hydrogen (1) and a volume of chlorine (35°5) form two
"O o) 1825 in the
relative weight of hydrochloric acid gas;–in other words hydro-
chloric acid gas is 18-25 times heavier than hydrogen. Similarly
volumes of hydrochloric acid gas. Hence (*
Aºd
2
water gas is (*= 9 times heavier than hydrogen, and ammonia
gas (;--) 8-5 times, and marsh gas (** =) 8 times heavier.
These numbers therefore constitute the relative weights of these
compound gases.
Unit of Wolume.—The Crith.-Hydrogen, being the lightest
known gas, is regarded not only as the unit of weight, but as the unit of
volume. A litre of hydrogen weighs 0.0896 grim., this number being
called a crith (ºp.6), a barleycorn).
(a.) The weight of a litre of any elementary gas, is found by mul-
tiplying 0.0896 grim. (i. e., the weight of a litre of hydrogen) by its
atomic weight. Thus—
1 Litre of oxygen weighs 0.0896 × 16 = 1,433 grim.
1 Litre of nitrogen ,, 0.0896 × 14 = 1.254 grim.
(6.) The weight of a litre of any compound gas is found by multiply-
36 FIANDBOOK OF MODERN CHEMISTRY.
ing 0.0896 grm. by half its molecular weight, inasmuch as the molecular
weight represents two volumes. Thus—
1 Litre of water gas (mol. wt. 18) weighs 0.0896 × 9=0.806 grim.
1 Litre of carbonic anhyd.(mol. wt. 44) ,, 0.0896 × 22=1971 grim.
1 Litre of marsh gas (mol. wi. 16) ,, 0.0896 × 8=0-716 grim.
II. A gramme (15:432 grains) of hydrogen at 0°C, and at 760 mm.
pressure measures 11.2 litres. Therefore the atomic weights of the
elementary gases, and half the molecular weights of the compound
gases represent in grammes the quantity necessary to occupy 11.2 litres.
(a.) 1 grn. Of hydrogen measures 11.2 litres,
16 grims. of oxygen measures 11:2 ,,
14 grms. of Initrogen measures 112 , ,
(3.) 9 (...) grims. of water gas measures 11.2 litres.
22 (...) ,, of carbonic anhydride measures 11.2 litres.
8 ( º) ,, of marsh gas measures 1 l'2
2
Relation between Atomic Weights and Specific Gravity.—
So far as solids and liquids are concerned, no relationship has as yet
been traced between atomic weights and specific gravities, but in the
case of both simple and compound gases the relationship is definite, and
obedient to fixed rules.
(a.) In the case of elementary gases and vapors we have said that the
atomic weights of the elements represent equal volumes of the elements at
5 5
the same temperature and pressure. Thus, if [H] = 1 ; then |o – 16
and |N = 14. Or, to state the same truth in another way,
1 grain of hydrogen, 16 grains of oxygen, and 14 grains of nitrogen:
occupy, the temperature and pressure being uniform, 44.473 cubic
inches. If, then, we regard the specific gravity of hydrogen as 1, and
employ it as the standard of comparison, it is manifest that the atomic
weights of the elementary gases and vapors are also their relative
weights, hydrogen being regarded as the standard of comparison.
But, in stating specific gravities, air, and not hydrogen, constitutes
our standard of comparison, and is regarded as equal to 1. Air having
a specific gravity of 1, hydrogen is found to have a specific gravity of
0.0694; that is, the specific gravity of air as compared to hydrogen, is
as 1 to 0-0694. Therefore, to find the specific gravity of any element-
ary gas or vapor, all that is necessary is to multiply its atomic weight
by 0-0694, the specific gravity of hydrogen.
To find the specific gravity of oxygen, chlorine, and nitrogen:
0-0694 × 16 (atomic weight of oxygen) = 1° 1104, Sp. Gr. of oxygen.
0-0694 × 35'5( 25 of chlorine)= 2:46:37, ,, of chlorine.
0-0694 × 14 ( 92 of nitrogen)= 0-9716, ,, of nitrogen.
RELATION BETWEEN ATOMIC. WEIGHTS AND SPECIFIC HEATS. 37
There are the following exceptions to be noted to this rule—
(1.) The vapor densities of phosphorus and arsenic compared to
hydrogen are twice their atomic weights; therefore in estimating the
specific gravities of these bodies the atomic weights must be doubled—
31–atomic weight of phosphorus; 0.0694×(31 × 2)= 4:3028, Sp. Gr. of phos. vapor.
75= 2 3 of arsenic ; 0-0694×(75×2)=10:410 ,, of arsenic ,
(2.) The vapor densities of mercury, zinc, and cadmium compared to
hydrogen, are one-half their atomic weights; therefore, in estimating
the specific gravity of these bodies the atomic weights must be
halved—
& * 200
200 = atomic weight of mercury; 0.0694× (*)= 6-94 Sp. Gr. of mercury vapor.
| 12 *
112 - 23 of cadmium; 0-0694 × (*)= 3-8864 , of cadmium ,
(3.) In the case of compound gases and vapors.—The molecule of a
compound body, it must be remembered, is always twice that of the
hydrogen atom. Therefore—
Molecular weight X 0-0694
•)
*/
OT Relative weight X 0-0694 = Sp. Gr.
Examples:
nel,” ׺ (HCl) = 1.2665 Sp. Gr. of hydrochloric acid gas.
II,0; 0-0694 ׺ (OH.) == 0:6246 Sp. Gr. of water gas.
II.N.; 0-0694 ׺ (NHI) = 0-5899 Sp. Gr. of ammonia gas.
2 3 0-0694 x * (CO.) = 1°5268 Sp. Gr. of carbonic acid gas.
4-
There are certain exceptions to this rule in such compounds as
PCl; (2)—SbCls—Hg2Cl2, where the molecule occupies 4 volumes and
not 2, although this compound of 4 volumes resolves itself by heat
into two compounds of 2 volumes each.
Relation between Atomic Weights and Specific Heats.-
The “specific heat” of a body is the “quantity of heat” that a body
gives out or takes in, whilst passing from one temperature to another.
This is ordinarily determined by taking equal weights of bodies and
estimating the quantity of heat required to raise them to a given tem-
perature.
(1.) For purposes of comparison the following standard is adopted
tn England, viz.:-
“The quantity of heat required to raise 1 lb. of water 19 C.”
This 1 pound of water is called “the unit of weight,” and the 19 C.
is called “the unit of heat” or “thermal unit.” It is clear, therefore,
that to raise 1 lb. of water from 0° C. to 100° C. would require
100 units of heat.
(2.) The standard of comparison in France is—
“The quantity of heat required to raise 1 kilogramme of water 18 C.”
\
38 HANIDBOOK OF MODERN CHEMISTRY.
A kilogramme being equal to 2.2 lbs., it follows that every French
unit of heat is equal to 2-2 English units of heat.
Water is chosen for purposes of comparison, because (excepting
hydrogen) it requires more heat to raise its temperature than any
other known substance.
Hence, the quantity of heat necessary to raise 1 lb. of water 1*C. is
called 1, and this constitutes our starting-point.
When we say, therefore, that the specific heat of iron is equal to
0.1138 and that of hydrogen to 3.4090, we imply that if it would take—
1'000 unit of heat to raise 1 lb. of water 19 C.; it would require
0.1138 ; 2 32 1 lb. of iron 1* C.; or
3'4090 2 3 7 2 1 lb. of hydrogen 19 C.
Now it is found that although the numbers obtained as the specific
heats of different bodies are very dissimilar, there is a remarkable
uniformity in the products of the specific heats when multiplied by
the several atomic weights. This number is termed the atomic heat of
the body, and in the case of the elementary bodies commonly varies
not more than from 6 to 7.
SPECIFIC PIEATs of ELEMENTARY BODIES.
Specific Heat. Atomic Product of
Elements. (that of W . tS Sp. Heat X
Water=1). eignts. At. Weight.
Lithium .. tº e tº e tº 0'9408 7. 6'59
Sodium . . & © e s tº e ()' 2934 23- 6-75
Aluminium * = * * & ſº 0-2143 27-4 5' 89
liquid § 4 • * 0-2120 4) T , 6-57
Phosphorus [..." . . 0-1887 | 31 | 5- 85
Sulphur . . e Q & Q & © 0-2020 32. 6 : 48
Potassium . . * * • * * 0- 1696 39. 6: 61
Iron gº º & $ & sº * & (): 1138 56. 6-37
Nickel * * * † & & tº tº (). 1086 58.8 6-37
Cobalt * * sº ſº e 9 * * (). 1070 58.8 6-28
Copper . . * * tº º tº G 0.0952 63-4 6:04
Zinc tº gº tº gº * e gº º 0.0956 6.5 °2 6 - 24
Arsenic .. tº ſº * & tº º 0-0814 75. 6-10
Selenium .. * * tº º • * 0.0762 79-4 6' 02
Bromine (solid) . . * 9 # * 0° 08:43 80. 6.75
Palladium . . * @ * = * g. 0.0593 106-6 6' 31
Silver * * & & tº sº & tº 0.0570 108- 6 - 16
Cadmium .. w º * * * * 0.0567 1 12- 6' 35
Indium .. * * * * * * 0 0570 113° 4 6-46
Tin tº ſº. tº e tº º fe tº 0.0562 I 18. 6.63
Antimony .. * * tº º * * 0-0508 122- 6 - 19
Iodine g & * * tº º & g 0.0541 127. 6'87
Tellurium .. # at * * s & 0-0474 128- 6° 06
Gold tº s • * 4 tº * * 0.0324 197. 6°38
Platinum . . § e tº s a q 0.0311 197'4 6- 15
solid . . tº g * - 0.0319 g 6'38
Mercury | liquid. . . . . . 0.0333 | 200 | 6'66
Thallium . . g tº & ſº sº tº ()' 03:35 204 - 6-83
Lead tº º * * * * * & 0.0314 207- 6-50
Bismuth . . & $ * * § & 0.0308 210° 6 "48
It will thus be seen that the specific heats of these several bodies
multiplied by their atomic weights, produce an almost constant
ATOMICITY OR QUANTIVALENCE. 39
product. We may conclude from this that probably all atoms require
the same amount of heat to raise their temperature one degree. This
result accords with the surmises of Dulong and Petit, who thought
that the atoms of all elementary bodies had the same atomic weight.
Thus far the law may be stated as follows: “The specific heats of
elementary bodies is inversely as their atomic weights.”
There are, however, some apparent exceptions, as will be seen in the
following table, although the results obtained by Professor Weber
point to the fact that these bodies at high temperatures obey the law
of Dulong and Petit. (“Quarterly Journal of Science,” Jan., 1876.)

Specific Heat Atomic s: #. of
(Water=1). Weight. ... º.º.
... Weight.
Boron tº º 0-2500 X 11 - 2.75
Hydrogen . . 3.29 X 1 - 3.29
Nitrogen . 0-27 X 14 - 3.78
Oxygen . . tº tº 0-23 X 16 - 3 : 68
charcoal (): 24 l 5 × 12 - 2.96
Carbon graphite 0-2008 X 12 - 2:41
| diamond • () 1469 X 12 - 1:76
Silicon - - * & e - . . . 0 1774 X 28 ~ 4-97
In the case of compounds of similar atomic composition and consti-
tution, the specific heats are also inversely as their atomic weights.
Atomicity or Quantivalence.—The terms quantivalence (quanti
and valeo), dynamicity, or atomicity imply, that although the symbol of
an element (such as O, N, etc.), represents an atom of that element,
the atom having an unchangeable relative weight (for of the absolute
weights of the atoms we know nothing with certainty), nevertheless,
that such symbol does not express “the valence ’’ or “chemical value,”
or “power” of such atom, this power varying with different bodies.
Thus in hydrochloric acid (HCl), 1 of chlorine is satisfied with, or,
in other words, has the same value as, 1 of hydrogen. Under no cir-
cumstances can 1 of chlorine combine with more than 1 of hydrogen.
But in Water (H2O) we find that 1 of oxygen is not satisfied with less
than 2 of hydrogen, whilst in marsh gas (CH) the carbon atom is
not satisfied with less than 4 of hydrogen. Thus it is evident that the
power of carbon, as represented by the symbol C, is chemically equal
to 4 hydrogens, or (H,), the symbol O being chemically equal to 2
hydrogens (H2), and the symbol Cl to 1 hydrogen (H). The terms
quantivalence, dynamicity, or atomicity express, therefore, the fact that
an atom of one element may be chemically equal to, and have the power
of fixing, one or more atoms of other elements.
Further, we must note that the term equivalent (ºguus, equal, and
valeo, I am worth) is not synonymous with atomic weight, for whilst
hydrogen, oxygen, and carbon have atomic weights of 1, 16, and 12
respectively, nevertheless, 1 of carbon is equivalent to 2 of oxygen
and to 4 of hydrogen, whilst 1 of oxygen is equivalent to 2 of
hydrogen.
40 HANDBOOK OF MODERN CHEMISTRY.
The value or atomicity of bodies is often indicated by what are
called graphie formulae, the valence of an element being represented by
lines or bonds, expressive of what Frankland calls its atom-fixing power.
Thus, Cl—, -0–, –– represent graphically chlorine as a
monad with one bond, oxygen as a dyad with two bonds, and carbon
as a tetrad with four bonds. Chlorine, we know, can only fix one
atom of hydrogen to form a molecule of HCl (thus Cl–H=HCl),
whilst oxygen can fix two hydrogen atoms to form a water molecule
(H–0–H=OH2), and carbon can fix four hydrogen atoms to form a
EI
marsh gas molecule, H–C–H=(CH4). Thus the lines are expres–
|
H
sive of the atomicity of a body, and are to be regarded as pictures
representing the number of bonds, and how they are severally utilized.
No element can exist with its bonds unconnected or dissatisfied. It
is clear, therefore, that the molecule of every element possessing an
uneven number of bonds (i. e., being a perissad) must consist of two
or more atoms united. You cannot have hydrogen in a free state
thus —TI; but you can have it thus, H–H. Hence we regard IIc
as the hydrogen molecule, and not H. In the case of an artiad, i.e., an
element possessing an even number of bonds, the molecule may consist
of one atom (monatomic), inasmuch as the bonds, by combining amongst
themselves, may satisfy each other, and so become latent. Thus, a
molecule of oxygen may be represented as —O— ; whilst, on the
`-----——-
other hand, it must be remembered that the oxygen molecule may also
be diatomic, represented thus, O=0, or triatomic (as in the case
O
of ozone), represented thus Co (polyatomic).
Glyptic formula are merely material illustrations of graphic formulae,
where atoms are represented by balls, and lines by Wires.
METHOD of DETERMINING THE QUANTIVALENCE OR ATOMICITY
of A BODY.
Agreeing to understand by the quantivalence of a body, the number
of univalent atoms with which the symbol representing its atomic
weight can unite, we determine this quantivalence in such Ways as
the following:—
(1.) By the number of hydrogen atoms with which a body can combine to
form a molecule.
Eacample. I of hydrogen combines with 1 of chlorine. Therefore
the valence of chlorine = the valence of hydrogen.
(2.) If an element will not combine with hydrogen, but will combine with
chlorine, its valence may then be determined by the number of chlorine atoms
with which it will combine to form a molecule.
METHOD OF I) ETERMINING QUANTIVALENCE. 41
Epample. 1 atom of silver (Ag) combines with 1 atom of chlorine,
and in that proportion only. But silver will not combine with hydro-
gen; inasmuch, however, as 1 of chlorine combines with 1 of hydrogen,
and l of chlorine also combines with 1 of silver, if ever silver could
be made to combine with hydrogen, we infer it would do so in the
proportion of 1 atom of hydrogen to 1 atom of silver. We may ex-
press these facts thus—
(1.) The valence of silver=the valence of chlorine;
(2.) The valence of chlorine=the valence of hydrogen;
Therefore (3.) The valence of silver=the valence of hydrogen.
It will thus be seen that hydrogen, chlorine, and silver are equi-
valent.
(3.) By the proportion of hydrogen which a body can replace in a saline
molecule.
Eacamples. (a.) A water molecule is made up of 2 atoms of hydrogen
and 1 of oxygen. One or both of the hydrogen atoms may be replaced
by an alkaline metal, such as potassium. Thus—
H n IT n. H l n rio. R. o –
#| 0 = H,0; i: ) o – RHo: #!o = K.0
It is clear, therefore, that the value or valence of potassium is
identical with the value of hydrogen.
(b.) Again : calcium, zinc, or barium may also be made to take the
place of hydrogen, but under such circumstances it will be found that
1 atom of these elements is equivalent to 2 atoms of hydrogen. Thus—
#} O = H,0; Ca"O (not Ca.0); Zn"O (not Zn20).
Hence, the valence of calcium or of zinc is double that of hydrogen,
inasmuch as 1 of zinc or 1 of calcium can replace 2 of hydrogen in a
molecule.
Looking, therefore, at these facts, it is clear that the elements have
very different values in their capacities for substitution displacement.
Agreeing to regard hydrogen as our standard of equivalence, it is
evident that the elements are susceptible of arrangement into groups.
Group I.
Certain elements are univalent; that is, 1 atom in chemical exchange
is equal in value to 1 atom of hydrogen or other univalent element.
Such bodies are called monad elements.
Group II.
Certain elements are divalent; that is, 1 atom in chemical exchange
is equal to, and may replace, either (a) 2 atoms of hydrogen, or 2
atoms of any other monad; or (b) 1 atom of any other divalent ele-
ment. Such bodies are called dyad elements.
42 HANIDBOOK OF MODERN CHIEM ISTRY.
Group III.
Certain elements are trivalent; that is, 1 atom in chemical exchange
is equal to (a) 3 atoms of hydrogen or other monad element; or to (b)
1 atom of a divalent element + 1 atom of a monad element. Such
bodies are called triad elements.
Group IV.
Certain elements are quadrivalent; that is, 1 atom in chemical
exchange is equal to (a) 4 atoms of hydrogen or other monad element;
or to (b) 2 atoms of oxygen or other dyad element; or to (c) 1 atom of
a dyad-1-2 atoms of a monad element; or to (d) 1 atom of a triad
+ 1 atom of a monad element.
Groups W. and VI.
Certain elements are quinquivalent and hearivalent; that is, 1 atom in
chemical exchange is equal to 5 and to 6 atoms of hydrogen or their
respective equivalents.
We have borrowed from Dr. Frankland’s Lecture Notes the fol-
lowing diagram, representing at a glance the atomicity of the elements.
The metalloids are printed in thick type, and the metals in ordinary
Boman type.
TABLE OF ATOMICITIES (Frankland,)

Monads. Dyads. Triads. Tetrads. Pentads. Hexads.
I. I. I. I. I. I.
Hydrogen. 0xygen. Boron. Carbon. Nitrogen. Sulphur.
Silicom. Phosphorus. Selenium.
II. II. II. Tin. Wanadium. Tellurium.
Fluorine. Barium. Gold. Titanium. Arsenic.
Chlorine. Strontium. Antimony. II.
Bromine. Calcium. III, II. Bismuth. Tungsten.
Iodine. Magnesium. | Thallium. Thorium. Molybdenum.
Zinc. Niobium. *---------
Tantalum. III.
III. III. Zirconium. Osmium.
Caesium. Didymium. Aluminium. Iridium.
Rubidium. Lanthanum. Indium. Ruthenium.
Potassium. Yttrium. Rhodium.
Sodium. Glucinum. III.
Lithium. Platinum. IV.
Palladium. Chromium.
IV. IV. Manganese.
Silver. Cadmium. IV. Iron,
Mercury. Lead. Cobalt.
Copper. Nickel.
Uranium.
Cerium.

Although we thus arrange elements in their several classes according
to their value as best we know them, it must not be supposed that
we are in a position to fix their several positions definitely. In some
cases the valence of an element varies : Carbon, for example, in marsh
METHOD OF DETERMINING QUANTIVALENCE. 43
gas is a tetrad (CºH). So also it is a tetravalent in carbonic anhy-
dride (CwO.), whilst in carbonic oxide (C"O) it plays the part
of a dyad. Nitrogen, again, may act as a monad, as in N2O, or
as a triad, as in NHs, or as a pentad, as in NH4C1. Admitting
that these variations are difficult of explanation and somewhat inter-
fere with general conclusions, we may note, as Dr. Frankland re-
marks, that the variation always takes place by the disappearance
or development of an even number of bonds. Thus nitrogen may
| N |
be a monad (–N), a triad (–N–), or a pentad (, N, ); it is never a
dyad, or a tetrad. Carbon may be a dyad (–C–), or a tetrad
(–C–), but it is never a monad or a triad. In short, a perissad is
never an artiad, or an artiad a perissad. Dr. Frankland explains
these variations by supposing that some of the bonds may unite and
become latent. Thus nitrogen with its five bonds ( N' ) becomes a
triad by the union of two ; thus ( N ). In this way Dr.
/ N
—’
*-
Frankland distinguishes between latent atomicity, or the number of
conjoined bonds; active atomicity, or the total number of bonds in
actual combination with other elements; and absolute atomicity, the sum
of the latent and the active atomicities. Whenever an element is
fully saturated, that is, has received its full value of other elements,
the body so formed is more stable than when its valence is not
fully satisfied. Thus CO2 is a more stable body than CO. Hence
the true valence of an element is always indicated by the largest
number of hydrogen or other monad elements with which it can
combine. The valence, moreover, must not be determined from oxides
or from sulphides, because each dyad, made up as it is of two units of
equivalency, neutralizes one unit in the compound it enters, and
introduces a second unit, leaving the equivalence as it was before.
For convenience these several groups are divided under the two
heads of Odds and Evens.
Monads.
(1.) Odds or Perissads (reptorooc, odd) { Triads.
l Pentads.
ſ Dyads.
Tetrads.
Hexads.
The quantivalence of bodies is usually denoted by placing dashes
or Roman figures to the right of the symbol. Thus H" with one
dash means that hydrogen is a monad; O" with two dashes that
oxygen is a “dyad; whilst C" shows carbon to be a tetrad, and so forth.
(2.) Evens or Artiads (&prioc, even)
44 IIANDBOOK OF MODERN CHEMISTRY.
Chemical Formulae,
The object of chemical formulae is to express the composition and
the probable constitution of a chemical substance. Formulae are
of two kinds—
(1.) Earperimental or empirical.
(2.) Theoretical or rational.
I. EXPERIMENTAL OR EMPIRICAL ForMULE.
An empirical formula represents merely by the smallest integers
the number of atomic proportions of the several elements present
in a body. It is the expression of the actual experimental results
of analysis. An empirical formula in no way represents the groupings
of the elements. We give an illustration in detail of the determina-
tion of the empirical formula of magnesic sulphate.
(1.) Determine percentage composition. On analysis, we should find
in every 100 parts of magnesic sulphate—
Magnesic oxide (magnesia) . . 16-26
Sulphuric anhydride . . . . . .32-52
Water . . . º . . . 51' 22– 1 00:00
(2.) Divide these numbers (i.e., the percentage numbers) severally by
their atomic weights. Thus, 40, 80, and 18 represent respectively
the atomic weights of magnesia, sulphuric anhydride, and water;
therefore—
16' 26 32°52 51-22
= .4065; ºf-4065; sº-2,845.
(3.) Reduce the quotients thus obtained to their simplest eayression.
Thus—
Magnesia. Sulphuric anhydride. Water.
The ratio of the numbers 0.4065 () - 4065 2-84.5
corresponds to 1 1 7
From which it is clear that the relative atomic proportion of magnesia
(MgO) to sulphuric anhydride (SO3) is as 1 to 1, and of these to water
(H2O) as 1 to 7. Thus, MgO +SO3 +H1,0; or MgSO11H1, represents
the experimental or empirical formula for magnesic sulphate.
Hence the rules to determine the empirical formula of a body may be
thus summarized—
(1.) Determine by analysis its percentage composition.
(2.) Divide the numbers so obtained by their atomic weights.
(3.) Teduce the quotients to their simplest expression.
II. RATIONAL OR THEORETICAL ForMUL.A.
Such formulae represent not only the elements present and their
atomic proportions, but the manner (according to every man's views
or fancies) in which these elements are grouped. Thus, magnesic
sulphate may be written MgO, SO3, 7 H2O, or MgSO4, H20,6H2O, and
CHEMICAL FORMUL.A. 45
in many other ways; and it may be judged if different opinions exist
as to the exact method of expressing the theoretical formula of so
simple a body as magnesic sulphate, what a play there is for imagina-
tion in the expression of the formulae of complex organic bodies. For
example, there are nineteen different ways of representing acetic acid
(C.H.O.). Such formulas are as yet merely theoretical formulas, and
although in many cases true, and in many other cases the approach
to truth, must be received with caution.
Of late what are called constitutional formulae, as suggested by
Dr. Frankland, have found favor with chemists, and, inasmuch as We
have in part adopted their use, it is necessary to explain them in detail.
A constitutional formula is designed to give us some idea of the
arrangement of atoms in a molecule. In a constitutional formula the
symbol of the principal element is placed first, thereby denoting that
the several elements, or compound radicals following it on the same
line, are held to it, as the principal element of the molecule, by what
Frankland terms bonds. We may thus regard the molecule as a
family, and the principal element, as the parent or head of the family.
Further, to distinguish constitutional formulae from molecular or
empirical formulae, the head of the family, or the principal bondholder
or bondholders are printed in thick type. A few illustrations will
render this clear:—
OTH, is the constitutional formula for water, and implies that the
dyad atom oxygen is the parent bondholder, or grouping element,
of the water molecule, and is combined by bonds to each hydrogen
atom. Graphically it may be symbolized thus, H–0–H.
SO. Hoe is the constitutional formula for sulphuric acid. Here
sulphur is the parent bondholder, having six bonds (hexad), four of
which are united with the four bonds from the two oxygen atoms
(oxygen being a dyad), and two with the bonds of the two half
molecules of hydroxyl (Ho).
|
Graphically it may be symbolized thus, H–0—S—0–H
|
O
It will thus be seen that constitutional formulae are merely methods
of representing glyptic and graphic formulae symbolically.
In expressing many constitutional formulae a bracket is used.
Thus, potassic chlorate (KClO3) is represented either—
Cl -
(a.) as {3}, which means that one bond from each oxygen
atom (oxygen being a dyad) is joined to 1 of chlorine and to 1 of
potassoxyl (Ko) respectively, whilst the two atoms of oxygen are
united together by 1 bond from each.
Graphically the con- (OCI ) may be expressed ſ O–Cl
stitutional formula (OKo j thus | *
O—Ko ; or
46 HANDBOOK OF MOIDERN CHEMISTRY.
O—Cl
ſool |
(3.) as ić K or graphically as O which implies—
O—K
that one of the bonds of the first oxygen atom is combined with the
monad chlorine, and the other with one bond from a second oxygen
atom, the other bond of which is combined with a third oxygen atom,
this last having its second bond united with the potassium atom.
Thereby all bonds are satisfied.
Substitution (Substitutus, put in another's place).
(A.)—Inorganic.—Having regard to the molecular constitution of
matter, we find that, in mineral chemistry, the several constituents
of a molecule may be replaced (i.e. substituted) by their equivalent of
other bodies, without changing the typical constitution of the original
molecule. Thus—
(1.) # | represents a molecule of hydrogen.
(a.) One hydrogen atom (monad) of this hydrogen molecule may be
replaced by a haloid atom (monad) to form the hydracids; thus—
HH ; HCl ; HBr ; HI; HF.
(3.) One hydrogen atom may also be replaced by an alkaline metal,
to form a hydride.
(2.) # | O (=H.0) represents a molecule of water.
(a.) One or both hydrogen atoms of this water molecule may be
replaced by an alkaline metal; thus—
Hydrates Oxides
TI * fº . Na . º – TNa
#| 0: #}o: *}o: #| 0 N: 0.
(3.) Two hydrogen atoms may be replaced by one of a dyad ele-
ment; thus—
TI
H
(y.) The dyad oxygen may be replaced by the dyads sulphur, sele-
nium, or tellurium; thus—
FI
#}o: #}s. #}se: #}Te.
| O ; Zn"O ; Ca"O ; Ba"O.
FI
(3.) #| N (=NH2) represents a molecule of ammonia.
H
(a.) The three hydrogen atoms of this ammonia molecule may be
replaced by three chlorine, bromine, or iodine atoms; thus-
NH, ; NCl3; NBr3 ; NI3.
*
SUBSTITUTION. 47
(ſ3.) A part only of the hydrogen may be replaced by a metal, or
by a compound radical; thus—
NH, ; NH.K (Potassamide); (SO2(NH3)2) (Sulphamide).
(y.) The nitrogen may be wholly or partially replaced by phospho-
rus, arsenic, antimony, and perhaps by bismuth.
EI
(4.) # C (=CH-) represents a molecule of marsh gas.
H
Here substitutions are endless, as we shall note more particularly
under organic chemistry.
(5.) In the formation of salts, the hydrogen of an acid is replaced
by one or more atoms of a metal or compound positive radical; thus—
(a.) Sulphuric acid contains two displaceable atoms of hydrogen
(H2SO4).
1 hydrogen may be displaced by 1 of potassium (monad) forming HKSO, (acid salt.)
2 hydrogens 3 * 3 × 2 of 3 3 ( , ) , K.S.0, (normal salt.)
2 hydrogens 3 * 3 y 1 of calcium (dyad ) , CaSO,
(B.) Phosphoric acid contains three displaceable atoms of hydrogen
(H3PO).
3 hydrogens may be displaced by 3 of silver (monad) Aga PO,
2 5 * 2 y 2 of sodium ( , ) HNa,PO,
I } } 3 y 1 of , ( , ) NaH2PO,
Similarly, 1 triad will take the place of 3 monads, or 1 dyad of
2 monads. -
(B.) Organic.—The substitution of compound radicals for elements,
forms a remarkable feature in organic chemistry. Liebig defined
organic chemistry as “the chemistry of compound radicals.”
(1.) One of the hydrogen atoms of a hydrogen molecule (HH) may
be replaced by such compound radicals as Methyl (CH3), Ethyl (C.Hs),
Propyl (C8H1), etc., whereby a hydride of the organic radical is
formed. Thus—
(CHA)H = Methyl-hydride : (C,EIs) II = Ethyl-hydride; (C.H.) H = Propyl-hydride.
Further, the hydrogen of these compounds may be replaced by
chlorine or cyanogen. Thus—
(CHA)Cl= Methyl-chloride; (C.H.)Cl– Ethyl-chloride; (C.H.)C1 = Propyl-chloride.
(CHA)Cy= Methyl-cyanide; (C.Hs)Cy= Ethyl-cyanide ; (C.H.)Cy= Propyl-cyanide.
(2.) In the alcohols and ethers, we find bodies constructed on the
water (H2O) type.
(a.) One hydrogen of a water molecule may be replaced by a com-
pound radical to form an alcohol; thus—
C# | O = Methyl alcohol ; º } O = Ethyl alcohol.
(3.) Both atoms of hydrogen may be replaced by two of the com-
pound radical to form an ether; thus—
§: | O = Methyl ether ; §: } O = Ethyl ether.
48 HANDBOOK OF MODERN CHEMISTRY.
(Y.) Or the oxygen may be replaced by sulphur, and perhaps by
Selenium; thus—
º S = Ethylic sulphydrate ; º | S = Ethylic sulphide.
(Mercaptan.) 21–1-5 (Sulphur ether.)
(6.) Or the oxygen may be replaced by silicon, or by a metal,
whereby the metallic ethyls, etc., are produced; thus—
CH,
CH,
(3.) Bodies constructed on the ammonia (NHA) type are found in
the amides and in the alcoholic ammonias.
(a) One or more atoms of hydrogen may be replaced by one or
more compound radicals, such as ethyl (C,Eſs); thus—
} Zn = Zincio methide. 9% | Hg = Mercuric ethide.
C.E. ſ. *ē
C.H.; C., H3
H | N = Ethylamine ; C., H3 |s = Diethylamine;
EI H
C.H.;
§ N = Triethylamine.
21-15 J .
(3.) One or more atoms of hydrogen may be replaced by an oxy-
dized radical, as in the “amides,” or else by different radicals; thus—
H ), N = Acetamide ; C.H.30 × N = Diacetamide;
EI (called a primary H (called a secondary
amide.) amide.)
C.H.30
§ N = Ethylic Diacetamide,
C2H5
(y.) The nitrogen may be replaced by arsenic, antimony, bismuth,
etc., as follows:–
CH, C. Eſs
CH3 } As = Trimethylarsine; C2Hg | Sb = Triethyl-stibine ;
CH3 C2H5
CH, o
EI
P = Methyl-phosphine.
EI -
(4.) In the case of the marsh gas (CHA) molecule, the substitutions
are without number, the hydrogens being replaced in almost endless
variety.
Isomerism (loog equal, piépoc a part).
Isomerism is a term applied to bodies containing the same ele-
ments, united in the same proportions, but differing more or less
widely in their physical, physiological, and chemical properties.
Isomerides are of two classes:— *
(1.) Where the percentage composition is similar, but the molecular
composition dissimilar (polymers);
(2.) Where both the percentage and the molecular compositions
are alike (metamers).
ISOMERISM. * 49
I. Isomerides having similar percentage but different molecular composition;
in other words, having different vapour densities (Polymerism). Examples
of such isomerides (polymers) are seen in the following cases : —
(a.) Cyanogen (CN or Cy), a poisonous gas, and Paracyanogen
(C"N" or Cy"), an inert solid, alike contain in every 100 parts—
Carbon 46:15; Nitrogen 53-85.
(3.) The chlorides of Cyanogen, viz.:-
CyCl = gaseous chloride of cyanogen,
Cy2Cl3 = liquid 3 y 3 y
CyåCls = solid 5 y 5 y
have a similar percentage composition, viz.:-
Carbon, 19:51; Nitrogen, 22.77; Chlorine, 57.72.
Further illustrations of polymerism may be found in the cyanogen
oxyacids (viz., cyanic, fulminuric, and cyanuric acids, and cyamelide);
also in the various hydrocarbon series, and in numerous other cases.
II. Isomerides having an identical percentage and molecular composition
(Metamerism). These bodies, consequently, have similar vapour
densities. Examples of such isomerides (metamers) are seen in the
following cases:–
(a.) Urea [(2NH.)CO] and ammonic cyanate [CN(NH,0)], both of
which are represented by the formula CH4N2O, contain in every 100
parts—
Carbon tº º – e G & tº º º 20:00
Hydrogen ... * * * e ºr tº 6-67
Nitrogen ... tº ſº º tº º º 46' 66
Oxygen ... ... ... 26:67–100.00
(3.) The “turpenes” (which include oils of turpentine, lemons, ber-
gamot, neroli, lavender, pepper, camomile, carraway, cloves, etc.),
have all a similar composition (C10H16).
(y.) Tartaric acid (which turns the plane of polarized light to the,
right, and is hence called dextro-tartaric acid); racemic acid (which has
no action on a ray of polarized light); paratarfaric acid (which turns
the ray to the left, and is hence known as levo-tartaric acid), have a
similar percentage and molecular composition (C,EI606).
(3.) Morphia (the active principle of opium) and piperine (the active
principle of pepper), are both represented by the formula C7H16NOs.
We may note that these isomerides are divisible into two classes:–
1. Bodies differing in physical properties, but behaving alike under the
action of chemical reagents. Such, for example, are the turpenes, a
series of true isomerides; and
2. Bodies differing in physical properties, and also behaving differently
under the action of chemical reagents. In such bodies we note the pre-
sence of different radicals. For example, propionic acid, methyl
acetate, and ethyl formate are isomeric (Cs FISO2), but their behaviour
respectively with potassic hydrate is vastly different. Thus—
IE
50 EIANDDOOK OF MODERN CHEMISTRY.
! Propionic acid with potassic hydrate yields potassic propionate.
2 Methyl acetate potassic acetate and methyl alcohol.
3 Ethyl formate potassic formate and ethyl alcohol.
Isomorphism (tooc equal, and poppi) a form).
Acids may frequently be substituted for acids, and bases for bases,
in a body, without the body undergoing any alteration of form. Thus,
in common potash-alum (K24]24SO4,24H2O), the K2 may be replaced
by Nag, or by (NH4)2, and the Al, by Fe, Mng, or Cra, etc., without
any change of form resulting. Bodies that crystallize in the same form,
and which are similar in chemical constitution, are termed Isomorphous.
It has been suggested (Blake, B. Assoc., 1846) that there is a rela-
tionship between the physiological action of bodies and their isomor-
phic condition. Thus, arsenic acid can replace phosphoric acid in the
human body, the latter acid being a normal constituent. Hence,
arsenic acid is not a poison; whilst arsenious acid, having no homo-
logue in the human body, acts as a poison.
55 35
5 3 2 3
Allotropism (äA\oc another, and Tpot) twist or turn).
The capability of compound bodies, having the same percentage
and molecular composition, of existing in more than one shape, to
which we have alluded under the term isomerism, finds its parallel
amongst the elementary bodies. Some elements assume various and
well marked modifications. Berzelius has termed this allotropism,
which bears the same relationship to the element as isomerism does to
the compound. The existence of carbon as charcoal, graphite, and the
diamond; the varieties of phosphorus; sulphur in its various modifica-
tions, or oxygen, as common oxygen and as ozone, are illustrations of
allotropism.
The Metric System (Unit of Length).
The metre (unit of length) is a bar of platinum deposited in the
archives of Paris measuring 39.37 English inches. It is adopted as a
*measure of length, surface, weight, and capacity.
I. As A MEASURE OF LENGTH.
Its multiples are marked by Greek prefixes, and its subdivisions by
Jatin prefixes.

In English In English In English |In English
Inches. Feet. Yards. Miles.
Millimëtre tº tº 0.03937 0-003281 0-0010936 || 0:0000006
Jentimétre tº º 0-39370 0.032809 0.0109363 || 0:0000062
Decimétre º 3-93708 0.328099 0.1093633 || 0-0000621
Mètre & 39-37079 3. 28.089() 1.0936331 || 0' 0006214
Décamétre * 393.70790 32-80.8992 I 0.9363310 || 0-006.2138
Hectomètre . 3937 ()7900 3.28° 0899.20 109-3633100 || 0-0621.382
Kilomètre tº is 39370-79000 || 3280-899.200 1093.6331000 || 0-62.13824
Myriomètre 393707-90000 || 32808.992000 || 10936-3310000 || 6’2138244
1 inch = 2.5399.54 centimetres. .
1 foot = 3-0470449 decimètres.
1 yard = 0.9143835 metres.
1 mile = 1.6093149 kilomètres.
THE METRIC SYSTEM.
51
II. As A MEASURE OF SURFACE.

In English
Square feet.
In English
square yards.
In English
3 CreS E
43560 sq.
feet.
1 square mêtre (Centiare)
100 square mêtres (Are) . .
10,000 square mêtres (Hectare)
10-764.299
1076'42993.4
107642-993.4.18
I-1960.33
1 19-6043.26
1 1960° 432602
0 00024.71
0- 0.247114
2°4711431
1 square inch = 6-4513669 square centimètres.
1 square yard = 0.83609715 square mêtre.
1 square foot = 9:28996.83 square decimétres.
1 acre
= 0°40'467102 hectare.
III. As A MEASURE OF CAPACITY.
A cubic decimetre (that is, a cube each side of which measures
3-937 inches) holds a litre of water at 4°C. (i.e., the temperature at
which water is at its maximum density).
gramme, or 1,000 grammes.
gramme of water at 4°C.
This litre weighs 1 kilo-
A cubic centimetre, therefore, holds a

In cubic | In pints= | In gallons In bushels
In cubic feet = 34-65923 =8 pints = 8 gallons
inches. 1728 cubic cubic =277-27384 =2218. 19078
inches. inches. cubic inches. cubic inches.
Millilitre or a cu-
bic centimètre. . 0-06 103 0-000035 0-00176 O'00022.01 0-0000275
Centilitre or 10
cubic centimètres 0.61027 0-000353 0.01760 0-002.2009 0.0002751
Décilitre or 100
cubic centimètres 6-10271 0.003532 0.17607 0° 0220,096 0-0027512
Litre or cubic deci-
mêtre tº e º & 61:02705 0.035317 1-76077 0-2200966 0.0275120
Décalitre (centi-
stère or 10 litres 610-27052 0-353166 17.60773 2-2009667 0-2751208
Hectolitre (Deci- -
stère or 100 litres 6102-70515 3:53.1658 176°07734 22-00966.76 2.75.12084
Kilolitre or cubic
mêtre . . . . 61027-05152 35-316581 1760-77341 220-0.966767 27-5120845
Myriolitre (Déca-
stère . . . 610270-51519 || 353-165807 || 17607-73414 2200 9667675 275-1208459
1 cubic inch = 16:386176 cubic centimétres.
1 cubic foot
1 gallon
= 28-315312 cubic decimètres.
= 4°543358 litres.
IV. As A MEASURE OF WEUGHT.
A cubic centimétre (that is, a vessel, each side of which measures
0.3937 inches) holds a quantity of water which at 4°C. (the maxi-
mum density of water) weighs 1 gramme (15:432 grains).
52
HANDBOOK OF MODERN CHEMISTRY.
:
MEASUREs of WEIGHTs.


In ounces | In pounds | In cwts.= | In tons=
In grains. Troy = | avoirdupois || 112 lbs.- 20 cwts.=
- 480 grains. |=7000 grs. 784.000 grs. 15680000 grs.
Milligramme tº º 0.01543 0-000032 || 0-0000022 (). 0000000 || 0-000000001
Centigramme .. 0.15432 0-000321 || 0-0000220 || 0-0000002 || 0-00000001
Decigramme tº ſº 1°54'323 0-003215 || 0-0002204 || 0-0000019 || 0-0000001
Gramme . . . . 15:43234 0-032150 || 0-002.2046 || 0-0000196 || 0-000001
Decagramme tº º 154'32349 0.321507 || 0:02.20462 || 0-0001968 || 0-0000098
Hectogramme . . 1543.23488 3.215072 || 0:2204621 || 0-0019684 || 0-0000984
Rilogramme. . . . . 15432-34880 32-150726 2-2046212 || 0-0196841 0.0009842
Myriogramme ... 154323:48800 || 321:507267 22:0462126 || 0:1968412 || 0-0098421
1 grain = 0.064799 grammes.
1 oz. troy =31. 103496 grammes.
1 lb. avoirdupois = 0:453495 kilogrammes.
1 cwt. =50-802377 killogrammes.
A kilogramme (=1000 grammes) is about equal to 23 lbs. avoirdupois and 1000
kilogrammes are nearly equal to 1 ton.
The following figure will represent the metre in this threefold
capacity as a measure of length, capacity, and weight.
3-937 inches = decimètre.
Measure of Length—
Measure of Capacity—
Measure of Weight—
A mêtre = 10 times the length of one side of this
figure.
Each side
(3-937 inches)
1 decimétre.
10 centimétres.
100 millimëtres.
-
-
-
--
-*.
-
A cubic vessel, each side having the dimensions of this figure
would hold 1 litre.
A cubic centimètre of water weighs
- 1 gramme = 15:432 grains.
1000 ,, = 1 litre or 15,432 grains.
Square
Centi-
mêtre.
-*
53
We shall consider in Section I. the metalloids, commencing with
Oxygen.
In each case the compounds that the body forms with those
elements already considered, will be examined in detail. Each
element and compound will be examined as far as practicable in the
following order: (1) Synonyms; (2) History; (3) Natural History;
(4) Preparation; (5) Properties; (a) sensible; (3) physical; (y)
chemical; (6) Tests; (7) Uses in Nature, Arts, and Medicine.
In Section II. we shall consider the metals, their compounds
amongst themselves (alloys and amalgams) and their compounds
with the non-metals (salts).
Section III. will be devoted to Organic Chemistry.
We shall examine the non-metals in the following order: —

Atomic | Relative Atomic | Relative
Symbol. Weight. Weight. Symbol. Weight. Weight.
Oxygen . . . . O. 16 16 Sulphur . . . . S 32 32
Fluorine . . F. 19 19 Selenium .. Se. 79.5 79.5
Chlorine .. Cl. 35' 5 35-5 Tellurium .. Te. 129 129
Bromine. . . . Br. 80 80 Carbon . . . C. 12
Iodine e tº I. 127 127 Boron. . . . . . B 11
Nitrogen . . N. 14 14 Silicon . . . . Si 28
Phosphorus P. 3l 62 Hydrogen . . l 1
54 HANDBOOK OF MODERN CHEMISTRY.
SECTION I.--THE METALLOIDs.
CHAPTER III.
OXYGEN.
OXYGEN:—Synonyms—History—Natural History—Preparation—Properties. OzoNE:
History–Natural History—Preparation—Properties—Tests—Quantitative Deter-
mination—Uses of Oxygen—Respiration—Combustion.
OXYGEN (O"=16).
Atomic weight=16. Molecular weight=32. Dyad” (H.0—Ag.0).
Molecular volume TT . Relative weight (H=1) 16. Specific
gravity (Air=1) observed 1.1056; theoretic (0-0693 x 16) 1:1088.
1 Litre weighs 16 criths (0.0896 grin. x 16)=1.4336 grim, at 0°C.
and 766 millimetres; 100 cubic inches weigh at 60° F and 30 B. P.
34-27 grains.
Synonyms: Spiritus Nitro-arius (Mayow, 1674); Dephlogisticated
air (Priestley, 1774); Empyreal air (Scheele, 1775); Pure air (Lavoi-
sier, 1777); Vital Air (Condercet, 1777); Oxygen (Lavoisier, 1778, from
6&c acid, and yévváw, I generate).
History (a),—The earlier investigators devoted much attention to
the nature of what they termed a calx, that is, tho residue left after
exposing a body to fire. Rey in 1630 thought a calx was formed by
the fixation of air; Boyle, in 1660, regarded it as due to the fixation
of heat; Hooke in 1670 again insisted that it was due to the fixation of
air; whilst Mayow in 1674 said it was the fixation of a substance
similar to what existed in saltpetre, which he termed the nitro-aerial
spirit. This in great measure, anticipated Lavoisier's discoveries
respecting combustion. His views were not, however, accepted,
being opposed to the dominating theories of Beccher and Stahl.
(b) Eaperimental facts.-Priestley, on August 1, 1774, was experi-
menting on the calx of mercury (HgC) by heating it in a glass bulb
over mercury with a burning glass, when he obtained oxygen, which he
named, in accordance with the Stahlian theory, “Dephlogisticated air.”
In 1775, Scheele, of Upsala, in Sweden, whilst examining the action
of sulphuric acid on peroxide of manganese (pyrolusite) obtained a
gas (oxygen) which he called “empyreal air,” because of the energy
with which it supported combustion.
Lavoisier (unfairly no doubt) claimed its discovery. He, however,
was the first to explain the true nature of the red precipitate, from
which Priestley originally prepared it, and showed that the process
was an indirect means of obtaining oxygen from the air. Further,
Lavoisier disputed the truth of the Stahlian theory, which taught
OXYGEN.—PREPARATION, 55
that when any substance was burnt, it gave out “phlogiston,” proving
by actual experiment that the products of combustion (the calx) were
heavier than the body burnt, and that therefore the body in burning
could not have given out anything, but must have taken in something.
The Stahlians, to meet this difficulty, imbued their phlogiston with
the property of levity. Lavoisier then propounded his new theory of
combustion, which was soon destined to overthrow the phlogistic
theory. This was, “that combustion was the combination of a burning
body with oxygen.” He moreover rejected Priestley's name, “de-
phlogisticated air,” and called it oxygen, or acid-begetter, inasmuch
as he believed it to enter into the composition of all acids, and to
constitute their acidifying principle.
Natural History.—Oxygen is the most abundant element in
nature. Except in atmospheric air, however, it is always found in a
combined state :-
(a.) The Mineral Kingdom.—The solid crust of the earth has three
chief constituents—carbonate of lime (CaCO3), of which # is oxygen;
clay (Al2O3), of which tº is oxygen; and silica (SiO2), of which
## is oxygen. Thus about one-half of the solid crust of the earth
is oxygen ; (2) of the water, or liquid part, ; is Czygen; and (3)
of the air or gaseous portion, # by volume or ; by weight is
Oxygen.
(3.) The Vegetable Kingdom.—About 3 of all growing vegetable
matter is water, 3 of which is oxygen ; whilst of the solid part, which
is principally cellulin (C6H10O3) #9, or about ; is oxygen.
(y.) The Animal Kingdom.—Water constitutes about 75 per cent. of
living animals, # of which is oxygen. Of albuminous matters,
about 4%;, or nearly 3 is oxygen.
Preparation.—(A.) JBy the action of heat on certain metallic oxides
and peroxides, as follows:–
(1.) Mercuric oride (HgC)); Priestley, 1774; (216 grains produce 16
grains of oxygen or 46-7 cubic inches).- -
Mercuric oxide = Mercury -- Oxygen.
(2.) Red lead (Pb,O, ; triplumbic tetroxide); Priestley, 1774; (655
grains produce 16 grains of oxygen)—
2Pb,04 F 6PbO + O2.
Triplumbic tetroxide = Plumbic oxide (Litharge) + Oxygen.
[2Fb Pbo", = 6PbO + O2].
(3.) Manganic perocide (Pyrolusite); Scheele, 1775; (261 grains
produce 32 grains of oxygen = 93.4 cubic inches)–
3MnO2 Mn30, + O3.
Manganic peroxide Trimanganic tetroxide + Oxygen.
[3]MnO2 Mn3O4 + Og º
E
56 HANDBOOK OF MODERN CHEMISTRY.
(4.) Baric perowide; Bousingault, 1851; (169 grains produce 16
grains of oxygen)— -
2Ba%)2 - 2Ba0 + O3,
Baric peroxide = Baric oxide + Oxygen.
2Paſ), F. 2 Ba0 + O2.
(5) Auric, argentic, platinic orides.
(B.) By the action of heat on certain salts rich in oxygen—
(1.) Potassic chlorate (Guy Lussac, 1814); (122.6 grains yield 48
grains of oxygen = 140:1 cubic inches).
The reaction occurs in two stages:–
(a.) A potassic perchlorate is first formed—
2KClO3 = ECCl + RCIO, + Oz.
Potassic chlorate = Potassic chloride + Potassic perchlorate + Oxygen.
OCl O Cl
[2 | OKo T ECCl + | + o,
OKO
(3.) The potassic perchlorate is then decomposed—
ECIO, - ICCI + 202.
Potassic perchlorate F. Potassic chloride + Oxygen.
OCl
| O - ECCl + 20...]
OKO
(2) When potassic chlorate is mixed with manganic or with some
other oxides it gives off its oxygen at a much lower temperature than
when heated alone. According to the experiments of Wiederhold
(Pogg Ann., crvi., p. 171), confirmed by Baudrimont (Jr. Pharmacie,
S. IV., xiv., p. 81 and 161) no perchlorate is formed under these con-
ditions. (See Catalysis.)
(3.) Zincic sulphate; (Deville and Debray) (161 grains produce 16
grains of oxygen)—
Zincic Sulphate = Zincic oxide + Sulphurous anhydride + Oxygen.
[2SO.Zno" = 22n() + 2SO, + Oc.]
(4.) Alkaline nitrates; (101 grains of KNO3 produce 32 grains of
oxygen = 93.4 cubic inches).
(5.) Permanganates with superheated steam (Marechal and Tessie du
Mothay); (316.2 grains of steam and KMnO, produce 64 grains of
oxygen)— -
4K.MnO, -i- 4H.0 = 8KEIO + 2Mn2O3 + 3O2.
Potassic + Steam = Potassic + Dimanganic + Oxygen.
permanganate hydrate trioxide.
[4MnO, Ko, +4OH, - 80KH + 2Mn2O3 + 3O2.]
If a current of air be passed over the red hot residue, the perman-
ganate will be reproduced.
(C.) By heating certain compounds rich in oaygen with sulphuric acid.
(1.) Manganic perovide and sulphuric acid, (87 grains of MnO2 pro-
duce 16 grains of oxygen)—
OXYGEN.—PROPERTIES. 57
2MnO2 + 2H2SO, = 2MnSO4 + 2 H2O + Oz.
Manganic peroxide + Sulphuric acid = Manganous sulphate + Water + Oxygen.
[2]MnO, + 2SO2Hoz = 2SO2Mno" +2OH2 + Og.)
(2) Potassic bichromate and sulphuric acid; (295 grains of potassic
bichromate produce 48 grains of oxygen)—
2K2Cr,0; + 8B.S.O. = 2K2SO, -- 20r.SSO, +8.H2O + 3O2.
Potassic + Sulphuric = Potassic + Chromic + Water + Oxy-
bichromate acid sulphate Sulphate gen.
CrO2Ko
2 & O + 8SO. Hoa–2SO.Koz-H2S4O6'Cr". Ovi)+8OH2 + 3O2.
CrO2Ko
(3.) Plumbic perocide and sulphuric acid; (239 grains of plumbic
peroxide produce 16 grains of oxygen)—
2PbO, + 2H2SO, F 2PbSO, + 2H2O + O2.
I’lumbic peroxide + Sulphuric acid = Plumbic sulphate + Water + Oxygen.
[2FbO2 + 2SO. Hoc = 2SO.Pbo" + 20 H2 + Og.]
(D.) By the action of various oxides on hydric peroxide :-
H2O2 + AgaO = H2O + Age + O2.
Hydric peroxide + Argentic oxide = Water + Silver + Oxygen.
[{3} + OAge oh, + Ag, 4 or
-
(E.) By the electrolysis of dilute sulphuric acid, oxygen being evolved
at the positive pole.
(F.) By passing a mixture of Steam and chlorine through a red hot
tube :-
2H2O + 2Cl3 = 4 HCl + Oc.
Water + Chlorine = Hydrochloric acid + Oxygen.
(G.) By passing chlorine through a hot solution of sodic or potassic
hydrate, containing a little chloride or nitrate of cobalt. The chlorine
converts the cobaltous hydrate into cobaltic hydrate, and subsequently
the liquid effervesces and evolves oxygen. (Fleitman.)
(H.) By dropping sulphuric acid into a red hot platinum retort —
2H2SO4 = 2Eſ..0 + 2SO. + Og.
Sulphuric acid = Water + Sulphurous anhydride + Oxygen.
(I.) By the action of the leaves of plants in sun-light on carbonic acid,
whereby the carbon is fixed, and oxygen set free (“Pharmaceutical
Journal,” July, 1873, p. 65).
Properties.—(a.) Sensible.—A colorless, odorless, tasteless gas.
(b.) Physiological.—If a rabbit be placed in pure oxygen at 75° F.
(24°C.), it will live for about three weeks, eating voraciously all the
time, but nevertheless becoming thin. The action of oxygen at 45° F.
(7.2° C.), is to produce narcotism, and eventually death. When
oxygen is cooled by a freezing mixture, it induces so intense a nar-
58 HANDBOOK OF MODERN CHEMISTRY.
cotism that operations may be performed under its influence.
(Richardson.)
Compressed oxygen is “the most fearful poison known.” The
pure gas, at a pressure of 3} atmospheres, or air at a pressure of 22
atmospheres, produces violent convulsions, simulating those of strych-
nia poisoning, and ultimately causing death. The arterial blood in
these cases is found to contain about twice the quantity of oxygen
that is normal. Further, compressed oxygen stops fermentation, and
permanently destroys the power of the yeast. (Paul Bert.)
(c.) Physical.—Oxygen is 16 times heavier than hydrogen. Its
experimental specific gravity is 1:1056, so that 100 cubic inches
weigh 34.27 grains. Oxygen is a permanent gas, i.e., it cannot be liqui-
fied, either by cold or by pressure. It refracts light less powerfully than
any other gas (O=0:8, air=1). Oxygen is an electro-negative body,
that is, it is attracted by the positive pole of the battery. It is the
only gas that is magnetic (?), although its magnetism at best is but
feeble, and is diminished by heat and increased by cold. Heat (as in
the case of all other gases) expands it 0:3665 times its volume for
every 19 C., and 0.002 times its volume for every 19 F. It is only
slightly soluble in water; 100 volumes dissolve 3 to 4 volumes of
Oxygen.
(d.) Chemical.—Oxygen has no action either on litmus or on turmeric.
It causes no precipitate with lime water. It forms red fumes of N2O4
with nitric oxide (N2O2). It is completely absorbed by a solution of
pyrogallic acid in strong caustic potash. It supports combustion
vigorously, but is not itself combustible;—hence Lavoisier's theory of
combustion, that it was “rapid oacidation.”
Action on the metalloids.-Oxygen combines directly with all the non-
metals except fluorine, with which it does not combine at all, and
the other haloid bodies, with which it only combines indirectly, that
is, through the intervention of a third body. It combines, however,
with none of the metalloids at ordinary temperatures, except with phos-
phorus, in which case the energy of oxidation may be so intense that
combustion results. If carbon, sulphur, or phosphorus be burnt in
oxygen, bodies are formed (viz., CO2, SO2, and P303), which, when
dissolved in water, redden litmus. All the non-metals, except hydro-
gen and fluorine, form, by their union with oxygen, anhydrides,
which, when dissolved in water, constitute acids. Hence, Lavoisier
taught “that oxygen was the acidifying principle of all acids,” a
theory we now know to be incorrect.
Action on the metals.-Oxygen combines directly, under certain con-
ditions, with all the metals, except gold, silver, and platinum (Noble
metals). Combination, however, does not usually occur at ordinary
temperatures, except in the case of a few metals, such as sodium,
potassium, barium, strontium, and calcium, and in some other cases
where the metals have been reduced to a state of minute subdivision
(pyrophoric). Only a very moderate heat, however, is usually re-
OZONE...—NATURAL HISTORY. 59
quired to effect a union. Iron, lead, etc., undergo superficial oxidation
in the air at common temperatures, but this is dependent on certain
circumstances that favor oxidation, such as the presence of moisture,
carbonic anhydride, etc.
When a metal combines with oxygen, it generally forms what is
called a base, that is, “a compound body capable completely or in part of
neutralizing an acid.” The compounds, formed by the union of the
alkaline metals with oxygen, are called alkalies or alkaline bases, as,
e.g., sodic oxide (Na2O) potassic oxide (K20), etc. These bodies are
very soluble in water. The other metals also form bases with oxygen,
but they are practically insoluble in water; nevertheless they are
capable either entirely or in part of neutralizing acids (ZnO-Fe2O3).
No non-metal ever forms a base by its union with oxygen, although
some metals form anhydrides by such combination. This anhydride
is always the highest oxide that the metal is capable of forming, as
e.g., stannic anhydride, SnO2—antimonic anhydride, Sb2O3, etc. There
are certain oxides that are neither acids nor bases, and are known
as “indifferent orides” from their similarity to salts. Such, for ex-
ample, are water (H2O), manganic peroxide (MnO2), etc.
Various methods have been devised for estimating the quantity of
free oxygen present in a mixed gas. In most cases the oxygen is re-
moved by absorbent agents, such as moist phosphorus or certain moist
metals (iron, lead, etc.); certain low oxides, such as Fe0 or N2O2
(Priestley); or a mixture of the last two bodies (Davy); the ammonio-
chloride of copper (Graham); pyrogallic acid dissolved in an alka-
line solution (Liebig); red-hot copper or iron (Dumas); cuprous
oxide (Cu30) in ammonia (“Chemical News,” vol. xxxiii., p. 5);
also by exploding the gas with hydrogen. These methods of esti-
mating oxygen will be referred to under the analysis of air.
Allotropic Oxygen: 0Zone (bºw, I smell).
*-mºmºsºm-º.
Molecular weight=48. Molecular volume TTI. 1 litre weighs 24 criths
(0.0896 grin. x 24) 2:1504.
History—Von Marum (1780) noticed that air or oxygen, through
which electric sparks had been passed, possessed a peculiar odor, and
rapidly tarnished quicksilver. Schönbein, of Basle, in 1840, showed
that this peculiar smelling gas was developed by exposing moist
phosphorus to air. Since 1840 Ozone has been further examined by
Marignac, De la Rive, Fremy, Becquerel, Andrews, etc.
Natural History (See OzoNE under AIR).
Nature of Ozone.—Schönbein, in the first instance, regarded ozone as
a peroxide of hydrogen (EI20s, or in old formula HOe); Baumert and
Williamson fixed H2Os as its composition, because water and oxygen, as
they supposed, were formed by its decomposition : (H2O3=H2O+O2).
Berzelius, Marchand, Erdmann, Marignac, De la Rive, Fremy, Bec-
querel, and Andrews afterwards showed that pure dry oxygen can
be ozonized, whilst Andrews proved that with proper precautions no
60 HANDBOOK OF MODERN CHEMISTRY.
water results from its decomposition. Schönbein afterwards regarded
ozone as permanently negative oxygen (O), there being, as he thought,
a permanently positive oxygen (O) (antozone), a body which has not as
yet been obtained in a free state (see page 63).
Chemists are now tolerably agreed that ozone is an allotropic
oxygen, where three volumes are condensed into two, one of the
volumes being in a different polar condition to the other two
(Gö6–two volumes) This view is confirmed by the observation
of Andrews that, when ozone is absorbed by mercury or by potassic
iodide, the volume of the gas is not affected.
OOO + Hg = Hg0 + 00
~~~~ ^*~~~
2 vols. Of Ozone, 2 vols. of Common O.
Preparation.—Ozone, however prepared, always contains a large
admixture of air or oxygen. The following are Some of the methods
by which it may be obtained:— -
(1.) By electrical agency. The silent passage of electricity through
damp oxygen, is the method best adapted for its generation. A small
induction spark, or the brush from the electrical machine, may also
be employed, but the long spark from the coil, on account of its high
temperature, destroys the ozone as fast as it is generated. Various
ozonizers have been invented, in order to secure this silent passage of
electricity through oxygen. That of Houzeau consists of a glass tube
filled with oxygen, a platinum wire being placed in the centre of the
tube, attached to One terminal of an induction-coil, whilst a second
wire is wound round the glass tube and attached to the other ter-
minal. Siemen's ozoniser consists of two glass tubes, one placed inside
but separate from the other by a small interval, through which a
stream of oxygen may be continuously passed. The internal tube
has its inner surface, and the external tube its outer surface, covered
with tin-foil. When these are connected with different poles of the
coil, a silent discharge takes place between them, whereby the ozoni-
zation of the intermediate oxygen is effected. By means of these
ozonizers, 60 to 120 milligrammes of ozone per litre of oxygen may
be obtained.
(2.) By the electrolysis of dilute sulphuric acid. The oxygen which is
set free at the positive pole by the electrolysis of dilute sulphuric acid
contains about ºn part of its volume of ozone, i.e., about 3 to 5 milli-
grammes per litre. The water mixed with the acid should be free
from all organic or other oxidizable matters, and the presence of a
little bichromate of potash in solution is said to assist its formation.
(Baumert.) • * . &
(3.) By slow combustion (Eremacausis): (a) of phosphorus in moist air
(Schönbein). The phosphorus employed should be freshly scraped,
and kept at a temperature of from 70° to 90°F. (21° to 82° C.) It
OZONE..—PREPARATION. - 61
should not be allowed to act on the same air for more than an hour,
otherwise the ozone first generated will be decomposed. The action
is more complete if the air in the vessel be slightly rarefied, the best
effects being produced by employing a mixture of hydrogen and oxy-
gen in the place of air. (3.) By the slow combustion of ether and volatile
oils. When the combustion of ether is effected by glowing platinum,
or by placing a hot glass rod in a bottle filled with the vapour, ozone
is produced, together with certain acid vapours. Aromatic plants and
flowers are also said to generate ozone (Mantegazza), although the
recent experiments of Kingsett indicate that hydroxyl, and not ozone,
is generated under these circumstances.
(4.) By the rapid combustion of all bodies containing hydrogen. The
generation of ozone under these conditions is supposed to be due to
the hydrogen molecule combining with a half molecule of oxygen (a),
leaving the other atom of oxygen free to combine with a second oxy-
gen molecule to form ozone (3). Thus—
(a.) H2 + O. = H2O + O ; (3,) O + O2 = Os.
Ozone is not formed by the combustion of carbon, inasmuch as carbon
combines not with half molecules of oxygen (O), but with complete
molecules (O.). (Thau.)
(5.) By the action of oxygen on fine particles and on large surfaces.
When lead pyrophorus is exposed to the air, it catches fire spontane-
ously, owing to the generation of ozone, by the action of air on the
finely-divided metallic particles.* Similarly, when phosphorus is dis-
solved in bisulphide of carbon, and the solvent allowed to evaporate,
the finely-divided phosphorus fires spontaneously.
(6.) By nascent action. The intense activity of nascent oxygen, it is
thought, may be due to the gas being ozonic. Probably the oxygen
set free by plants from the decomposition of carbonic anhydride is
also ozonic. (De Lucca, “Pharmaceutical Journal,” July, 1873, p. 65.)
Possibly to this may be traced the bleaching action of morning dew.
Properties of Ozone.—(a.) Sensible. A colorless gas having a
peculiar phosphorus-like odor (ěčw, I smell).
(3.)—Physiological. Its special action in respiration will be discussed
further on (page 64). It acts as an intense irritant to the eyes and
nose, and rapidly proves fatal to animal life. (Thénard and Schönbein.)
(y.) Physical.—Ozone consists of 3 volumes of oxygen condensed
into 2 volumes; hence its density must be 1A times the density of
common oxygen; 1 litre, therefore weighs (8 x 3) 24 criths (see page
35). It decomposes slowly in the presence of moisture at 212°F.
(100°C.), but decomposes instantly at a temperature of from 450° to
500°F. (232° C. to 260° C.), the ozone becoming ordinary oxygen.
Ozone is only slightly soluble in water. At 32°F. (0°C.) 100 volumes
of water dissolves # volume of ozone (Carius). It is not soluble in
Solutions of acids or alkalies.
* Possibly this action may be due to the carbon present absorbing oxygen, and so
bringing it within the sphere of affinity.
62 HANDBOOK OF MODERN CHEMISTRY.
(3) Chemical—Ozone is a powerful oxidiser. This action depends
on its desire to throw off one of its oxygen atoms, and so return to
the condition of ordinary oxygen. It bleaches litmus, and is almost
as powerful a supporter of combustion as ordinary oxygen.
(1.) Action on the Non-metallic Elements.-These are as a whole but
little and but slowly affected by it. It rapidly oxidizes the com-
pounds of hydrogen with phosphorus, sulphur, and selenium.
(2.) Action on Metals.—None of the metals, except mercury, are
affected by dry ozone, whilst in the presence of moisture, nearly all the
metals (except gold and platinum) are oxidized by it. Even metallic
silver is converted into a peroxide. It is to be noted that, under these
circumstances, no contraction of the gas results, the ozone returning
from the triatomic to the diatomic condition of ordinary oxygen.
(3.) Action on Mineral Compounds.-Ozone converts the protoxides
and protosalts of lead, tin, iron, manganese, etc., into peroxides and
persalts. Some peroxides decompose ozone, and are themselves, at
the same time, partially reduced. Thus the peroxides of copper, man-
ganese, and barium, etc., exhibit this catalytic action on ozone:—
BaO2 + Og = BaO + 202.
The sulphides and selenides are also oxidized by it. It decomposes
iodide of potassium, iodine being set free.
(4.) Action on Organic Matter and on Organic Compounds.—Organic
bodies generally are speedily oxidized by ozone. It bleaches indigo,
converting it into isatin; tincture of guiacum is turned green by it ;
cork and caoutchouc are speedily acted upon. Putrid flesh is de-
odorized. Strychnia and aniline assume various tints under its action.
It is absorbed by turpentine. It has no action on paraffin, which
may therefore be used for joining apparatus used in its generation,
and in experiments upon it.
Special Tests for Ozone.—(1.) White bibulous paper soaked in a
solution of 1 part of potassic iodide, 5 parts of starch, and 100 parts
of water, constitutes the common ozone test-paper. Ozone displaces
the iodine from its combination, the iodine thus set free blueing the
starch. For determining the presence of ozone in the air, Schönbein
employs moist ozone papers, whilst Moffatt prefers them dry. The
fallacies to this as a test for ozone, are the presence in the air of
chlorine or of the oxides of nitrogen.
(2.) Houzeau's Ozonometer consists of neutral litmus paper, soaked in
a dilute solution of potassic iodide, the potash set free by the ozone
turning the paper blue. A piece of the litmus paper without iodide, is
also exposed to the air at the same time, a comparison of the two
papers indicating how far the action on the iodide paper may be due
to ammonia in the air, and not to the action of ozone.
(3) A solution of sulphate of manganese is turned brown by ozone.
(4.) A colorless solution of a protosalt of thallium is turned yellow by
ozone, but not by the oxides of nitrogen (“Intellectual Observer,'
1867, p. 399).
ANTOZONE. . 63
Quantitative Determination.—This is made either (1) by means
of a weighed quantity of dry mercury, which rapidly absorbs ozone,
or (2) by estimating the amount of iodine liberated in a solution of
potassic iodide of known strength, a little hydrochloric acid being
added to prevent the absorption of carbonic acid:—
O3+2FCI+ H2O=O2+I+2KHO.
AntoZone.
Schönbein first, and afterwards Brodie, directed attention to the fact
that oxygen appears to exist in certain compounds, not only in a state
different from, but actually antagonistic to, ozone. Schönbein termed
this form of oxygen, antozone. Brodie was of opinion that the dif-
ference between ozone and antozone depended on the oxygen in the
two cases being in different polar conditions, its polarity being deter-
mined by the body with which it was associated (Odling, p. 125).
For example; (a.) The oxygen existing in peroride of manganese
(MnO.), in peroxide of lead (PbO2), in chromic acid (H2CrO,), and in
imanganic acid (HMnO,), was regarded as ozonic, for in a nascent state
it was found to color strychnia and guiacum ; whereas—
(3.) The nascent oxygen evolved from the perovides of barium, of
strontium, of calcium, and of hydrogen, on the contrary, was incapable of
coloring strychnia or tincture of guiacum. And, further, the oxygen
obtained from this latter series seemed to be in some respects abso-
lutely antagonistic to, and destructive of, the ozone obtained from the
former series, combining with it to form common oxygen. Thus,
peroxide of hydrogen is decomposed by the oxides of mercury, silver,
gold, or platinum, these latter oxides being themselves reduced during
the process, whilst ozone was found to decompose perovide of hydrogen
leaving water, and perocide of barium (BaO2) leaving Ba0, and common
oxygen in each case.
These facts suggested the notion that the oxygen present in these
bodies must exist in different polar or electrical states, and that the
antagonism was due to the power of the one to neutralize the other.
Thus—
(1.) (a.) Ozone and perovide of hydrogen.
—-H — + --- — + -- —
OOO + H200 F. 200 –– H2O
Ozone + Peroxide of = Common + Water.
hydrogen OXygen
(6.) Ozone and perovide of barium.
— +— + -- - - — -Hi -- —
OOO + BaOO -- 2OO + l3aO
Ozone + Raric - Common + Baric oxide.
peroxide ONygen
(2.) (a.) Perovide of hydrogen and perovide of manganese.
+ — -- + -t- + — + –- + —
MnOO + H200 = MnO + H2O + OO
Peroxide of + Peroxide of = Manganese + Water + Common
manganese hydrogen oxide OXygen.
64 IIANDIBOOIK OF MODERN CíIEMISTRY.
(B.) Perowide of hydrogen and the ovides of the noble metals.
+ — — + —-- + — + — --—
AgAgO + H2OO = Ag Ag -- H2O + OO
Argentic + Peroxide of = Silver + Water + Common
oxide hydrogen oxygen.
From this it was inferred that oxygen was capable of existing in at
least three states, which were represented as follows—
– + —
(1) Common oxygen : O or 00;
(2.) Ozonic oxygen : O or OO-HO = oão 5
+ +— + +—-H
(3.) Antozomic oxygen: O or OO-HO = OOO.
The recent researches of W. Babo, Weltzien, etc., have, however,
proved beyond a doubt that this peculiar body, called antozone by
Schönbein, is, after all, merely peroxide of hydrogen (p. 209).
Uses of Oxygen.-(a.) In nature oxygen acts as the great burner
up of dead organic matter. We see eremacausis or slow oxidation
taking place in the decay of wood (dry oxidation), in the formation of
humus and peat (wet oxidation), and in the change of wood into coal
(wet and imperfect oxidation). In nitrification we see the action of
oxygen producing nitre. Oxygen effects the resinification of the fixed
and volatile oils, illustrated in the drying of paint, in the occasional
firing of greasy rags, and more generally in the formation of resins.
The acetification of alcohol, again, is an oxidizing action : thus—
Alcohol + Oxygen = Acetic acid –H Water.
JRESPIRATION.
Dy the act of respiration the oxidation of tissue is effected. This is
a process common to all animals. Oxygen must be brought, by some
means or another, into contact with the blood, and by it with the body
generally. In some animals we find for this purpose a minute series
of tubes, along which air is conveyed through the system. In fish,
the water containing oxygen in solution, passes through the gills, and
coming into contact with a fine membrane, upon the opposite side of
which the blood of the animal circulates, there occurs a free inter-
change of gases. In some animals, as in frogs, respiration is, in
great part (and in the higher animals in a lesser degree), cutaneous
transpiration ; whilst in animals generally the lungs constitute the
principal machinery for effecting the proper oxygenation of the
blood. In respiration the changes produced are threefold; (1) a
visible or color change; (2) a physical or heat change, resulting from
chemical combination; and (3) a chemical change. The facts of
respiration were collected slowly; Mayow (1674) proved the taking
in by the lungs of something present in the air; Black (1757)
proved the return of something to the air during exhalation ; whilst
Lavoisier proved that the active gas taken in by the lungs, was
oxygen, and that the gas returned was carbonic anhydride. He was
further of opinion that the animal heat was the result of a process
OXYGEN–RESPIRATION, 65
of combustion, the union of carbon and oxygen. But he noted that
the carbonic anhydride given back to the air, only accounted for a
portion of the oxygen taken from the air.” Hence arose a theory of
diffusion, which regarded respiration as a purely physical act. This
may be stated as follows:—The venous blood, rich in carbonic
acid but poor in oxygen, passes into the minute pulmonic capillaries,
external to which is a mixed gas (the air), containing very little
carbonic acid, but rich in oxygen; hence an interchange of gases takes
place to establish equilibrium. More recent experiments, however,
have shown that breathing is not merely a physical, but a chemical
act. In the red blood-corpuscles a Compound exists called “haemo-
globin.” This body has a purple color in venous blood, but is capable
of combining chemically with oxygen to form a vermilion red body
called “oxyhaemoglobin,” the coloring matter of arterial blood. The
active agent in respiration is this haemoglobin, a body remarkable
for the ease with which it both combines with, and also delivers up,
oxygen. Asphyxia means the non-oxygenation of the purple haemo-
globin. Other gases, such as carbonic oxide, are also capable of
combining with it, forming “carbonic oride hapmoglobin,” which is of a
like red color to oxyhaemoglobin, but, unlike it, in that, when once
formed, the haemoglobin cannot part with the carbonic oxide, in the
same way that it can with oxygen. Hence the cause of death in
poisoning by this gas.
Experiments (some teach) have shown that the blood corpuscles
possess the power of ozonizing the oxygen inhaled, peroxide of hydro-
gen being formed by its combination with water. This compound is
again decomposed into water and oxygen, which oxygen in its nascent
state serves for the purposes of oxidation. It is certain that both
blood and haemoglobin have the power of setting free the oxygen ab-
sorbed by oil of turpentine, and that blood globules act similarly on
peroxide of hydrogen. The nascent oxygen thus evolved is capable of
acting on such bodies as potassic iodide and starch, tincture of guia-
cum, etc. In fact, Schönbein taught that the function of the blood
corpuscles was the chemical excitement of the oxygen of the respired
air. If haemoglobin be mixed with alcohol or heated to 212°F., it then
loses the power of decomposing the peroxide. Thus it is held that there
is perpetually going on, in the animal organism, this formation and
destruction of ozone and peroxide of hydrogen. The solution of the
corpuscles and their alteration into other products is believed to be
due to the ozone. These products have no longer any plastic property,
and in this way Schmidt believes that the fluidity of the blood is
maintained. (Schönbein, Schmidt, Schreiber, etc.)
The quantity of oxygen required for respiration is important. It
* Herbivorous animals are said to exhale carbonic acid in volume equal to the
oxygen taken in, but carnivorous animals exhale a volume of carbonic acid 40 per
cent, less than the inhaled oxygen.
F.
66 HANDBOOK OF MODERN CEIEMISTRY.
varies with sex, age, diet, exercise, etc. The following facts are
important :— -
I. The Carbon daily consumed as food, and daily evolved as Carbonic
Acid. (Dr. E. Smith.)
Carbon consumed in Carbon evolved by lungs
Adult Man. diet daily. daily ascó.”
OZS. grains. OZS. grains.
In idleness * - t tº e º 8-72 3815 7-85 3434
With ordinary labour . . 13:00 5688 9 : 11 3985
With active work . . . . 15-60 6825 12-90 5644
The 3985 grains of carbon evolved per day from the lungs by a
man in ordinary work is equivalent per hour to about 1240 cubic
inches of carbonic acid.
Carbon consumed per hour by males (Andral and Gavarret).
Up to 8 years of age • * ... 77 grains per hour.
From 8 to 15 . . w & - - . . 133 , 33
,, 15 to 20 . . º e • * ... 175 , 35
,, 20 to 40 . . a tº - - ... 185 , * }
,, 40 to 60 . . • & - - . . 155 , 53
,, 60 and over . . * - ... 95 ,
Females consume somewhat less, viz., 98 grains per hour from 15 to 40.
II. The oxygen daily consumed by the food taken by an average man.
(The following results are the mean of the observations of Dumas,
Liebig, Regnault, Lassaigne, Scharling, and Smith):--
ozs. cubic feet.
Oxygen consumed by the 9 ozs. of the carbon of food . . 24 = 17-73
2 3 75 , # oz. , hydrogen , . . 4 = 2.95
Total of oxygen consumed daily tº º . . 28 = 20.68
This is at the rate per hour of
1489 cubic inches of oxygen ; or
7445 , ,, of air.
III. Normal air contains 0.04 per cent. (or 4 parts in 10,000) of
carbonic acid. Air containing 4 per cent. of carbonic acid (the quan-
tity present in expired air) is perfectly irrespirable; air containing 1
per cent. of carbonic acid is extremely distressing; air containing
0.1 per cent. may be regarded as polluted.
IV. It follows that the quantity of air used per hour (7445 cubic
inches) plus that vitiated by the 1240 cubic inches of carbonic acid
expired, must be—
At 4 per cent. of CO., 38,445 cub. in. = 22.22 cub. ft.
At 1 , , ,, 131,445 , , = 76-08 , ,
At 0-1 , , , , 1,247,445 , , =723-64 ,
W. The quantity of air required for respiration by an ordinary man,
is equal to that contained in a room 9 ft. square and 9 ft. high, re-
newed every hour, whilst for good breathing it should be renewed
every half-hour. When, therefore, we fix 300 cubic feet as the space
per head in sleeping-rooms, it is manifest that this must be regarded
as the very minimum, and implies thorough ventilation.
OXYGEN-COMBUSTION.
67
WI. In these calculations the carbonic acid from the lungs is the
only product considered. There is also, however, the carbonic acid
given off from the skin, etc., which should also be taken into account.
It may be noted that a horse consumes about 13 times as much
oxygen as a man; that is, he requires about 19,000 cubic inches of
oxygen, and 95,000 cubic inches of air, per hour.
(a.) Use of oaygen as an agent of combustion :
The following table shows the quantity of oxygen consumed, the
CO2 produced, and the air vitiated by the combustion of 1 lb. of the
following substances—


Cubic ft. of
º g Cubic ft. of Heat pro-
Cubic ft. of Cubic ft. Carbonic Air vitiated duced #.
One pound of Oxygen of Air Acid hatis C
coj, | c.s.led.|Acid (CO3)|(that is 003 || 9f water
produced | =l perct.) raised 10°F.
Newcastle Coal . . 30 - 15 1 50-75 25-62 2713 1159
Dry Wood 15-85 79.25 15:30 1609 676
Dry Turf 17-15 85-75 16:51 1737 579
Coke . 28-14 140-70 28. SS 3129 1255
Charcoal 31 - 26 156-30 31 - 11 3.267 1409
Camphine 38-90 194-5 27. 2974' 5 1957
Benzol 36-3 181 - 5 29 - 1 3091 - 5 1820
Spermaceti 37-0 185' 0 25.2 2705-0 1759
Wax . . 37.7 188: 5 25-6 2748-5 1581
Stearic Acid 34-6 173.0 24-0 2573-0 1705
Stearin . . 34°4 172.0 24 - 2 2592.0 1800
Paraffin . . 40 - 5 202.5 27-0 2.902.5 2133
Paraffin Oil 40-5 202.5 27-0 2902-5 21.33
Rape Oil 38.7 193 - 5 24-3 2623-5 1775
Sperm Oil 38.7 193 - 5 24-3 2623-5 1775
1 cubic foot of common
coal gas = 14 candles 1, 17 5-85 0-55 60-55 65
1 cubic foot of cannel
coal gas = 20 candles 1.56 7-80 0-83 90-80 76
The following table shows the oxygen consumed, the carbonic acid
produced, and the air vitiated, by the combustion of certain bodies,
burnt so as to give the light of 12 standard sperm candles, each
candle burning at the rate of 120 grains per hour each :—


Burnt tº give light ºf cubic ft of Culiº ſt". "...º.º.
12 candles = to 120 Oxygen of Air A . º i. *:::
grains per hour. coºd, consumed. |Acid (0%) (that is 00,
produced. =l per ct.)
Cannel Gas 3:30 16:50 2.01 217-50
Common Gas 5.45 27:25 3° 21 348-25
Sperm Oil 4-75 23-75 3-33 356-75
Benzole . . 4 * 46 22-30 3'54 376-30
Paraffin . . 6-81 34-05 4' 50 484-05
Camphine is 6-65 33-25 4-77 510 - 25
Sperm Candles . . 7.57 37.85 5-77 614-85
8X , , , 8:41 42-05 5-90 632-25
Stearic , 8-S2 44 - 10 6.25 ($69-10
Tallow , 12:00 (30-00 8-73 933-00
Heat pro-
duced in lbs.
of water
raised 10°F.
68 IHANDBOOK OF MODERN CHEMISTRY.
It would thus appear that, of the substances named, cannel gas
vitiates air the least, and tallow candles the most, and that the order
of their vitiating effect, is also very nearly the order of their heating
effects.
Regnault has shown that the same heat which will raise 1 lb. of
water 19 F., will raise 49 cubic feet of air (= 3-6 lbs.) 19 F.; or,
again, that the heat that will raise 1 cubic foot of water (=62:23 lbs.)
1°F., will raise 3,054 cubic feet of air (= 283-71 lbs.) to the same
extent.
(3.) Use of oaygen as an oasidizing body.—Endless illustrations of this
action might be given.
(y.) Use of oaygen in medicine.—“Searle's oxygenated water,” and
“Gardner's peroxide of hydrogen,” have been used in medicine, but
their efficacy is doubtful.
Lastly, we note that the regular supply of oxygen in the air is
maintained by plant-life, the carbon being retained by the plant, and
the oxygen evolved for the animal. Thus—
12CO2 + 11H2O = ClaſſocOil + 120g,
Sugar.
69
CHAPTER IV.
TEIE EIALOGENS OR EIALOID ELEMENTS.
FLUORINE. CHLORINE : Compounds of Chlorine and Oxygen—Hypochlorous anhy-
dride—Hypochlorous acid—Chlorous anhydride—Chlorous acid— Chloric per-
oxide—Chloric acid—Perchloric acid. BROMINE : Compounds of Bromine with
Oxygen and Chlorine. IODINE : Compounds of Iodine and Oxygen—Iodic acid
—Periodic acid—Compounds of Iodine and Chlorine — Generalization on the
Halogens.
FLUORINE (F = 19).
Atomic weight, 19. Atomicity monad () (as in HF). Relative weight
(H=1)19. Specific gravity (Air = 1), (theoretical 0-0693 × 19)
1-3186. 1 litre weighs 19 criths (0.0896 × 19) = 1.7024 grims.
100 cubic inches weigh (estimated) 40'87 grains.
Synonyms.-Fluoric radical (Berzelius); Fluoricum : Fluorine (Sir
H. Davy, from Fluor Spar).
History.—Davy in 1808 suspected hydrofluoric acid to be a com-
pound of oxygen with a combustible base. In 1812 and 1813 he
obtained by the electrolysis of the acid, hydrogen at the negative pole,
and free fluorine at the positive pole. He was unable, however, to
collect the fluorine, owing to its intense action on the vessels used in
the experiment. The Messrs. Knox, of Dublin, in 1836, and Davy,
in 1840, obtained fluorine by electrolysing hydrofluoric acid in fluor
spar bottles. In 1858 Phipson is also stated to have obtained it, by
heating hydrofluoric with nitric acid. It has been examined at
different times by Fremy, Baudrimont, Kammerer, and by other
chemists.
Natural History.—It is never found in nature in a free state.
(a.) In the mneral kingdom it is tolerably abundant, both as fluor or
Derbyshire spar (CaF2), and as cryolite (6NaF,Al,Fe). It exists also
as a fluoride of cerium, and is found in certain minerals, such as
Wavellite, mica, fluor, apatite, topaz, etc. It is also present in sea
and in many mineral waters. (3.) In the vegetable Kingdom it occurs
in numerous plants, and particularly in the siliceous stems of grasses.
(y.) In the animal kingdom it is found in the teeth, bones, milk, blood,
urine, etc. Bone contains about 2 per cent. of fluoride of calcium
(CaF2).
Preparation.—1. By the electrolysis of hydrofluoric acid in fluor
spar vessels. (Davy and the Messrs. Knox.)
70 HANDBOOK OF MODERN CHEMISTRY.
2. By the action of sulphuric acid on a mixture of peroxide of
manganese and fluor spar. -
2H2SO4 + MnO2 + CaF2 = MnSO, -- CaSO4 + 2 H2O + F2.
Sulphuric + Manganic + Calcic = Manganic + Calcic + Water + Fluorine
- acid peroxide fluoride Sulphate Sulphate
[2SO, Hos-- MnO, + CaF2 =SO.Mno" +SO.Cao"+2OH. H. F.,.]
3. By electrolysing fused potassic fluoride. (Fremy.)
4. By heating for 24 hours, at 170° F (77°C.), in an hermetically-
sealed tube in which the air has been previously displaced by iodine
vapor, a mixture of iodine with an excess of argentic fluoride, an
iodide of silver and a fluoride of iodine (IFs) being formed. (Kam-
merer.)
Properties.—(a.) Sensible. A gas said to have a yellow color,
like chlorine, but that produced by Kammerer’s process is colorless.
Its odor is very powerful.
(6.) Physiological.—Its action on the animal body is very deleterious
and irritating.
(y.) Physical.—It has an estimated specific gravity of 1:3186;
100 cubic inches should weigh, therefore, 40.87 grains, and a litre
17024 grims.
(6.) Chemical.—It combines with every known element, except oxy-
gen. Its action on all bodies, especially on silicon (glass), and on the
metals, is intensely energetic. The difficulty of collecting it is so
great, that an accurate study of its properties is rendered almost im-
possible. Tt is said to be absorbed by caustic potash, potassic fluoride
and hydric peroxide being formed (2KEIO + F = 2KF + H2O2).
It has no special uses.
CHLORINE (Cl = 35.5).
Atomic weight, 35-5. Molecular weight, 71. Molecular volume, TT|.
Atomicity monad () (HCl). Irelative weight (H=1) 35'5. Specific
gravity (Air = 1) observed, 2.47; theoretic (0.0693 x 35.5), 24601.
1 litre weighs 35.5 criths (0.0896 grin. x 35-5) = 3, 1808 grims. 100
cubic inches, at 60° Fah. and 30 J3.P., weigh 76.3 grains.
Synonyms. — Dephlogisticated marine acid (Scheele); oaygenated
muriatic acid (Berthollet); oacymuriatic acid (Kirwan and Pearson);
muriaticum, or muriatic radical, (Berzelius); Chlorine (Davy, from
X\wpoc, green).
History.-Discovered by Scheele (1774) when acting on peroxide
of manganese (pyrolusite) with hydrochloric acid. It was further ex-
amined by Berthollet (1785), and named by him “oxygenated muri-
atic acid,” because, when placed in sunlight, he found that the moist
gas split up, as he supposed, into oxygen and muriatic acid. Thénard
(1809) showed, however, that it was impossible to effect this de-
composition with dry chlorine, whilst Davy (1810) further proved its
elementary nature. -
CFILORINE. 71
Natural History—It is never found free in nature. (a.) In the
mineral kingdom, it occurs in combination with sodium and with other
metals, in salt mines, in sea water, and in various horn-minerals, such
as the chlorides of lead, silver, mercury, etc. In volcanic districts it
is found combined with hydrogen. (3.) In the vegetable kingdom, it is
not an abundant element; but in (y) the animal kingdom, it is found in
all secretions. Its absence in the urine in pneumonia, constitutes a
peculiarity of that disease.
Preparation.—The first process described is the common labora-
tory process, and the process of the B. P. for the preparation of liq.
chlori. The first three are trade processes, the second being that
commonly used in the manufacture of chloride of lime.
(1.) By heating a mixture of manganic peroxide and hydrochloric
acid. (Scheele.) The reaction takes place in two stages:—
MnO, + 4HCl = MnGl, + 2 H2O.
(a.) Manganic peroxide + Hydrochloric acid = Manganic tetrachloride + Water.
[MnO2 + 4HCl = MnOl, +2OH2]
MnOl, - MnOl. + Cl2.
(3.) Manganic tetrachloride = Manganous chloride –H Chlorine.
[MnOl, – Mn Cl, –H Cle].
In Weldon's process, (which is employed in dealing with the “still
liquors” of bleaching-powder factories), the MnGle formed as above,
is decomposed by lime:—
§ MnCl2 + CaO = MnO + CaCl2.
This MnO is then mixed with more lime, and air blown through the
mixture, whereby the MnO is converted into MnO2, which may be
again used for generating chlorine with hydrochloric acid.
It has been suggested by Schlösing to prepare chlorine by heating
the peroxide of manganese with a mixture of nitric and hydrochloric
acids. Chlorine is evolved, whilst the manganous nitrate formed, yields,
when heated, MnO2 and nitric acid, which may be again used to
decompose fresh hydrochloric acid.
(2.) By heating a mixture of sulphuric acid with manganic per-
oxide and common salt. In this process the whole of the chlorine
present is liberated.
2NaCl + MnO, + 2 H2SO, = Na.SO, + MnSO, + 2.H2O + Cls.
Sodic + Manganic + Sulphuric = Sodic + Manganic + Water + Chlo-
chloride peroxide acid sulphate sulphate rine.
[2NaCl-- MnO, + 2SO. Ho. =S0,Nao, +SO, Mno"+2OH, -- Cle.]
(3.) By passing air and hydrochloric acid gas through red-hot
tubes. (Oxland.)
2HCl + Air (O and N.) = H2O + Cl2 + N.
This process has been improved by Deacon (“Journ. Chem. Soc.,”
X., 725), who passes the mixed air and hydrochloric acid gas over
fire-bricks, which are first soaked in a solution of cupric sulphate or of
72 HANDBOOK OF MODERN CHEMISTRY.
cupric chloride, and afterwards dried. The cuprous chloride first
becomes cupric chloride (a), which, by an increased heat, gives up its
chlorine, and again becomes cuprous chloride (3). Thus—
(a) Cu.C., + 0 + 2HC = 2CuC, H. H.O.
Cuprous chloride + Oxygen + Hydrochloric acid = Cupric chloride + Water.
(3.) 20uCl4 = Cu2Cl2 + Cl2.
Cupric chloride = Cuprous chloride + Chlorine.
It will be remarked that in this process, the chlorine is mixed
with twice its bulk of nitrogen, but for trade purposes this admixture
is of no importance.
(4.) By the action of heat on hydrochloric acid and potassic bi-
chromate. (Rogers.)
R2Cr,0; -- 14 FICl = 2KCl + 2CrCl3 + 7H2O + 3Cl2.
Potassic + Hydrochloric = Potassic + Chromic + Water + Chlorine.
bichromate acid chloride chloride
CrO.Ko CrCl
| O + 14EICl = 2KCl + | §: +70H.4 3Cl]
CrO.Ko 3
5.) By the electrolysis of hydrochloric acid.
y y
2HCl = H2 + Cl2.
+
(6.) By fusing together ammonic nitrate and ammonic chloride.
(Maumené.)
4NH4NO3 + 2NH4C1 = 12H2O + 5N2 + Cls.
Ammonic nitrate + Ammonic chloride = Water + Nitrogen + Chlorine.
[4]NVO2(NVH10) + 2NH,Cl =12OH, -i- 5N, + Cl2]
(7.) By heating certain chlorides, such as the chlorides of platinum,
palladium, and gold. Thus—
(a.) PtCl, - PtCl2 + Cl2. (3) PtCl4 = Pt -- Cla.
(8.). By heating a mixture of magnesic chloride and manganic per-
oxide. (Binks and Macqueen.)
2MgCl2 + MnO2 = 2MgO + MnOl. -- Cla.
Magnesic -- Manganic = Magnesic + Manganous + Chlorine.
chloride peroxide oxide chloride
[2]MgCl2 + MnO2 = 2MgO + MnCl2 + Cls.]
Properties.—(a.) Sensible.—Chlorine is a yellowish-green gas,
having an insupportable odor.
(3) Physiological,—It is poisonous and intensely irritating, even
when largely diluted with air. A bird dies in an atmosphere con-
taining 5 per cent. It rapidly disorganizes all tissues.
(y.) Physical.—It has an experimental specific gravity of 2:45, and
a theoretical specific gravity of 2:46. 100 cubic inches, at standard
temperature, weigh 76.3 grains, and 1 litre 3, 1808 grims. It is one of
the heaviest bodies known, gaseous at ordinary temperature.
A pressure of 4 atmospheres (=60 lbs. on Square inch) converts it
CEILORINE. 73
into a yellowish green liquid, which has a specific gravity of 1:33. It
has never been solidified, but remains liquid at a cold of –220°F.
(–140°C.). Liquid chlorine may be prepared either by heating
crystals of the hydrate (Cl2, 10H2O), or of platinic chloride (PtCl4)
placed in one end of a sealed tube, whilst the other end is immersed
in ice and salt.
If the spectrum be passed through chlorine, it will be found that
the blue end is cut off and Fraunhofer's lines disturbed. Chlorine
does not conduct electricity; it is an electro-negative body, and passes
to the + pole of the battery after oxygen and fluorine.
Solubility in water.—The solubility of chlorine in water is as
follows:–
At 50° F (10°C.) water absorbs 2:585 times its bulk of the gas.
At 59° F (15°C.) , ,, 2:368 ,, 2 y
At 104°F. (40°C.) , , ,, 1865 ,, 5 y
(Schönfeld.)
(6.) Chemical.—Chlorine combines with every elementary body.
The moist, but not the dry, gas bleaches litmus and turmeric. It is
neither combustible, nor a supporter of combustion, but when largely
diluted with air, it supports the combustion of a vigorously-burning
taper, the chlorine combining with the hydrogen of the hydro-carbon,
and setting free the carbon.
Action on the non-metals.-Phosphorus catches fire in chlorine
spontaneously, forming PCls. Sulphur burns in it feebly. Selenium,
boron, and silicon combine with it when heated. It does not combine
directly either with carbon or with oxygen.
Combinations with hydrogen. — Chlorine has a very strong affinity
for hydrogen. Its oxidizing property depends upon this affinity for
the hydrogen of water, oxygen being thereby liberated. A mixture
of equal volumes of hydrogen and chlorine, combine with explosion
either by a spark, or when exposed to direct sunlight or to any other
light, such as the electric or magnesium lights, containing a good
supply of actinic rays; whilst the gases unite quietly when exposed to
the light of a gas-flame or of diffused daylight, hydrochloric acid in
each case being formed.
Action on hydrogenous compounds. – The following reactions of
chlorine on compounds of hydrogen should be noted :—
(1.) A taper burns in dilute chlorine with a smoky flame, the
chlorine combining with the hydrogen and liberating the carbon. If
a jet of chlorine be allowed to play on the flame of a spirit lamp, it
becomes luminous, from the solid carbon particles being set free. (2.)
Turpentine vapor (CoEIG) catches fire in chlorine, carbon in large
quantity being disengaged (CoHig-H 8Cle=16|HC1-i-Cho). (3.) If a
mixture of chlorine and olefiant gas (C.H.) be fired, carbon is set
free (C4H4+Cl,-4HCl·HCs). (4.) A mixture of chlorine and marsh
gas (CHA) under the influence of sun-light forms chloroform (CHCls)
74 - IHANTOBOOIC OF MODERN CHEMISTRY.
and tetrachloride of carbon (CC1,), (5.) Ammonia solution is decom-
posed by chlorine, nitrogen being liberated—
8NH3+3Cl2=6(NH,Cl)4-N2.
By its action on a solution of ammonic chloride, chlorine forms the
highly explosive body, chloride of nitrogen. (6.) Water is decom-
posed by chlorine. Berthollet originally supposed chlorille to be
a compound of oxygen and hydrochloric acid, his experiments being
conducted on moist chlorine, whereas it was proved by Davy, that the
chlorine decomposed the water, fixing the hydrogen (as HCl) and
setting free the oxygen. Thus, oxygen may be obtained by passing
steam and chlorine through a red-hot tube (see page 57 F.).
Action on organic bodies.—The enormous affinity of chlorine for
hydrogen renders its action on organic bodies very powerful. These
actions may be thus classified—
(1.) The chlorine may be simply added to the hydrogen compound. Thus—
C.H. (etheme or olefiant gas)+Cl2=C.H.Cle (etheme chloride).
(2) A portion of the hydrogen may be displaced, but without the substitution
of chlorine for it. Thus—
C.H.80 (alcohol)+Cl2=C.H.0 (aldehyd)+2HCl.
(3.) A part or all the hydrogens of a compound may be displaced,
chlorine being substituted for them.—This is seen in the following cases—
(a.) The action of chlorine on marsh gas (CHA).
CH4+ C1 =CH2Cl (methyl-chloride) + HCl.
CH4+ Cl2=CH2Cl2 (formyl-bichloride) + 2 HCl,
CEI -- Cla–CHCls (chloroform) + 3FICl.
CH,-- Clº-CC), (tetrachloride of carbon) +4EICl.
(3) The action of chlorine on acetic acid (C.H.O.).
C.H.O.--Cl–C.H.C10. (monochloracetic acid) + HCl.
C.H.O.--Cl2=C.H.C).O. (dichloracetic acid) +2HCl.
C.E.O.--Cla–C.HCl2O, (trichloracetic acid) + 3HC1.
(4) This substitution may be only partial,—Thus, in the action of
chlorine on alcohol, 5 hydrogens are replaced by 3 chlorines.
C.HsO4-8Cl=C.Cls HO-H 5HCl.
Alcohol. -
It will be noted that this affinity of chlorine for hydrogen on the
one hand, and the universal presence of moisture in bodies on the
other, renders chlorine indirectly a very powerful oxidizing agent.
Thus—
2H2O+2Cl2=4HCl·HO2.
We may here note some of the results of this oxidizing action of
chlorine.
(1.) Various chemical combinations may be effected thereby, as in the
formation of acetic acid from aldehyd.
C.H.0 (aldehyd)+H,0+Cl2=C.H.O. (acetic acid)+2HCl.
CHILORINE. 75
(2.) Its bleaching power, depends on the action of the nascent oxygen
set free, by the chlorine combining with the hydrogen of the water.
Absolutely dry chlorine has no bleaching action, but in the presence
of moisture every organic coloring matter, except carbon, is bleached
by it. Mineral colors are not generally acted upon. In the case of
indigo, which chlorine bleaches rapidly, it changes it first into isatin,
and afterwards into the yellow-tinted chlor-isatine. The following
equations represent this action—
(a.) CeBIANO (indigo) + H20+ Cl2=CaRIANO.(isatine) +2HCl.
(ſ3.) CaFIANO.(isatine)+Cl2=CalT,CINO,(chlor-isatine) + HCI.
Further, a coloring matter bleached by chlorine is destroyed, and
cannot, as in bleaching by Sulphurous acid, be restored by the action
of other re-agents.
(3.) Its power of disinfection, again, is an oxidizing action, and
depends upon its power of breaking up ammonia and sulphuretted
hydrogen, as well as organic matters generally.
Thus it would appear that the chemical activity of chlorine, depends
on its affinity for hydrogen, and its power of oxidation, the result of
that affinity.
Action on the metals and metallic orides, etc.—(a.) Its action on the
metals is energetic. Powdered antimony, arsenicum, finely divided
iron, and Dutch leaf (copper and zinc), light spontaneously when
dropped into chlorine. Sodium and magnesium burn in it, forming
NaCl and MgCl2, Gold (as leaf gold) combines slowly with it,
forming AuCls.
(B.) Metallic oxides, where the affinity between the oxygen and
the metal is feeble, are easily decomposed by chlorine. Thus—
H20+3Hg.0 (mercuric owide) + 2Cl2=2|Hg.0, HgCl2 (mercuric oxy-
chloride) + 2 HC10.
(y.) Chlorine is absorbed by a solution of caustic potash, potassic
chloride and potassic hypochlorite being formed.
Cl, -- 2KHO=ISC1-i-KClO + H2O.
If an aqueous solution of chlorine be cooled to 32°F. (0°C.), a
solid crystalline hydrate (Cl210H2O) is formed. This hydrate may be
seen when chlorine is collected by displacement over very cold water
on a cold day. The gas is thus rendered foggy, but clears rapidly on
the application of a moderate warmth.
Tests.-Its odor, color, and bleaching properties constitute the chief
tests for chlorine in an uncombined state. When free, or combined
with a metal, it may be known as follows:–
(1.) Mercurous nitrate gives a white precipitate (mercurous chloride
or calomel), which is insoluble in nitric acid, and is turned black by
ammonia.
(2.) Argentic nitrate gives a white curdy precipitate (AgCl), soluble
in ammonia, and insoluble in nitric acid. Free chlorine produces, with
76 EIANDBOOK OF MODERN CHIEMISTRY.
an argentic nitrate solution, a trace of argentic chlorate as well as
argentic chloride. -
6AgNO3 + 3Cl2 + 3H2O = 5AgCl + AgClO3 + 6HNO3.
Fallacies.—Bromides, iodides, and cyanides. (1.) The bromide of
silver is of a reddish color. (2.) An iodide is known by its reaction
on starch paste, when the iodine is set free by the addition of a trace
of chlorine water, or else by the reaction of the iodide on palladic
nitrate. (3.) A cyanide is known by the formation of prussian blue,
when acted on by a mixed per- and protosalt of iron.
Estimation.—Chlorine is determined quantitatively as argentic
chloride, every 100 parts of which contain 24.74 parts of chlorine.
Uses.—(a.) In nature, none,
(b.) In the arts, chlorine is largely used as a bleaching agent for
linen and cotton cloth. Wool or silk cannot be bleached with chlo-
rine, on account of its injurious action on the fabrics, hence in these
cases sulphurous acid is employed. The use of chlorine as applic-
able to the arts was first suggested by Berthollet, in 1785. Chloride
of lime, as it is called, is the form in which it is Ordinarily employed.
Any acid will liberate the chlorine from this compound.
(e.) In medicine, the dilute gas is used as an inhalation (vapor chlori,
B.P.), i.e. moist chlorinated lime from which the carbonic acid of the
air sets free a little chlorine. The solution of chlorine (liquor chlori,
B.P.), rapidly decomposes, and should be preserved in dark blue
bottles. When freshly prepared, it contains more than twice (2-3)
its bulk of chlorine, and about 0.75 per cent. by weight.
(d.) As a disinfectant its action is very intense, owing to its power
of breaking up offensive effluvia. If chloride of lime be used for the
sick room, a quarter of a pound should be dissolved in about a gallon
of water; a piece of flannel dipped in the clear liquor should then be
freely exposed to the air of the room, from which, by the action of
atmospheric carbonic acid, a small but regular evolution of chlorine
will take place. For active disinfection, some hydrochloric acid and
peroxide of manganese should be mixed on a plate, and placed on a
hot brick; the room must then be closed, and left for some hours.
Everything metallic should be previously removed from the room.
(e.) In its chemical reactions chlorine acts in the presence of water
as a powerful oxidizer, protoxides being by its action converted into
peroxides, sulphur into sulphuric acid, etc.
COMPOUNDS OF CHLORINE AND Oxygen.
Chlorine and oxygen are both strongly electro-negative, and have
great affinity for hydrogen. Hence their affinity for each other is
but slight. The compounds when formed are unstable, and their
direct union has not been effected. Possibly there are seven oxides of
chlorine, as follows:–
FIYPOCHLOROUS ANIHYDRIDE. 77
º * Constitutional
The Anhydride + H20 forms the Acid. formula for the Acids.
1. Cl.0 or OCl, Hypochlorous. 2HC10. OCIEI or CIHo.
2. C],02 (?). (?). (?).
3. Cl,0a or ) 0. Chlorous. 2IIC10. | OH 9* O(|EIO.
OC]. l
OCl.
4. C1.0, or 3. Chloric peroxide.
OC1. C
OC1
5. Cl,0s (?). Chloric. 2HC10. (99. , |3:
* | OH | OHo.
6. C],0s (?). (?). (?).
2 - 6 ſº
7. C1,0, (?). Perchloric. 2HGo, )3 or 3%
(8H l OHO.
Nos. 1, 3 and 4 (viz., Cl2O, Cl2O3 and Cl2O4) are the only anhy-
drides that have been isolated. The others are either non-existent or
exist only in combination.
There are four oxygen acids which have been regarded for obvious
reasons as a series of oxides of hydrochloric acid.
Hypochlorous Anhydride (Cl40 = 87) (OCls.)
Molecular weight, 87. Molecular volume, TT . Relative weight
(H = 1), 43-5. Specific gravity (Air = 1) theoretic, 3-01. Liquid
boils at 68°F. (20° C.). 1 litre weighs 43.5 criths (0.0896 × 43.5)
= 3-8976 grims., and 100 cubic inches 93.0 grains.
Preparation.—1. By passing dry chlorine over dry mercuric oxide -
contained in a cold tube. (Pelouze.)
2Hg.0 + 2Cl3 = FIg,Cl.0 + C].O.
Mercuric oxide + Chlorine = Mercuric oxychloride + Hypochlorous anhydride.
|HgCl
[*Hgo + 2Cl3 = { O + OCle. |
ligol
2. By abstracting the water from hypochlorous acid, with glacial
phosphoric acid.
2EIC]O — H.O = C],0.
Hypochlorous acid — Water = Hypochlorous anhydride.
3. It is believed by some to be produced in making the euchlorine
of Davy, on adding hydrochloric acid to potassic chlorate, but of this
there is much doubt.
Properties.—(a.) Sensible and Physiological.—A deep yellow gas,
deeper in color than chlorine. It has a sweet taste, and is intensely
Suffocating when breathed.
78 HANDBOOK OF MODERN CBIEMISTRY.
(3.) Physical. —Its specific gravity is 3.01. Two volumes of chlorine
and one volume of oxygen form two volumes of the gas (water type).
100 cubic inches weigh 93 grains, and 1 litre 3-897 grammes. By
pressure and by the cold of ice and salt (–4°F. or —20° C.), it may
be condensed into a red and explosive liquid, which boils at 68°F.
(20°C.) Both light, and a very slight heat, such as the warmth of
the hand, decompose it. Water dissolves about 200 times its bulk,
forming a yellow solution, which has an acrid taste.
(y.) Chemical.—It bleaches litmus and indigo more powerfully than
chlorine. It is decomposed by a spark, or by the action of any sub-
stance having an affinity for chlorine or for oxygen.
Hypochlorous Acid, (HClO = 52-5) (OCIH or CIHo.)
Synonym.—Hydric hypochlorite.
Preparation.—(1.) By the action of water on hypochlorous anhy-
dride.
Cl2O + H.O = 2ECIO.
Hypochlorous Anhydride + Water = Hypochlorous acid.
[OCl. + O.H.- 2001H.]
(2.) By passing air, charged with hydrochloric acid gas, through a
solution of potassic permanganate, acidulated with sulphuric acid,
and heated on a water bath. The product is to be collected by distil-
lation. In this reaction HClO is formed from HCl, by direct oxida-
tion (2HCl + O. = 2EICIO).
(3.) By mixing together mercuric oxide, water, and chlorine, and
distilling.
3HgO + H20 + 2C1, = 2Eſg0, HgCl, + 2.HClO.
Mercuric oxide + Water + Chlorine =.Mercuric oxychloride + Hypochlorous acid.
HgCl
O -
[3Hg.0 + OH, -- 2012 = { Hg + 2ClFIo.]
O
HgCl
(4.) By distilling a hypochlorite with an oxy-acid.
CaCl2O2 + H2SO4 = CaSO, -ī- 2FICIO.
Calcic hypochlorite + Sulphuric acid = Calcic sulphate + Hypchlorous acid.
[Ca(OCl)Cl + SO. Ho, - SO.Cao" + 2CIHo.]
Properties, (a.) Sensible. — A yellowish-red, chlorine-smelling
liquid, having an acrid but not a sour taste,
(3) Physiological—It acts as an intense irritant poison, and browns
the skin. *
(y.) Physical.—It boils at 19°F. (– 7° C.), giving off a heavy
yellow vapor. It is decomposed by light, into chlorine and chloric
acid.
(3) Chemical.—The gas given off when the acid is heated, is very
unstable and highly explosive. The acid has a powerful bleaching
CHILOROUS ANEIYI)RIDE. 79
action; its intensity in this respect being double that of the chlorine it
contains, evolving as it does double the oxygen (which in the nascent
state is the true bleaching agent) set free by ordinary chlorine.
Thus— -
(a.) Cl2 + OH. = 2EICl + 0 (action of common chlorine).
(3) CIHO = HCl + O (action of hypochlorous acid).
It is decomposed by carbon, iodine, sulphur, selenium, phospho-
rus, arsenic, and antimony; carbonic, iodic, sulphuric, selenic, phos-
phoric, arsenic, and antimonic acids being respectively formed.
If a piece of ammonic chloride be placed in the acid, the oily and
highly explosive chloride of nitrogen is formed.
If the acid or any of its salts be heated with hydrochloric acid,
both acids are decomposed.
HCl + HClO = H2O + Cla.
Action on the metals.-This varies in a remarkable manner. Iron
combines with the oxygen of the acid, and sets free chlorine. Silver
combines with the chlorine of the acid, and sets free oxygen. Copper
and mercury combine with both the chlorine and the oxygen.
Action on metallic compounds.-Plumbic oxide combines with the
oxygen, forming PbO2, and sets free chlorine. Argentic oxide (Ag30)
combines with the chlorine, forming AgeCle, and sets free oxygen.
Argentic chloride, by its presence alone, and without being itself
decomposed, sets free both oxygen and chlorine, in a gaseous form,
from the acid.
On several organic bodies the acid acts vigorously. Thus, urea is
broken up by its action. -
CNºo + 3HClO = CO2 + 3BHCl + 2.H2O + No.
I'ê8.
It forms with bases the salts known as hypochlorites, which are
of great importance in the arts. “Chloride of lime” is prepared by
bringing chlorine into contact with recently-slaked lime, and is
either a calcic chloride mixed with calcic hypochlorite—
(CaCl2 + Ca2C10), or (Ca"Cl2 + Cao’Clo),
S-' S-N-7
Calcio Calcic
chloride. hypochlorite.
or, as some think, a calcic oxydichloride, or, as it is called, a calcic-
chloro-hypochlorite (Ca(OCl)Cl) or (CaOCl).
ſ OCI
Chlorous Anhydride (Cl:0s = *f; l
Cl.
Molecular weight, 119. Molecular volume (anomalous) ||T|. Relative
weight (H = 1), 59.5. Specific gravity, theoretic, 4:117; observed,
4-070. 1 litre weighs 39:7 criths (0.0896 × 39:7) = 3:5571 grins.,
and 100 cubic inches 126'57 grs.
80 HANDBOOK OF MOIDERN CHEMISTRY.
History.--Discovered by Millon (1842).
Preparation.-1. By deoxidizing chloric acid with nitrous anhy-
dride.
2HClO3 + N303 - Cl2O3 + 2HNO3.
Chloric acid + Nitrous anhydride = Chlorous anhydride + Nitric acid.
OC1
| | 3}, + N.O. = }} + NoHo
OCl
2. By heating a mixture of potassic chlorate, arsenious acid, and
nitric acid. The nitrous acid (formed by the arsenious acid becoming
oxidized at the expense of the oxygen of the nitric acid) acting on the
chloric acid (produced by the action of the nitric acid on the potassic
chlorate) deoxidizes it, and becomes again converted into nitric acid.
HaAsO3 + 2 HNO3 + 2KClO3= HaAsO! -- 2KNO3 + H2O. -- Cl2O3.
Arsenious + Nitric + Potassic = Arsenic -i- Potassic + Water + Chlorous
acid acid chlorate acid nitrate anhydride.
As Ho3 + NO2Ho + 2 =ASOHo3+ 2NO2Ko- OH2 + O.
OKO OC1
(Tartaric acid may be used in the place of arsenious acid, when
carbonic acid will be generated.)
Properties. It is a yellowish green gas, very irritating when
breathed, and stains the skin yellow. It may be condensed by an
intense cold into a red liquid (Sp. Gr. 1-33), which is very unstable
and explosive, and boils at a temperature a little above the melting
point of ice. Water dissolves ten times its bulk of the gas, forming
chlorous acid.
It is a powerful oxidizing and bleaching agent. A heat of 134°
F. (57 C.) decomposes it into its constituent gases. Most of the
non-metals decompose it. The metals have but little action upon it,
except arsenicum, which decomposes it, and mercury which absorbs
it. The solution of the gas, however, oxidizes most metals, forming a
mixed chlorate and chloride.
Chlorous Acid (HClO3 = 68-5). (OCl Ho.)
Preparation,-By acting on chlorous anhydride with water.
Cl.0, H. H.O = 2 HClO3.
Chlorous anhydride + Water = Chlorous acid.
OCI
« O + O.H. = 2001 Ho.
lool
Properties.—The acid is unstable. It is decomposed even by car-
bonic anhydride. It is a powerful oxidizing and bleaching agent,
CHLORIC PEROXII) E. 81
and acts on all metals, forming chlorates and chlorides. It is pre-
cipitated as plumbic or argentic chlorite with plumbic or argentic
nitrate. It forms salts called Chlorites. They may be known from
the hypochlorites, by their bleaching power not being destroyed by
the action of nitric acid and arsenious anhydride.
ſ OCI
Chloric Peroxide (Cl2O, - 135). l 8
OCl.
Relative weight 33°75. Specific gravity, theoretic, 2.335; observed,
2.3227. Boiſing Point, 68° F (20°C.).
Synonyms.-Perocide of Chlorine; Chloric diocide; Hypochloric acid;
Perchloric oride.
History.--Discovered by Davy in 1815.
Preparation,-1. By the action of sulphuric acid on potassic
chlorate.
3KClO3 + 2 H.S.O. = KClO4 + 2KHSO, -i- OH, -i- Cl2O,
Potassic + Sulphuric = Potassic + Hydric potassic + Water + Chlºric
chlorate acid perchlorate sulphate peroxide.
| OC |QCl go
OKO * x- * *- O
ORCO OC]
2. By heating a mixture of Oxalic acid and potassic chlorate to 149°
F. (65°C.). (Calvert.)
Properties.—(a.) Sensible and Physiological.—A deep yellow green
gas, having a strong chlorine odor and a sweet taste. It is excessively
irritating.
(3.) Physical.—It has a specific gravity of 2:36; 100 cubic inches
weigh 73°16 grains. By a slight pressure, or by a cold of —4°F. (–20°
C.), the gas condenses into a red explosive liquid. At a heat of 140°F.
(60°C.) it explodes, the gases formed occupying a volume one-third
greater than the original gas. It may be preserved in the dark, but is
decomposed by light. Water dissolves 20 times its bulk of the gas.
(y.) Chemical.—It is a powerful oxidising and bleaching agent.
Its action on many bodies, such as mercury, phosphorus, sugar, and
turpentine, is energetic. It neither forms an acid nor salts. It is ab-
sorbed, however, by alkaline solutions, a chlorite and a chlorate being
formed. Thus— -
Cl2O, H- 2ICHO
Chloric + Potassic
RC10. -- KClO3 + H2O.
l’otassic + l’otassic + Water,
–
peroxide hydrate chlorite chlorate
OCl
O *- C Cl
O + 20KH = {3}. + |8. + OH.g.
OCI
G
82 HANDBOOK OF MODERN CEIEMISTRY.
Synonyms.-Oaymuriatic acid, hydric chlorate.
History.-Discovered by Chenevix (1802). Its properties were
studied by Guy Lussac (1814). º
Preparation.—(1.) A large excess of chlorine is first passed into a
strong solution of potassic hydrate, thus producing a potassic chlorate.
This is decomposed, the potassic chloride being previously separated
by crystallization with hydrofluosilicic acid.
(a.) 6KHO + 3Cl3 = 5KCl -- KC10, + 3H2O.
Potassic hydrate + Chlorine = Potassic chloride + Potassic chlorate + Water.
6OKH + 3Cl. = 5|KCl + KClO3 + 3OH2.
(3.) 2KClO3 + H2SiF6 = 2EIC10s + K2SiF6.
(It is, perhaps, best to form a baric chlorate, and to decompose this
with its equivalent of sulphuric acid. After filtering off the baric
sulphate, the acid filtrate must be carefully concentrated by evapora-
tion.
Properties.—(a.) Sensible and Physiological,—A syrupy liquid, having
a strong chloroid smell, a very acid taste, and a powerful corrosive
action on the body.
(3.) Physical-Light decomposes it. It is freely soluble in water.
A heat of 100°F. (38°C.) breaks it up into oxygen, chlorine, perchloric
acid, and water. Thus—
Chloric acid = Perchloric acid + Water + Oxygen + Chlorine.
(y.) Chemical.—Chloric acid is a powerful acid, and even chars paper.
It rapidly oxidizes organic matter, but it does not bleach. It is
monobasic, like nitric acid. The anhydride has not been isolated.
It forms salts called chlorates, which are largely used both in medi-
cine and in the arts. The acid itself has no uses.
Perchloric Acid (HClO4 = 100°5). | OI’
Molecular weight, 100'5. Specific gravity, 1782.
Synonyms.—Hydric perchlorate.
History.— Discovered by Count Stadein (1814).
Preparation.—(1.) By distilling potassic perchlorate, with three
times its weight of sulphuric acid. -
2KClO4 + H2SO4 = 2 HClO4 + K.SO4.
Potassic perchlorate + Sulphuric acid = Perchloric acid + Potassic sulphate.
OCl TOCI
2 |: + SO. Hoe = 2 |: -- SO.Koz
OFCO OHo
The impure acid thus formed is then rectified.
BROMINE, - 83
(2.) By the action of heat on chloric acid (prepared by decomposing
baric chlorate with sulphuric acid), whereby perchloric acid, together
with chlorine, oxygen and water are formed. (See Chloric Acid.)
Properties.-(a.) Sensible and Physiological. — A colorless liquid,
having a very sour taste, even when very dilute. It produces frightful
burns when applied to the skin. It turns yellow by keeping, from the
liberation of the oxides of chlorine.
(3.) Physical.—Very volatile. It has a specific gravity of 1782 at
60°F. (15.5°C.). It remains liquid at —31°F. (–35°C.).
(y.) Chemical.—The anhydride is unknown. When very dilute it
reddens litmus, but does not bleach vegetable colors. In this diluted
form it is the most stable of the chlorine oxides. It dissolves iron and
zinc, setting free hydrogen. The pure acid is one of the most powerful
oxidising bodies known, an explosion resulting when a single drop is
brought into contact with any organic substance. In sealed tubes it
undergoes spontaneous decomposition and bursts the tubes. It
decomposes when distilled. It forms with water a white, silky, crys-
talline hydrate (HClO4, H.,0) (Crystals of Serullas). This hydrate
is decomposed by a heat of 280° F (110°C.) into the pure acid
(HClO4) which distils over, another hydrate (HClO4.2H2O), a thick
oily liquid remaining in the retort, which is not volatile at a lower
temperature than 397°F. (203°C.).
The acid forms salts called perchlorates (M'C101),
There are several compound oxides of chlorine, the most important
of which is euchlorine. This was discovered by Davy, and is pre-
pared by heating together hydrochloric acid and a chlorate. It is
probably a mixture of chlorine and chloric peroxide. It is a yellow
explosive gas.
BROMINE (Br.).
Atomic weight, 80. Molecular weight, 160. Molecular volume Ti.
Atomicity monad () (HBr—RBr—AgBr). Relative weight (H=1)
80. Specific gravity (Air=1) of vapor, theoretic, 5:536, observed,
5-54. Specific gravity of liquid (Water = 1) at 32°F., 3,187. Fuses
at —4 F. (–20°C.) Boils at 145.4°F. (63.0°C.).
Synonyms.-Muride (muria, brine), Balard; Bromine (Boſpoc, fetid),
Guy Lussac.
History.—Bromine was discovered by Balard, of Montpellier, in
August, 1826, in “bittern,” the mother liquor of sea water, and was at
the time supposed to be a compound of chlorine and iodine. After-
wards Balard, Loewig, and Serullas together, proved its elementary
Inature.
Natural History.—It never occurs in nature in a free state, (a.) In
the mineral kingdom it is invariably found in company with chlorine
compounds. Sea water contains 0-9 to 125 grains of MgBr, per
84 HANDBOOK OF MODERN CHEMISTRY.
gallon. The Dead Sea water is specially rich in bromine compounds.
So also are the mineral springs of Kreuznach, Kissengen, Kershall,
etc. Bromine is also found mineralized with silver, zinc, and cadmium.
It is found in most samples of rock-salt, and also in coal. (Bussy.) (3.)
In the vegetable kingdom it is found more or less in all sea plants; and
(Y.) In the animal kingdom it is found in sponges, liver of cods, etc.
Preparation.—Bromine is usually obtained from the mother liquor
of the springs of Kreuznach, Schönbeck, etc.
(1.) The old process used in preparing it is as follows —
(a.) Chlorine is first added to the liquor to set free the bromine
2KBr + Cl. = 2KCl + Br.
(b.) The solution is then shaken up with ether, and after standing,
the ethereal layer containing the bromine is decanted.
(c.) Caustic potash is now added, and heat applied, whereby the
bromine is converted into potassic bromide and potassic bromate—
6|KEIO + 3 Bra = 5KBr + ICBPOs + 3H2O.
Potassic hydrate + Bromine = Potassic bromide + Potassic bromate + Water.
|QK
6OKH + 3 Br,
-
löB,
(d.) The residue is now ignited, in order to convert the potassic bro-
mate into potassic bromide :-
(2KBrO3 = 2IBr -- 30.).
(e.) The potassic bromide is now dissolved in water and distilled
with manganic peroxide and dilute sulphuric acid, when bromine
distils over— -
2KBr + 2 H.S.O., + MnO2 = K.S.O., + MnSO, -- 2H20+ Br.
Potassic + Sulphuric + Manganic = Potassic + Manganous + Water + Bromine.
bromide acid peroxide sulphate sulphate
2KBr +2SO. Hoo-H MnO2 =SO.Ko. -- SO.Mno"+2OH.-- Bro.
(f) The bromine is then re-distilled with calcic chloride in order to
free it perfectly from water.
(2.) The new process of Desfosses, as modified by Mohr and Loewig
consists in distilling the mother liquor at once with manganic peroxide
and dilute sulphuric acid, the distillate being afterwards rectified with
calcic chloride.
Broperties.—(a.) Sensible and physiological.-Bromine is a dark red
liquid, evolving red fumes at ordinary temperatures. It is the only
liquid non-metallic element, mercury being the only liquid metallic
element. Its odor is foetid and irritating, and its taste acrid and
caustic. It stains the skin a permanent yellow. It is an active poison.
(3.) Physical.—Liquid bromine has a specific gravity of 3:187, and
its vapor of 5'54. The vapor is evolved at ordinary temperatures.
It boils at 145.4 F. (63°C.), and freezes to a brown crystalline solid at
—4 F. (–20°C.). 1 part of bromine is soluble in 34 parts of water, the
solution having a specific gravity of 1:024. The solution rapidly
BROMINE. 85
decomposes under the influence of sunlight into oxygen and hydro-
bromic acid. It is also soluble in alcohol and ether.
(y.) Chemical.—These are in many respects similar to chlorine. As
an oxidizing agent it bleaches litmus and indigo. A taper introduced
into the concentrated vapor burns badly and with a smoky flame.
Phosphorus and some of the metals take fire when brought into
contact with it. Turpentine vapor decolorizes bromine vapor, hydro-
bromic acid being formed. Here its affinity (like that of chlorine) for
hydrogen, and its power of displacing it is to be noted. It rapidly
attacks organic matters, staining them a yellow color. It combines
with all elementary bodies, forming bromides. It also combines with
water, forming a hydrate (Brz, 10H2O).
Tests.-(a.) In a free state—Bromine is set free from its compounds
by chlorine. It may be known by its red color, and by forming a
yellow compound with starch.
(3.) In combination.—(1.) Plumbie acetate gives a white precipitate of
plumbic bromide (PbPro). (2.) Argentic nitrate gives a yellowish-
white precipitate of argentic bromide (AgBr) which is insoluble in
dilute nitric acid, and of difficult solubility in dilute ammonia.
Uses.—In the arts, bromine is used in photography. In medicine, the
bromide of ammonium (NH, Br) (ammonii bromidum, B. P.), the
ferrous bromide (Febr.), the potassic bromide (KBr), as well as a
solution of bromine (10 minims in 5 ozs. of water) are officinal.
Bromine is a disinfectant, its power being dependent on its affinity
for hydrogen, and its consequent oxidising properties. -
CoMPOUNDs of BROMINE AND OxYGEN.
These are probably analogous to the oxides of chlorine; there
should be, therefore, four acids and their anhydrides:—

Anhydride. + H20 form Acids. º
1. Br,0 OBr, Hypobromous. 2HBrO. OBTBI or BrEIo.
2. Br,0s | . . . Bromous. 2HBºo, 3; or obºito.
OBr *
3. Br,0s e tº Bromic. 2HBrO, | O or 3.
löH ( OHo.
OBE OBr,
4. Br,0, tº a Perbromic. 2HBrO, º OI’ | O
OH OHo.
The first anhydride (Br,0) is the only one known.
Hypobromous Acid (HBrO) may be formed either by agitating
mercuric oxide with bromine water (Balard), or by adding bromine to an
argentic nitrate solution (Dancer). It is a yellow liquid, easily decom-
posed by heat; it bleaches powerfully.
86 HANDBOOK OF MODERN CHEMISTRY.
Bromic Acid (HBrO3).—The anhydride is unknown. It may be
prepared like chloric acid; also by passing chlorine through bromine
water (Br, 4-5Cl2 + 6H.0 = 2 HBrO, + 10HCl). It is decomposed
by heat.
Perbromic Acid (HBrO4) may be prepared by adding bromine to
a solution of perchloric acid. It is a colorless oily liquid, and the
most stable of the oxides of bromine.
CoMPOUND OF BROMINE AND CHLORINE.
Bromous Chloride (BrCl32) is prepared by passing chlorine through
liquid bromine. It is a reddish, volatile, very unstable, pungent
liquid, soluble in water, the solution possessing considerable bleach-
ing power.
IODINE (I = 127).
Atomic weight, 127, Molecular weight, 254. Molecular volume, TT .
Atomicity monad (), (HI); occasionally triad (ICl2). Relative
weight (H = 1), 127. Specific gravity of solid iodine, 4.947; of
vapor, theoretic, 87884; observed, 8-7 16, Melts at 225° F. (107°
C.), and boils at 347° F (175° C.).
History.—Iodine was discovered by Courtois (1812), a French
saltpetre manufacturer, on adding sulphuric acid to the waste liquor
of kelp. Courtois gave some of it to Desormes and Clement, who
published their researches respecting it (1813). It was further
examined by Vauquelin, and also by Davy and Guy-Lussac (1813
and 1814).
Natural History.—It never occurs in nature in a free state. (a.)
In the mineral kingdom iodine is found in sea water as calcic iodide, but
to a less extent than the bromine compound (1 in 250,000: Sonstadt).
It is supposed to be the active principle of many mineral springs where
it is present in combination with potassium, sodium, and magnesium.
The spring at Rey, near Freistadt, contains 0.819 part, and that at
Halles 0.426 part of magnesic iodide in 10,000 of water. It is also
found in the Bath, the Cheltenham, the Leamington, and the Bon-
nington springs. It is found mineralised with zinc (Silesian ore), lead,
mercury, and silver (Mexican ore). It is found in rock salt, in many
limestones and dolomites, in Chili nitre (and hence occasionally con-
stitutes an impurity of nitric acid), and occasionally in coal. (3.) In
the vegetable kingdom it is found in sea-weeds as an alkaline iodide,
extracted by them from sea-water.
Iodine in 100 parts
of dried plant.
Laminaria digitata... tº ſº tº 4 * * * * * 0.47
Laminaria saccharina tº ſº ºr & º º tº tº gº 0.16
Fucus vesiculosus ... • * tº 6 s is tº º tº 0-01
Fucus nodosus e i & tº a tº * * 0. * * * 0.04
IODINE. - 87
Scotch and Irish sea-weeds contain more iodine than English sea-
weeds. It is said to be present in fresh-water plants that grow in
running streams (Chatin). (y.) In the animal kingdom, it is found in
marine animals, and notably in sponges, oysters, etc. It is an inva-
riable constituent of cod liver oil (0.04 to 0-32 per cent.).
Preparation.—(1) Process of Wollaston, as modified by Whytelaw.
(a.) The sea-weeds found on the Scotch coast (specially the lami-
naria digitata,) are collected during the summer months, dried by
exposure, and then burnt without flame, in order to prevent, as far as
possible, any loss of sodic iodide. The ash constitutes what is called
“kelp,” or “warec.” A ton of good kelp made from the laminaria
digitata will yield from 10 lbs. to 15 lbs. of iodine.
(b.) The kelp is first lixiviated with boiling water, whereby about
50 per cent. of solid matter is dissolved, consisting of sodic car-
bonate, sulphate, sulphite, and sulphide, besides sodic, potassic and
magnesic chlorides and iodides.
(c.) The solution is then filtered and evaporated to a smaller bulk,
in order to separate the sodic carbonate (Scotch soda). It is after-
wards still further evaporated to separate the sodic sulphate and
chloride.
(d.) The residual liquor (Sp. Gr. 1.33 = iodine ley) is now mixed
with about one-eighth of its bulk of oil of vitriol, and allowed to
stand for 24 hours, whereby carbonic and sulphurous acids, and sul-
phuretted hydrogen are evolved, and sodic sulphate and much free
sulphur separated.
(e.) The liquid is then filtered and put into a leaden still (iodine
still) with manganic peroxide, and heated at a temperature not ex-
ceeding 212°F. (100° C.). In this way the formation of chlorine is
prevented, and the iodine is obtained as a sublimate.
2NaI + MnO, + 2 H2SO4 = Nass0, -i- MnSO, + 2 H2O + Ic.
Solic + Manganic + Sulphuric = Sodic + Manganic + Water +Iodine.
iodide oxide acid sulphate sulphate
2NaI + MnO2 + 2SO, Hos =S0,Nao. --SO, Mno" + 2011, + Is.
(f) The iodine is now purified by resublimation. Commercial
iodine generally contains more or less chloride, cyanide, and bromide
of iodine. *
(2.) A second process, occasionally adopted, is throwing down the
iodine, with a subsalt of copper, as a diniodide of copper. In
practice, cupric and ferrous sulphate are mixed with the iodine ley.
The subiodide of copper (CuI) formed is then distilled with manganic
peroxide and sulphuric acid, whereby iodine is liberated— -
"Cu'...I., + 2MnO. H. 4H.S0, − 20uSO, -i- 2MnSO, + 4H.0 + I.
(3.) Emil Becht's Process (Prize Essay, Florence, 1849). When the
solutions are very poor in iodide, Bechi sets free the iodine with nitro-
hydrochloric acid, and then filters the liquid through recently ignited
lampblack. The lampblack is then washed with a potash solution,
88 . - HANDBook of MODERN CHEMISTRY.
and the solution evaporated to dryness, the iodine of the solid residue
being afterwards liberated by distillation with manganic peroxide and
. Sulphuric acid.
(4.) The iodine is sometimes thrown down from the solution by first
adding a little chlorine or nitro-hydrochloric acid, and afterwards raw
starch, which sinks to the bottom, carrying the iodine with it.
(5.) The iodine, after being liberated with chlorine, is sometimes
extracted from the aqueous solution by shaking it up with benzol.
The benzol solution is then treated with a solution of potash, when
potassic iodide and potassic iodate are formed (a), from which the
iodine may be precipitated with hydrochloric acid (B).
(a.) 6RHO + 3T. = 5KI + KIOA -- 3 H2O.
(3.) 5]&I + KIO3 + 6HC1 = 6.KCl + 3H2O + 3T.
(6.) In Stanford's process for the preparation of iodine, the winter
weeds (said to contain the most iodine) are dried under cover, sub-
mitted to hydraulic pressure, and heated in iron retorts, the gas set
free, being collected and utilised.
Properties.-(a). Sensible.—Iodine is a black solid, having con-
siderable metallic lustre, and crystallizing in acute rhombic octahedra.
Its odor is peculiar, and its taste acrid. It stains the skin yellow.
The vapor is a bright violet.
(3.) Physiological,—It is an irritant and caustic poison. The vapor
is irritating to the lungs, but when largely diluted with air, it has
been found in certain cases to act beneficially (vapor iodi, B. P.).
(y.) Physical.-Solid iodine has a specific gravity of 4947, and the
vapor 8-716. The vapor of iodine is the heaviest vapor known, 100
cubic inches weighing 270°32 grains. Iodine volatilizes both at
ordinary and at high temperatures unchanged. It fuses at 225° F.
(107°C.). It boils, when perfectly dry, at 347°F. (175° C.), but when
distilled with water it volatilizes at 212°F. (100° C.). It is a non-
conductor of heat and electricity. Its solution in carbonic disulphide
is found to be opaque to light rays, but transparent to heat rays.
Iodine is dichroic. If the vapor be freely diluted with air, it transmits
the red and blue rays of light, and absorbs the green ; but the con-
centrated vapor absorbs the red rays, the blue only being transmitted.
Seven thousand parts of water at 60° F. (15-5° C.), dissolve one part
of iodine, forming a pale brown liquid, which, in the presence of
oxidizable matter, rapidly decomposes, hydriodic acid being formed.
Hot water dissolves a larger quantity. The presence of saline
matters, and specially of potassic iodide, greatly facilitates solution.
Lugol's solution (liquor iodi, B. P.) consists of 20 grs. of iodine, 30
of potassic iodide, and 1 oz. of water. Iodine is far more soluble in
alcohol and ether than in water. If water be added to its solution
in ether or in alcohol, some of the iodine will be precipitated. A
spirituous solution with potassic iodide, forms the tinctura iodi (B. P.)
It is even more soluble in chloroform, in benzol, in carbonic disulphide
IODINE. . . . -- . 89
and in carbonic tetrachloride, the solutions in these liquids being
black, and depositing iodine on evaporation. - -
(6.) Chemical.—An aqueous solution of iodine bleaches litmus and
indigo slightly. A taper introduced into iodine-vapor is immediately
extinguished. Iodine more readily combines with oxygen than either
chlorine or bromine. It forms iodic acid when boiled with nitric
acid, neither chlorine nor bromine being oxidized when similarly
treated. Nevertheless, direct union between oxygen and iodine
cannot be effected.
Iodine forms one compound with chlorine. Phosphorus takes fire
when brought into contact with iodine. It combines with sulphur
forming a black crystalline body (S.I.), used in medicine. Its action
on hydrogen is not intense, presenting, in this respect, a marked
contrast both to chlorine and to bromine. Although the metals
generally are attacked by iodine, nevertheless its action on the metals
is weaker than that of either chlorine or bromine. Hence it may be
displaced by them. If iodine and iron suspended in water, be heated
together, an iodide of iron is formed, a compound used in medicine
(ferri iodidum, Fels) as a pill (pilula ferri iodidi), and a syrup (syrupus
ferri iodidi). Iodine forms no definite hydrate with water.
As regards its action on organic bodies, it will sometimes be found
to combine with the organic body, and sometimes to oxidize it by
combining with hydrogen. But it never displaces hydrogen directly,
although it may at times indirectly.
Tests, (a.) In a free state only.—It changes starch a blue color
(iodide of starch). [This action of starch on free iodine was dis-
covered by Colin and Gaultier de Claubry. 1 part of iodine in a
million parts of water may be detected by this means.] Note in
respect of this reaction that—
(1.) Combined iodine is unaffected by starch.
(2.) Iodine when present in combination may be set free by the
addition of a trace of chlorine water, when the blue iodide of starch
is formed (2RI+ Cl2=2|KCl +I).
(3.) If too much chlorine be added to the solution, it will bleach the
blue iodide of starch, and thus the reaction be obscured (Is H-6H.0+
5Cl2=2|HIO,-- 10HCl).
(4.) The color may be partially restored by adding a trace of
sulphurous acid to the solution (2HIOs--4H2O+5SO =5H,SO,--Is).
(5.) But if an excess of sulphurous acid be added, the color will
again disappear (I, + 2 H20+SO2=2|HI+ H2SO4).
(6.) The color of the blue iodide of starch disappears on heating
the solution to 177° F. (80° C.), but on cooling, the color is partially
restored. If the liquid be boiled, the color does not re-appear.
(7.) The blue color is also destroyed by the addition of alkalies.
Iodine turns mecomine of a blue color.
(b.) In combination.—The following salts give precipitates as fol-
90 IT ANDBOOK OF MODERN CHEMISTRY.
lows: Plumbic acetate, a yellow; argentic nitrate, a yellowish-white;
mercurio chloride, a red; palladic nitrate, a brown; (1 in 50,000); a little
chlorine water and starch, a blue color.
Uses.—In the arts.-Iodine is used in photography, and also in the
laboratory as a test reagent for starch. In medicine it is used as a
resolvent. Courdet of Geneva first suggested the use of the ashes of
sponge as a curative agent. It is employed officinally in various
forms and combinations, such as potassic iodide, liquor iodi, un-
guentum iodi, and tinctura iodi, the iodide of sulphur being also used
as an unguent, and the iodide of iron as a pill and syrup. As a
disinfectant its action is powerful. (Richardson.)
CoMPOUNDs of IoDINE AND Oxygen.
Two compounds of iodine and oxygen at most (viz., I,05 and I,07),
and probably only one (viz., I,05) have been prepared. This latter
may be formed by the action of heat on iodic acid (HIO3). This
serves to illustrate the greater affinity of oxygen for iodine, than for
chlorine or for bromine.
Iodic Acid (ETIO3 = 176).
Preparation,-(1.) By the action of chlorine on iodine suspended
in water (Liebig)—
I, + 5Cl2 + 6H2O = 1OPIC| + 2 HIOs.
Iodine + Chlorine + Water = Hydrochloric acid + Iodic acid.
OI T
[I. + 5Cl2 + 6OHe = 10HCl + * {3},
(2.) By the action of strong nitric acid on iodine. The solution is
afterwards evaporated to dryness.
Properties.—(a.) Physical.—A white solid, having a sour taste,
crystallizing in hexagonal tables (I2O3.H2O:Aq) which are very
soluble in water. Heated to 266°F. (130°C.) it becomes I,05, H2O,
and at 338° F (170° C.) I.O., is formed. At a temperature of 698°F.
(370°C.) it is decomposed.
(3.) Chemical.—It first reddens and afterwards bleaches litmus. It
slowly oxidizes most bodies. It does not blue starch, until acted on
with reducing agents, such as SO3, H.S, etc., when it is decomposed,
iodine being set free, which will then act on starch to form the blue
iodide of starch.
Iodic acid is a monobasic acid, and forms iodates.
{QI
Periodic Acid (HIO) = 192). KO
löHo.
Preparation.—In the process for the preparation of periodic acid
there are several distinct steps to be noted:—
(a) Chlorine is first passed through a solution of sodic iodate con-
taining free soda, (Liebig.)
GENERALIZATION ON THE HALOGENS. 91
2Naſo, + 6NaHO + 2C, a 4NaCl + Na,I.0, 4 &H.O.
Sodic iodate + Sodic oxide + Chlorine =Sodic chloride-– Sodic perio- + Water.
date (basic).
| 8s. + 6ONaH + 2Cl. = 4NaCl + Na, I.O., + 3OH.
(3.) The insoluble basic sodic periodate formed, is collected and
treated with argentic nitrate.
Na, I.O.) + 4AgNO3 F. 4NaNO3 + Agaſ. Oo.
Sodic periodate + Argentic nitrate = Sodic nitrate + Argentic periodate
(basic) (basic).
(y.) The basic argentic periodate formed, is then dissolved in nitric
acid, when a neutral argentic periodate is obtained.
Ag, I.Oo + 2HNO2 = 2AgIO, H- 2Agn Os + H2O.
Argentic periodate + Nitric acid = Argentic periodate + Argentic nitrate + Water.
(basic) (I.eutral)
(6.) This neutral argentic periodate is now boiled in water, when
periodic acid and basic argentic periodate is formed.
Argentic periodate + Water = Argentic periodate + Periodic acid.
(neutral) (basic)
Properties.—Periodic acid is a crystalline solid, very soluble in
water, and easily decomposed by heat.
COMPOUNDs of IoDINE AND CHLoRINE.
A protochloride of Iodine (ICl) may be obtained either directly or by
heating a mixture of iodine and potassic chlorate—
(I, + 3RClO3 = KClO4 + KIO3 + KCl + O., H- ICl).
It is a dark red, oily liquid, solidifying easily. The solid is very
deliquescent, and is easily decomposed by water.
The terchloride of Iodine (ICl3) is prepared by heating I2O3 with
hydrochloric acid (I2O3 + 10HCl = 2Cl2 + 5.B.O + 2ICls). It is a
solid crystalline body, and melts at 77° F. (25°C.) It has no action
on starch. When heated, it gives off chlorine.
The tetrachloride of Iodine (IC],) is supposed to be formed when the
protochloride is decomposed (81C1 = 2LCl1 + 3Ts).
A pentachloride of Iodine (ICl3) is also supposed to exist.
Iodine is believed to combine with bromine, forming IBr and IBrs.
GENERALISATION ON THE HALOGENs (that is, bodies forming salts, like
common salt), OR SALT RADICALS (so called from their forming salts by
direct contact with the Metals), CHIEFLY WITH REFERENCE To CHLoRINE,
BROMINE AND IoDINE.
(l.) In nature these bodies are never found in a free state. Where
one is present, all are usually present; as e. g. in sea-water, in mineral
Springs, in marine plants, and in marine animals, etc.
92 HANDBOOK OF MODERN CHEMISTRY.
(2.) They are all monad elements, one volume of the haloid element
combining with one volume of hydrogen, to form two volumes of
gaseous hydric acids, as HCl ; HBr ; HI; HF ; all of which acids
are closely allied in their properties.
(3.) They all attack organic bodies, replacing and displacing hy-
drogen.
(4.) They all decompose water, forming compounds with the hy-
drogen, and setting free ozonic oxygen.
(5.) They all bleach, oxidize, and disinfect, by reason of their action
On Water. -
(6.) They all act energetically on the metals, forming typical salts,
which are very comparable as mono-, sesqui-, and per-salts.
(7.) They exhibit a remarkable sequence of properties.
Chlorine is a yellow gas.
(a.) Form and color. & Bromine is a red liquid, boiling at 145.4°F.
Iodine is a black solid, boiling at 347° F.
Chlorine, 2.47.
(ſ3.) Specific gravity. ( Bromine, 5:54,
liii. 8-72.
ſºhlorine, 35'5.
Bromine, 80-0.
Iodine, 127-0.
[NotE.—The intensity of affinity seems to decrease, as the combining
number increases.]
(y.) Atomic weights.
* Compound of H and Cl, very stable.
(3) Compounds with 2 y Fſ and Br, less stable.
hydrogen. j } H and I, less stable than H.Br.
3 5 H and F, somewhat unstable.
(e.) The reactions of the salts of the metals also exhibit a peculiar
sequence :—
Fluoride of silver, very soluble in water.
Chloride of silver, insoluble in water, soluble in ammonia.
Bromide of silver, 3 y ? ) slightly soluble in ammonia.
Iodide of silver, 5 y 3 y insoluble in ammonia.
Compounds of O and F, non-existent.
(...) The oaty-com- } } O and Cl, very unstable.
pounds. 3 y O and Br, less unstable.
5 y O and I, stable.
[NotE.—The stability of the oxygen compounds is in the inverse order
to the stability of the hydrogen compounds.]
(m.) Their nitrogen compounds are all explosive.
(0.) Chlorine is the most electro-negative of the haloids, and dis-
places bromine from its compounds; bromine stands next, and
displaces iodine; nevertheless, in oxy-compounds, iodine will displace
chlorine.
93
CHAPTER W.
NITROGEN.
NITRoges:–Atmospheric Air—Its Constituents—Compounds of Nitrogen and
Oxygen–Nitrous oxide—Hyponitrous acid-Nitric oxide–Nitrous anhydride—
Nitrous acid—Nitric peroxide—Nitric anhydride—Nitric acid—Compounds of
Nitrogen and the Haloids—Compounds of Nitrogen with Oxygen and the
Haloids.
Atomic Weight, 14. Molecular Weight, 28. Molecular volume, [T].
Atomicity—Pentad (*), Triad ("); Monad () —NYH,Cl; N "H3;
N.O. Relative Weight (H=1) 4. Specific gravity, 0-9713. 100 cubic
inches weigh 30. 137 grains, and 1 litre 1 2561 grammes.
Synonyms.-Azote (Lavoisier); Nitrogen (Chaptal).
History.—It was long ago noticed that a combustible body in
burning vitiated the air. The Stahlians believed that this vitiation
was due to the “phlogiston” liberated by every substance in the act
of burning; hence they termed an air so vitiated “phlogisticated
air.” Dr. Rutherford (1772) of Edinburgh, struck by the change pro-
duced in atmospheric air by respiration, suggested that it was a
compound of two gases and not an element, and that in the act of
breathing, one of these gases was abstracted. Scheele and Lavoisier
(1777) independently, proved that air was a mixture of the newly
discovered oxygen with another gas which Lavoisier termed azote (a
and ºw)). This azote, Chaptal (1789) recognised as a constituent of
nitre and of nitric acid, and he therefore named it nitrogen.
Natural History.—(a.) In the mineral kingdom, nitrogen is found
in a free state in the air (to the extent of about 79 per cent. by
volume), and also in gaseous volcanic emanations. It is found in
combination with oxygen and bases, in nitres, and also with hydrogen,
as ammonia, in air and water. (3.) In the vegetable kingdom it is present
in small quantities in combination in most products of plant-life, as
in albumen, the various alkaloids, etc.; and (y.) In the animal kingdom
it is found in all fluids and tissues, and plays an important part in
the phenomena of life.
Nitrogen present in various animal substances.
Per cent. by | Per cent. by
Weight of weight of
| Nitrogen. Nitrogen.
Cartilage 15:0 Gluten. . a $ * * 16' 0
Fibrim 15° 4 Legumin * * - - 16' () to l8' 0
Albumen 15'5 | Gelatin tº º $ 8 1 S-3
Casein 15.7
Urea (CH, N,0) • * 46.7 Sarcosin (C, H, NO.). 15-7
Kreatin (C, H, N,0) , , 32° 1 Leucine (CelT1:..N.O.) , , 12. 2
Kreatinin (CII,N,0) , . 37: 1 Tyrosin (CAHMNO3) . . 7.7
94 FIANDBOOK OF MODERN CHEMISTRY.
Preparation.—(1.) Ay abstracting oxygen from atmospheric air by
one or other of the following methods : —
(a) By the active combustion of phosphorus.
(6.) By the slow combustion of phosphorus in moist air.
(y.) By the action of moist iron or some other metallic filings.
(6.) By the action of moistened alkaline sulphides.
(e.) By the action of potassic pyrogallate.
(4.) By admixture with nitric oxide (N.O.) and subsequent washing.
(m.) By passing the air over red hot iron, or copper turnings, or
best of all, over finely divided copper reduced by hydrogen from the
powdered oxide (Cu, + (4N2=O.) air=2010-1-4N.).
(2.) By the decomposition of ammonia or of its salts by such methods
as the following:—
(a.) By passing chlorine through an excess of an ammonia solu-
tion—
8NH3 + 3Cl3 = 6NH,Cl + No.
Ammonia + Chlorine F Ammonia chloride + Nitrogen.
[8]NH3 + 3Cl3 = 6NH4Cl + N.J.
(ſ3.) By heating ammonic nitrite—
NH, NO. = 2.H2O + No.
Ammonic nitrite = Water + Nitrogen.
[NO(NH,0) = 20 H. H. N.].
(y.) By heating together ammonic chloride and potassic nitrite—
ICNO, -i- NH,Cl = KCl + 2 H2O + N2.
Potassic nitrite + Ammonic chloride = Potassic chloride + Water + Nitrogen.
|NOKo + NH,Cl = FCCl + 2CH2 + N.].
(6.) By heating together ammonic chloride and ammonic nitrate
(Maumené's process for getting chlorine) (see page 72).
The chlorine in this case may be got rid of, by washing the
products with an alkali.
(e.) By heating together ammonic chloride and potassic dichro-
Imate— r
K.Cr20, -i- 2NTIAC1 = Cr.03 + 4H2O + 2KCl + No.
Potassic + Ammonic = Chromic + Water + Potassic + Nitrogen.
dichromate chloride oxide chloride
ſ CrO. Ko
| O + 2NH4C1 = Cr.03 + 4OH, -i- 2KCl + Nºll
| CrO.Ko
Properties.—(a.) Sensible.—A colorless gas, without odor or taste.
(B.) Physiological.-It is not a poison (for we breathe it freely), but
it will not support life. In the air it serves the purpose of a diluent,
thereby rendering the oxygen less stimulating.
(y.) Physical.—Its specific gravity is 0-9713. It is therefore a little
lighter than air; 100 cubic inches weigh 30, 119 grains (by calculation
30-033 grains), and 1 litre 1 2561 grims.—14 grains of nitrogen measure
at standard temperature and pressure 46-7 cubic inches.
Nitrogen is a permanent gas; that is, it cannot be liquefied by
NITROGEN.--ATMOSPFIERIC AIR. 95
cold or by pressure. It is very slightly soluble in water—100 vols.
absorb at 32°F.(0° C.), 2-03 vols.; and at 60° F. (15°C.) 1.48 vols.
(Bunsen).
(6.) Chemical.-The chemical properties of nitrogen are remarkable
for their negative character. It has no action on litmus or turmeric ;
it neither burns itself nor allows a taper to burn in it; and it does not
whitem lime water. Upon ocygen it is without action under ordinary
conditions, but if sparks be transmitted through a mixture of Oxygen
and nitrogen, or if nitrogen mixed with hydrogen or ammonia gas
be burnt in an atmosphere of Oxygen, nitric acid is formed.
Upon chlorine and the haloids it has no action, unless nascent,
when explosive compounds result. [Memo. Deing a permanent gas,
and so feebly adapted for combination, many of its compounds are
explosive.]
Upon phosphorus, sulphur, selenium, carbon, etc., it has no action,
except in the case of carbon, with which, at a red heat, in the presence
of alkalis and alkaline earths, it forms metallic cyanides (M'CN.)
It is said to combine directly with boron and silicon.
Upon hydrogen it has no action, unless the hydrogen be nascent,
when ammonia is formed.
Upon the metals it has no action, except in the case of tungsten,
titanium, magnesium, and tantalum, all of which burn in it when
heated, metallic nitrides being formed.
It has no action on organic bodies.
Tests.--In a free state we know it by its negative characters; in
combination as nitric acid or as ammonia it may be recognised by
the special tests for these bodies.
In organic compounds we estimate it quantitatively from the ammonia
formed by the combustion of the organic matter with soda-lime. If
the nitrogen be present in the body as an oxide, it must then be
determined as free nitrogen by processes to be hereafter described.
(See Organic Analysis).
Uses.—These are confined to Nature as a diluent in air, and as a
constituent of tissues.
ATMOSPHERIC AIR.
History.—(a.) Ancient opinions.—The air was originally regarded as
an element. The ancient chemists made no distinction between the
various elastic fluids, calling them all air, and this commºn air. In
1640, Van Helmont observed differences in airs, and he adopted the
Word gas or gaz, to distinguish them. (Thus gas-pinque, gas-siceum,
gas-fatiginosum, gas silvestre — De Flatibus.) In 1650, Maequer
popularised the word gas, and distinguished a gas from a vapor. In
1660 Boyle suspected a difference in the composition of different gases,
from their differences of combustibility, etc.
96 FIANDBOOK OF MODERN OFIEMISTRY
(ſ3.) Modern opinions.—In 1772, Rutherford discovered nitrogen, and
in 1774, Priestley discovered oxygen. In 1777, Lavoisier proved that
air consisted of a mixture of these two gases, in the proportion of 1
volume of oxygen and 4 volumes of nitrogen. His experiment in
proof consisted in boiling mercury for several days in a given bulk
of air, noting the loss, the quantity of the calx of mercury formed, and
the quantity of oxygen produced on heating the calx. About the
same time Scheele and Priestley independently arrived at similar con-
clusions, the former absorbing the oxygen with potassic sulphide, and
the latter with nitric oxide. More careful experiments were after-
wards conducted by Cavendish (1781), Prout, Biot and Arago, Dumas
and Bousingault, Regnault and others.
Properties—(a.) Physical—The specific gravity of air is regarded as
1 ; that is, it is regarded at 0° C. and at 30° Bar. Pr. (766 mm.) as the
unit and standard of comparison for gases and vapors.
Weight of the air.
100 cubic inches weigh (Prout) tº º * * 4 º' ... 31' 117 grains.
3 y 3 * 5 x 3 y (Biot and Arago) & & * } s & 31 - 074 $ 3
5 * 3 3 33 2 3 (Dumas and Bousingault) . . . , 31-086 ,,
3 3 2 3 5 y »; (Regnault) g ºt $ tº gº tº tº $. 30-935 y 3
2 3 3 * 35 , (Mean of the four observations) . , 31°053 ..
Taking the mean of these experiments, 1 litre of air weighs at 0°C.
and 760 mm., 12936 grim., and 1 cubic foot, 536-6 grains. Air is
therefore 14:45 times heavier than hydrogen, and 816 times lighter
than water.
The average pressure of the air on the surface of the earth, and at
the level of the ocean is equal to 15 lbs. on the square inch, that is,
the air is capable of supporting a column of mercury of 30 inches or
760 mm., or a column of water of 34 feet. As we ascend, the pressure
diminishes with the density, it being halved for every 3.4 miles. It
follows, therefore, that whatever may be the extent of the air, one-
half of the atmosphere must be confined to about 3.5 miles of the
earth.
The average temperature of the air in England is 60°F. (15:56°C.)
But this varios at diſſerent heights, the temperature decreasing 1°F.
for every 300 feet, or 1° C. for every 550 feet.
The limit of perpetual snow in this country is about 6,000 feet, and in
the tropics at the equator 15,000 feet.
Air is a refractor of light, hence the existence of twilight.
(3) Chemical.—Air is a mechanical mixture of nitrogen, oxygen
and other gases, as proved by the following circumstances —
(a) On mixing oxygen and nitrogen in their proper aerial pro-
portions, neither change of volume, nor heat, nor electricity results.
(b.) The relative amounts of oxygen and nitrogen present in the
air are not their combining weights, or any multiple thereof.
ATMOSPHERIC AIR. 97
(g.) When air is shaken up with fresh boiled water, the gases
dissolve in their normal proportions, i.e., as 1 of nitrogen to 1-87 of
oxygen; and not in the proportion in which they are contained in air,
viz., as 4 of nitrogen to 1 of oxygen.
Composition.
General average Analysis of Air (Miller).
Oxygen . . w - * * tº º . . 20 - 61
Nitrogen . . * * º ºg • * . . 77-95
Carbonic anhydride * * • 4 $ tº • 04
Aqueous vapor . . * * * * , , 1 “40
Nitric acid & o • * * *
Ammonia. . . * * tº tº * @ traces.
e Carburetted hydrogen , , 4 º'
and in ſ Sulphuretted hydrogen .. • * traces.
towns l Sulphurous anhydride .. * *
Constituents of the Air.
(1.) Oxygen and Nitrogen.—The proportion of these gases respectively
present in air may be estimated in various ways: —
(A.) By re-agents which absorb the or/gen at ordinary temperatures and
leave the nitrogen, as follows :-
(a.) By mixing a given bulk of air with a given bulk of nitric
oxide (N.O.) in a graduated tube standing over water. The oxygen
present in the air combines with the nitric oxide (N.O.) to form
nitric peroxide (N.O.), which is dissolved as soon as formed by the
water in the tube.
Erample.—Suppose that to 5 volumes of air we were to add 5
volumes of N.O., we should find that 3 volumes would be immediately
absorbed by the water, leaving only 7 volumes in the tube. Of every
3 volumes of N2O, so absorbed 1 volume we know is oxygen. It
follows, therefore, that 1 volume of the 5 volumes of the original air
was oxygen.
There are many sources of error in this process. The N.O., may con-
tain N2O, whilst N.O.s may be formed in variable proportion, as well
as N2O4. This process of analysis therefore, although considerably im.
proved by Falconer, Fontana, Cavendish, Humboldt, Guy Lussac,
Thénard, and others, is wanting in accuracy.
(3.) By exposing a given volume of air to the action of an alkaline
sulphide. (Scheele; improved by De Marti.)
(y.) By exposing a given volume of air to the action of moist lead
shot. (Saussure.)
(6.) By exposing a given volume of air to the action of sheet copper
and dilute sulphuric acid. (Guy Lussac.)
(e.) By introducing a piece of phosphorus into a given volume of
air standing over water. (Berthollet and Parrot ; Achard ; Brunner ;
Reboul, etc.)
(4.) By a solution of nitric oxide in ferrous sulphate (4 Fe S0, 4-N.O.),
a brown liquid being formed which rapidly absorbs oxygen. (Sir H.
Davy.) -
H
98 HANDBOOK OF MODERN CHEMISTRY.
(m.) Either by an ammoniacal solution of cuprous sulphate, prepared
by passing S0, through an ammoniacal solution of CuSO, and dis-
Solving the precipitate formed in ammonia; or by a solution of
cuprous oxide (Cu,0) in ammonia. (Graham.)
(6.) By a strong solution of pyrogallic acid (C12H606) in caustic
potash (potassic pyrogallate).
(B.) By agents which absorb the owygen at high temperatures and leave
the nitrogen.—A given volume of air is first passed (1), over calcic
chloride, then (2), over caustic potash, and finally (3), over ignited copper
reduced from its oxide, severally contained in glass tubes accurately
Weighed before the experiment is commenced. The increase in the
Weight of the calcic chloride tube indicates the moisture, of the caustic
potash tube the carbonic anhydride, and of the copper tube the oxygen
severally contained in the volume of air operated upon. The residual
gas, which is nitrogen, may be collected in an exhausted and weighed
globe, the increase in the weight of which gives the nitrogen. (Dumas
and Boussingault.)
(C.) By exploding the air with hydrogen in an eudiometer. (Regnault,
Bunsen, Frankland, Williamson, Angus Smith, Russell, etc.)—
Every 1 volume of oxygen requires 2 volumes of hydrogen to form
2 volumes of water gas (H,0).
Eacperiment.—To 100 volumes of air add 50 volumes of hydrogen,
and explode. The 150 volumes will shrink (water being condensed)
to 87 volumes;
150 – 87 – 63 volumes loss;
Of these 63 volumes of H2O condensed, one-third is oxygen;
Therefore * = 21 volumes of oxygen in 100 volumes of air.
[MEMO. —We may here note, that conversely the quantity of hydro-
gen present in a mixed gas may be estimated by exploding the gas with
oacygen and noting the loss, two-thirds of which is hydrogen.]
This combination of oxygen and hydrogen may be effected slowly
by using pellets of spongy platinum.
Results of Analysis.—By experimenting on common air the follow-
ing results were obtained by Dumas and Boussingault and by
Regnault:—


Dumas and In round
Boussingault. Regnault. Mean. numbers.
B l Nitrogen . . 79. 19 79-07 79. 13 79
y volume oxygen .. 20:81 20-93 20.87 21
100 : 00 100 : 00 100.00 100
B ight | Nitrogen . . 76.99 76 87 76-93 77
Y Weis" (oxygen .. 23:01 23: 13 23:07 23
100'00 100 : 00 100 : 00 100
ATMOSPEIERIC AIR. 99
The proportions of oxygen and nitrogen present in the air, have been
found not to vary more than from 20:80 to 20.97 per cent. by volume.
This uniformity is dependent on the operation of winds and upon diffu-
sion, by which gases mix in opposition to gravitation, and when mixed
remain so. -
The chief differences in the percentage volume of oxygen that have
been observed are as follows:—
Vol. of oxygen
per cent.
By nºw at Marburg º . . .
Chamounix (3,000 feet) e - a ... 20'894
By Frankland Grand Mulets (11,000 feet) ... ... 20-802
Top of Mont Blanc (15,732 feet) ... 20.963
By Miller Taken in a balloon at 18,000 feet ... 20.880
(2.) Ozone.—The presence of ozone in the air may be detected by
test papers. (See page 62.) The general facts relating to ozone may
be stated as follows:—
1. More ozone is present during the night than during the day,
and most of all is found at day-break.
2. More is found in winter than in summer, and least in autumn.
3. More is found at high than at low levels.
4. More is found on the sea coast, and specially when the wind is
blowing from the sea, than inland.
5. More is found in the country than in towns.
6. More is found after a thunderstorm than at any other time;
least of all is found on damp foggy days.
7. More is found with western than with eastern winds.
8. The maximum quantity of ozone in the air, never exceeds
rºot, part its bulk (Houzeau). Its chief source is atmospheric
electricity, and as minor sources the action of aromatic plants and
flowers, etc. (See Glaisher's remarks in Appendix to Cholera Reports
of Board of Health, 1855, pp. 71–73, 89, 90.)
3. Aqueous vapor.—This is determined by instruments called hygro-
meters (i)poc, moisture, and puérpov, a measure), hygroscopes, or psychro-
meters (lùxoc, cold). A large number of common things such as sea
weed, catgut, whipcord, etc., are hygroscopic, and are consequently
used as weather instruments.
Daniel's hygrometer, the action of which depends on cooling the air
by the evaporation of ether until moisture begins to be deposited,
and Mason's wet and dry bulb thermometers, are the common instruments
in use for measuring the hygroscopicity of the air. The actual amount
of moisture in air may be estimated, by passing a given volume of air
through a weighed tube containing calcic chloride, its increase of
Weight after the experiment indicating the amount of moisture present
in the volume of air operated upon.
General facts respecting moisture—(a.) Air rarely contains its full
100 EIANDBOOK OF MODERN CHEMISTRY,
saturated amount of moisture, except in very cold weather or in very
hot tropical seas; in such cases the air is very oppressive.
(b) If the air were saturated with moisture, the amount present
would be as follows:–
Amounts of Aqueous Papour in 1,000 volumes of Air when Saturated.
One cubic foot of air saturated (Bă = 30.)
1000 vols. of dry Iſ)00 vols. Of
Tº. air º * º: *
- •. ja Lll I'3t f eC †) tall &lſ]. Vå I). - *
(degrees). (Volun,es). C tºº." º º And it weighs
(cubic inches). (grains). (grains).
10 1002-3 1 - 12 1 '9354 0.84 592-94
20 1 003 : 6 2.29 3.957.1 1:30 580:26
30 I 005: 6 5.57 9' 62.50 1.97 567-99
40 1008-3 8'23 14:2214 2-86 556° 03
50 10 12.0 11.76 20:32.13 4 - 10 544.36
60 10 17-3 17:06 29:4797 5-77 532-84
70 1024 - 4 23.82 4 1 6 10 8' 01 521-4 1
80 1034 - 1 32.98 56' 9890 I (). 98 509-97
90 104.7-0 43.93 75-9] 10 14 '85 498:43
100 1063.9 60-07 103.80 10 19 - 84 486.65

(c.) The most comfortable degree of saturation is from 66 to 70 per
cent. More than this checks evaporation from the body, whilst less
causes too great evaporation, thereby parching the mouth and drying
the skin.
(d.) It has been noted that in certain places, remarkable as health
resorts, the degree of saturation is singularly uniform.
(4.) Carbonic acid.—This is always present in air.
mated in different ways: —
(a.) By passing a given volume of air through a carefully-balanced
tube containing caustic potash. The aqueous vapor must first be got
rid of by passing the air over chloride of calcium. The increase in
the weight of the tube containing caustic potash, indicates the amount
of CO2 present.
(3.) Shake up a gallon bottle of the air to be examined, with a
known quantity of lime water. It is only necessary to determine
afterwards how much of the lime water remains unneutralized by a
standard solution of Oxalic acid. (Pettenkofer.)
(y.) By noting the degree of turbidity produced when a given
volume of air is passed through a given bulk either of lime water or of
baryta water.
(8.) By shaking up half an ounce of baryta water (consisting of one
half of a cold saturated solution and one-half water) with different
bulks of the air under examination. The least turbidity indicates—
It may be esti-
With 23 ozs. Of air , , tº e ... 0-04 CO, per cent.
9 * } * (). 10 55
5 ?? tº ſº (): 20 3 y
3% 5 J tº º tº ſº , , () 30 37
2} 3 y is tº tº tº , , 0°40 7 5
2 3 * º 0 (30 y 2
1 * , (j '90 }}
ATMOSPFIERIC AIR. 10 !
General facts relating to carbonic acid in the air.—(a.) A normal at-
mosphere contains 4-5 volumes of CO2 in 10,000 of air (i.e., 0.04 to
0-05 per cent.).
(b.) The proportion of carbonic acid is greater at high than at low
altitudes. (Frankland). -
Chamounix ... 3,000 feet, 6-3 parts of CO2 per 10,000.
Grand Mulets ... 11,000 ,, 11:1 } }
Mont Blanc ... 15,732 ,, 6' 1 } }
(e.) The proportion is slightly greater on the surface of the ocean by
day than inland (from the action of the sun on the water P). Lewy
found 47 parts per 10,000 in the air at the middle of the Atlantic.
(d.) The proportion of carbonic anhydride present in the air varies
greatly.
Proportions of carbonic acid in the air per 10,000 parts.
Average parts
In cities and towns — per 10,000.
London (2.8–4:3) . . Q & tº º tº e ... 3-4
Manchester (4:9–15). . tº tº tº e # tº , , 5-4
Munich. . e tº tº 0. * - * tº Q & . . 5:0
Madrid (3-0–8-0) .. * - e e * * . . 5-2
Paris (3.6—5:1) * * © º * - tº in . , 4-3
In dwelling-houses :-
By day (large rooms) (5:4–87) . . & & , , 6-8
22 (small rooms).. tº º • * sº º . . 12:7
By night (common rooms) . . tº e is s , , 13-4
7 3 (bed rooms) (28–50) 0 tº & , , 36°0
..In schools —
By day, English (9:7–31) . . tº e tº º ... 21.5
} 3 French (27–47) . . e e w is . . 24-7
} } German * * tº e tº e & ſº ... 39'2
In mills and workshops (28–30) tº º tº e tº e . . 29' 1
Places of public resort :-
london law courts (4.8–19-8) tº e * tº . . 12:3
London theatres (7-6–32-0).. a tº tº e , , 14-9
Manchester theatres (10-2–27-3) . . tº e ... 14-8
Paris theatres (23–43) tº º tº a tº tº , , 33-0
(e.) Expired air contains from 350 to 500 parts per 10,000, or
an average of 425 parts in 10,000 of air.
(f) Roscoe states that the air in rooms never contains more than
0.5 per cent, or 50 parts in 10,000, owing to diffusion and to the
porous nature of the walls.
(g.) When a chafing dish was lighted and left to burn until the
carbonic acid had been generated in sufficient quantity to extinguish
the fire, the proportion of CO2 was found to be 14 per cent, or i ,400
parts per 10,000 of air.
(h.) Here it will be well to note the vitiating effects on air of
different kinds of fuel and illuminating agents.
102 HANDIBOOK OF MODERN C {l EMISTRY.
Carbonic acid produced, and air vitiated per hour.
Carbonic acid Air vitiated
produced and used
(cubic inches). (cubic feet).
A man . . & ſº * * tº e º º tº tº © e 1,201 723
A horse or cow tº g u tº * . tº º • * 14,750 8,591
Batswing burner (3 feet per hour cannel gas) . . 4,304 2,513
Fishtail or Agrand (5 , , 3 2 common gas) . . 4,752 2,779
Moderator lamp, consuming 643 grains oil per hour 3,857 2,410
Paraffin 5 y } } 400 3) 75 - - 2,666 1,658
,, candle 3 5 120 2 3 3 y = - 800 498
Spermaceti candle , , 130 2 3 3 * * * 809 502
Composite 35 53 140 33 2 y - - 829 515
Wax ?? 5 ) 168 , 2 y - - 1,062 670
Tallow 35 2 3 143 5 5 3 * * * 858 529
(i.) Lastly, we may note that the quantity, according to Pettenkofer,
which marks the boundary line between pure and impure air is 0:1
per cent. If, therefore, we find more than 10 parts of CO., in 10,000
parts of air, we should be justified in regarding that atmosphere as
unwholesome.
(5.) Ammonia.-This is generally present in air, although commonly
but in small quantities. It was first observed by Liebig. It may be
estimated by passing a known volume of air through a known quan-
tity of dilute sulphuric acid, contained in a tube filled with glass
beads. The amount of acid left unsaturated must be afterwards
determined.
Proportions of ammonia (NHA) found in 1 million parts of air.
Fresenius (by day) © º * - * * * * 0 - 09S
} } (by night) • * tº - tº º tº º 0 - 169
Groeger . . * - • tº tº o * - tº tº 0.383
Remp * * tº e © tº tº º tº tº º e 3-880
Letheby and Tidy * - , , from 4° 101 to 6:203
(Wide “Quarterly Journal of Agriculture,” 1849, p. 160.)
Ammonia is always more abundant in the air in dry than in wet
weather, in town than in country, and in summer than in Winter.
Proportions of ammonia found in 1 million parts of rain water.
Parts per 1 million.
Boussingault (Liebfrauenberg) . . © tº º º 0-80
Lawes and Gilbert (Rothamstead) • tº 4 - 1-00
Barral and Boussingault (Paris) . . Q & ... 3 to 4
Letheby and Tidy (London Hospital) . . . . 4 to 6
(6.) Nitric acid—This is always present in small quantities in the
atmosphere, and specially during a thunderstorm, electrical discharges
determining the union of the nitrogen and oxygen. Its presence may
also be due to the action of ozone on atmospheric ammonia. The
acid is present in rain water to the extent, at times, according to
Messrs. Lawes and Gilbert, of 3.71 parts in a million.
NITROGEN-COMPOUNDS WITH OXY GEN. 103
Probably ammonia and nitric acid are the source from which plants
take their nitrogen, inasmuch as they seem to be unable to assimilate
the gas when presented to them in a free state.
(7.) Sulphurous and sulphuric acids.-These are always present in
the atmosphere of towns where coal is burnt, and may often be seen
upon our windows in the form of ammonic sulphate. Coal contains from
about 0.75 to 4 per cent. of sulphur, the quantity present in common
coal being on an average 1.5 per cent. Coke contains from 0-6 to 2 per
cent. of sulphur, the average quantity being 1:25 per cent. Coal gas
contains from 12 to 40 grains of sulphur per 100 cubic feet, the average
being 20 grains. In certain localities where sulphur is burnt or metals
refined, there is often at times a large escape of sulphurous acid into
the air. The rain which falls on the roof of the London Hospital
College contains from 0-942 grain to 4' 357 grains of sulphuric acid
(H2SO4) per gallon. This is equivalent to from 13:46 to 62.24 parts
per million.
(8.) Organic matters, etc.—Certain organic vapors, floating particles,
germs of fungi, etc., are found in the air, and are revealed by every
beam of direct sun-light. That such organic particles are present,
the development of mould and of infusoria in organic solutions abund-
antly testify. Tyndall's researches have shown the power of cotton
wool in filtering off these solid particles.
(9.) Saline matters.-These are found in the air, and especially in
the immediate neighbourhood of the sea.
Compounds of Nitrogen and Oxygen.
These gases have but little tendency to combine directly, neverthe-
less by indirect combination they form a very complete series of
chemical compounds, which may be thus tabulated :-
THE OxIDEs of NITROGEN.
Oxides—formula. Name. Acids. Formula of acids.
N.0 or ON, Nitrous oxide +H,0}=Hyponitrous acid 2HNO or NHo (?)
NO
;4--> ; Ro T -
INO Nitric oxide No acid
NO
NO) Nitrous acid HNO, or NOPſo |
N,0, or No. Nitric peroxide |+H,0|= and
and
Nitric acid HNO, or NO, Ho
N0,
()
NO,
N20s or
NO
N.0a or | O Nitrous anhydride |+H,0} = Nitrous acid | 2HNO, or NOHo
|
R
| Nitric anhydride |+H,0|= Nitric acid 2HNO, or NO. Ho
104 |HANDIBOOK OF MOIDERN CIIFMISTRY.
Nitrous Oxide (N2O=44). (ONA).
Aſolecular weight, 44. Molecular volume, TT . Relative weight
(H=1), 22. Specific gravity observed, 1.527. 1 Litre weighs
(0.0896 × 2.2) 1971 grºms., and 100 cubic inches 47.34 grains.
Synonyms.-Dephlogisticated nitrous air (Priestley); nitrous oride
and laughing gas (Davy); protocide of nitrogen (most chemists); nitrogen
nvonoacide.
History.—Discovered by Priestley (1776) when acting on N.O.
with iron filings. Examined by the Dutch chemists (1793) and proved
by them to be a compound of nitrogen and oxygen. Its physiological
action was investigated by Davy (1809) at the Clifton Pulmonic Insti-
tution.
Constitution N |N| + |o] = |No|
14 14 + 16 = #4 or 22.
2
Preparation.—(1) Dy the action of iron filings on Initric oxide
(N.O.). (Priestley.)
(2.) By heating ammonic nitrate at a temperature of 470° F.
(243° C.). (Berthollet and Davy.)
N.B.- If the temperature be above 500°F. (260° C.) other changes occur, nitric
oxide and nitrogen being evolved, and a mixture of ammonic nitrite and nitrate sub-
liming. If ammonic chloride be present, the N20 will be contaminated with chlorine.
NH, NO3 - 2H2O + N.O
Ammonic nitrate - Water + Nitrous oxide
[NO.(NVH.,0) = 20 H. H. ON.]
It may also be prepared by heating ammonic chloride with dilute
nitric acid (Sp. Gr. 1-2).
(3) By the action of weak nitric acid (Sp. Gr. 1:2) on granulated
zinc. (Grotthus.)
10HNO3 + Zn, = 4(Zn2NOs) + 5H2O + N.O
Nitric acid + Zinc = Zincic nitrate + Water + Nitrous oxide
TN.O.,
[10No.Ho + Zn4 = ''. + 50H2 + ONs. |
NO.
(4.) By decomposing nitric acid with a hydrochloric acid solution
of stannous chloride.
(5.) By passing nitric oxide (N.O.) through a solution of sulphurous
anhydride.
When the gas is required for inhalation it should be purified by passing it first
through a potash solution to get rid of acid vapours, and then through a ferrous
sulphate solution to get rid of nitric oxide.
Properties.-(a.) Sensible.—A sweet-tasted gas, without color or
odor.
NITROGEN-COMIPOTNIDS WITH OXYGIZN, 105
(3) Physiological.—When breathed it induces transient intoxication,
with strong muscular exertions and uncontrollable laughter (laughing
gas). If the inhalation be continued it produces complete anaesthesia,
brief as to time, and harmless as to after effects. The liquid and
solid nitrous oxide blister the skin when brought into contact with
it. (Davy, Roget, Southey, Kingslake, Wedgewood, etc.).
(y.) Physical.—It has a specific gravity of 1:527 (calculated 1522)
—100 cubic inches weigh 47.34 grains (or as calculated 47 18 grains),
and 1 litre 1971 grims. At a temperature of 45° F (7°C.), and under
a pressure of 50 atmospheres (800lbs.), it becomes a colorless liquid,
having a specific gravity of 0-908, and boiling at — 126°F. (–88°C.).
It has the smallest refracting power of any known liquid (Faraday).
When the liquid is exposed to the air its evaporation is so rapid that
it freezes itself, becoming a white flaky solid which melts at—148° F.
(—100° C.). If liquid nitrous oxide be dissolved in carbonic disulphide
and evaporated “in vacuo,” the lowest known temperature is pro-
duced (–220°F.) It is decomposed when heated in a porcelain tube
or when exposed to the action of electric sparks.
The gas is freely soluble in water;-100 volumes at 32° F. (0°C.)
absorb 30 volumes of the gas; at 60°F. (15-5°C.) it absorbs 78 volumes,
and at 75° F (24°C.) 60 volumes. It is more soluble even in alcohol,
in ether, and in the volatile oils, than in Water.
(6.) Chemical.— Nitrous oxide is a neutral body without action on
litmus or turmeric. It is not combustible, but supports combustion.
A taper, phosphorus, charcoal, and sulphur burn in it as vividly as they
do in oxygen. It is essential, however, that the combustible body
should be burning freely when introduced, as otherwise the tempera-
ture will be insufficient to decompose the gas, this being a necessary
condition to render it a supporter of combustion.
Nitrous oxide may be known from oxygen as follows:—
(1.) It does not form red fumes with nitric oxide.
(2.) It is very much more soluble in Water.
(3.) It is not absorbed by potassic pyrogallate.
(4.) When phosphorus is burnt in it, the residual gas (nitrogen) is
identical in volume with that of the original gas, for—
o
|N
N
+
= | No
*-
whereas this is not the case when phosphorus is burnt in oxygen.
With hydrogen, nitrous oxide explodes volume for volume—
|No|| + |H| H = Hºoli BNN
In this manner the composition of the gas may be proved and its
quantity in mixture estimated.
106 EIANTDBOOK OF MODERN CHIEMISTRY.
On the metals nitrous oxide has no action in the cold, but the alka-
line metals, as well as zinc and iron, when heated burn in it freely.
If potassium be burnt in the gas the metal becomes oxidized, and it
will be noted that the bulk of nitrogen that remains when the com-
bustion is complete, will be equal to the bulk of the gas originally
employed.
Uses.—In medicine it is used as an anaesthetic. It is most important
that the gas for this purpose should be pure and well washed in
potassic and ferrous sulphate solutions.
In the laboratory the intense cold produced by the action of carbonic
disulphide on its solid or liquid form is valuable in research.
Hyponitrous Acid (HNO = 31). (NHo.)
This acid has never been isolated. If, however, an alkaline nitrate
be treated with sodium amalgam, a nitrite is first formed (NaNO3),
which is afterwards further reduced to the state of hyponitrite (NaNO).
On neutralizing the alkaline solution with acetic acid, and adding
argentic nitrate, a yellow precipitate of argentic hyponitrite (AgNO)
is formed. The sodic hyponitrite solution, heated with acetic acid,
gives off nitrous oxide. (Divers, P.R. S., 1871.)
Nitric Oxide (N.O.). (N3 or N.O.)
|
Relative
Molecular weight, 60. Molecular volume (anomalous)
weight, (H=1), 15. Specific gravity, 1-039. 100 cubic inches weigh
32.21 grs., and 1 litre 1.344 grºms.
Synonyms, LWitrous gas (Priestley); Binowide and Deutocide of
Nitrogen; Nitrogen Dinozide; Azotyl, Nitrosyl.
Preparation.—(1.) By the action on copper (with or without heat)
of dilute nitric acid (Sp. Gr. 1-2). Other metals may be used instead
of copper, such as lead, mercury, silver, bismuth, etc., but in these
cases a stronger acid is required.
3Cu + 8BINOs - 3Cu N.06 + 4H2O + N2O2.
Copper + Nitric acid = Cupric nitrate + Water + Nitric oxide.
NO.
[3Ca + 8NO.Ho = 3 (Cuo" + 4OH2 + 'N"20e |
NO.
(2.) By decomposing nitre with ferrous chloride or with ferrous
sulphate in their respective acid solutions.
(a.) 6FeCl,+ 8BICl -- 2KNO3 = 3Fe2Cl6 +4H2O+ 2KCl + N2O2
Ferrous + Hydro- + Potassic = Ferric + Water-HPotassic-H Nitric
chloride chloric acid nitrate chloride chloride oxide.
| 6FeCl2 + 8][ICl +2NO.Koz=3 | #: +4OH2+2KCl-i- No.
NITROGEN-COMPOUNDS WITH OXYGEN. 107
(3)6FeSO,--5H,SO,4-2KNO,-8(Fe3SO)+2HKSO,44H.0+N.O.
Ferrous + Sulphuric + Potassic = Ferric + Hydric potas- + Water + Nitric
sulphate acid nitrate sulphate sic sulphate oxide.
6SO, Feo" + 5S0, Ho, +2NO, Ko = 3S,0s Fe,o" +2SO, Hoko-H 40H2 + N20,
(3.) By passing ammonia gas over heated manganic peroxide.
5MnO, + 2NEI3 = 5MnO + 3FI2O + N2O2
Manganic peroxide-- Ammonia = Manganous oxide + Water + Nitric oxide.
[5]MnO2 + 2NHa = 5MnO + 3OH2 + 'N'.0...]
Properties.—(a) Sensible and physiological.—A colorless gas having
a strong and disagreeable odor. It produces violent irritation
when breathed (Davy). It destroys life if respired for more than a few
Seconds.
(3.) Physical.--Nitric oxide consists of equal volumes of nitrogen
and oxygen united without condensation. That is, 2 vols, of NO,
weighing 30, consist of 1 volume of N= 14, and 1 volume of O-16.
It follows, therefore, that NO and not N.O. is its true formula.
|NONO
|No|No
|N N | + |O 0 | =
Its specific gravity, both by experiment and by calculation (15×
0-0693) is 1:039. 100 cubic inches weigh 32.21 grains, and 1 litre
1.344 grims. It cannot be liquefied by cold or by pressure. It is the
most stable of all the nitrogen oxides, and is consequently the oxide
most commonly formed by the decomposition of the other oxides.
For neither a red heat (or, indeed, any heat short of a white heat)
nor electric sparks decompose it when the gas is quite dry, although
in the presence of moisture both heat and electricity decompose it. 100
volumes of water dissolve 5 volumes of the gas, and 100 volumes of
alcohol 27-4 volumes.
(y.) Chemical.—Provided no free oxygen be present, nitric oxide is
neutral both to litmus and turmeric. It neither burns nor supports
combustion unless the combustible body, when introduced, be burning
sufficiently energetically to effect its decomposition. Under such
circumstances carbon burns in it freely, forming nitrogen and carbonic
anhydride; and also phosphorus, leaving pure nitrogen.
Its special characteristic is its affinity for oxygen. The red fumes
of nitrous anhydride (N2O3) and nitric peroxide (N.O.), formed by its
combination with oxygen, distinguish it from all other gases. The
proportions of these two gases formed when nitric oxide is mixed
with oxygen vary, and, inasmuch as they have different solubilities,
it is not possible to estimate the oxygen accurately in any mixture by
this means (see page 97). It has no action on hydrogen at ordinary
temperatures. A mixture of equal volumes of hydrogen and of nitric
oxide, burns when ignited, with a green flame, but without explosion:
whereas a mixture in like proportion of hydrogen and nitrous oxide
108 IHANDIBOOK OF MODERN CHEMISTRY.
explodes. When, however, a mixture of nitric oxide and hydrogen
is passed over heated platinum black, ammonia is formed
(N2O2+ 5H2=2NE134-2H2O). Mixed with the vapor of carbonic di-
sulphide it burns with an intensely white light.
Potassium and sodium, when heated, burn in the gas. It is also
decomposed in the presence of moisture by red-hot iron and tin, the
residual gas (nitrogen) constituting in each case one-half of the
original gas. Moist iron and moist zinc slowly decompose it, nitrous
oxide (N2O) being formed.
Solutions of ferrous and chromous salts absorb it freely, forming a
dark Olive-brown compound, consisting of four parts of a ferrous or
chromous salt with two parts of nitrous oxide (4 FeSO, N.O.) (Péligot).
These solutions absorb oxygen freely, and, when heated, evolve their
nitric oxide unchanged.
Other metallic salts (such as stannous and mercurous salts) also
absorb the gas, but with mutual decomposition. They cannot there-
fore, as in the case of ferrous and chromous salts, yield the nitric
oxide after absorption in an unchanged state.
The gas is absorbed by nitric acid, a red, green, or blue solution
resulting, the color depending on the dilution of the acid. Pro-
bably in these cases a higher nitrogen oxide (N2O) is formed.
Nitric oxide has a basylous character, and, like the alkaline
metals, is capable of replacing hydrogen in many compounds. Thus,
like sodium, it will replace one of the hydrogens of alcohol:—
C.H2(OH) — C, H2(ONa) – C.H3(O(NO)).
Alcohol *- Sodic ethylate wº- Nitrous ether.
Nitric oxide forms two chlorides, viz., chloride of azotyl or nitrosyle
(NOCl) and bichloride of azotyl (NOCl3). Corresponding to sodic
oxide (Na2O) there is an oxide of nitric oxide, viz., nitrous anhydride
[N.0, or (NO),0]; corresponding to sodic hydrate (NaHO), there is
nitrous acid ((NO)HO); and corresponding to hydric-sodic sulphate
(NaHSO) there is (NO)HSO,.
Its only use is in chemistry, as a test for the presence of free oxygen.
TN'"O
Nitrous Anhydride (N209) {Q
N”O
Molecular weight (probable), 76. Molecular volume, (probable) |TTI.
Specific gravity (theoretic) 2-63.
Synonyms. Nitrous acid (Davy, Graham, Gmelin, Berzelius,
Miller); Pernitrous acid (Guy Lussac); Hypomitrous acid (Turner,
Brande, and Liebig); Nitrous oride (Watts); Nitric trioaide (Roscoe);
Nitrogen triovide (Fownes, Roscoe).
Preparation, (1.) By mixing four volumes of dry nitric oxide
NITROGEN–COMPOUNDS WITH OXYGEN. “ 109
(N.O.) with one volume of dry oxygen, and cooling the mixture to
0°F. (—18°C.), (N2O2+0=N2O3).
(2.) By the action of arsenious anhydride upon nitric acid.
As Os -- 2HNO3= As, O3 + H2O + N2O3
Arsenious anhydride--Nitric acid=Arsenic anhydride-- Water + Nitrous anhydride.
[As.O., 4-2NO. Ho- As2O3 + OH2 + N2O3]
(3.) By the action of strong nitric acid on silver.
6HNO3 + 2Age = 4AgNO3 + 3EI2O + N2O3
Nitric acid + Silver = Argentic nitrate + Water + Nitrous anhydride.
[6NO.Ho + 2Age = 4NO. Ago + 3OH. -- N2O3
(4.) By heating together one part of starch and eight parts of nitric
acid (1-2 specific gravity).
Properties. (a.) Sensible and physical.—A deep red gas, condensing
at 0° F. (–17.8 C.) to a blue liquid, which evolves red fumes.
(3.) Chemical,—Nitrous anhydride combines with sulphurous an-
hydride to form white flakes, such as occur in the oil of vitriol leaden
chamber (SO2+N2O3). The gas is soluble in nitric acid, forming a
colored solution. By the action of a little ice cold water on the gas,
nitrous acid is formed, the liquid becoming blue (N2O3 + H2O=2HNO2).
This acid is a very unstable body, the addition of an excess of water
even at ordinary temperatures, decomposing it into nitric acid and nitric
oxide (3N20s-i-H2O=2HNO3+2N2O3).
Nitrous Acid (HNO3) (NOHO).
Molecular weight, 47.
Preparation.—(1.) By mixing a little ice cold water with nitrous
anhydride—
N20s + H2O = 2 HNO.
Nitrous anhydride + Water = Nitrous acid.
[N,0s + OH. = 2NOHo.]
(2.) By the oxidation of ammonia; as, e.g., by placing a red-hot
platinum wire in a mixture of air and ammonia gas, or by shaking up
a few drops of ammonia solution with metallic copper in a bottle con-
taining air. (Schönbein.)
Properties.—Nitrous acid is an ill-defined and unstable compound.
It forms salts called nitrites. Of these salts, as of the acid itself, our
knowledge is imperfect. Potassic nitrite (KNO.) is obtained by
heating potassic nitrate (KNOs) so as to drive off some of its oxygen.
Nitrous acid imparts the red color to nitric acid, acquired by it on ex-
posure to light. It is decomposed by water into nitric acid and nitric
oxide. -
The acid, as well as acidulated solutions of the nitrites, acts both as
a reducing and as an oxidizing agent; thus— -
(a.) As an oxidizing agent (4.HNO3=2N.O. --2H20+0.) it de-
colorizes indigo, converts ferrous into ferrie salts, oxidizes iodides,
and liberates iodine from potassic iodide,
110 HANDBOOK OF MODERN CHEMISTRY.
(6.) As a reducing agent (2HNO2+O,-2HNO2) it acts on per-
manganates and chromates, and sets free metallic gold and mercury
from their combinations.
Nitric Peroxide (N2O, or NO2) | $3. or 'N:VO,.
*º-º-º-º-º-º-mºmº
Molecular weight, 92; Molecular volume, TTI or |-|-| Specific
gravity at 3092 F. (154°C.)=1:58. 1 litre weighs (0.0896 × 23)=2:06
grims., or (0.0896 × 46)=4-12 grms.
Synonyms. Nitrous acid (Turner, Brande, etc.); Hyponitric acid
(Gmelin); Nitrous gas (Berzelius); Perowide of nitrogen (Graham,
Odling, etc.); Pernitric oride; Nitrogen tetrovide (Roscoe); Nitryl (be-
cause of its basylous action).
History-First obtained by Davy by mixing nitric oxide with
Oxygen.
Preparation. (1.) By mixing two parts of nitric oxide with one
part of oxygen. The mixture must be passed into dry and ice cold
tubes (Péligot).
(2.) By heating very dry plumbic nitrate. (The N20, in this
process is mixed with one-fourth its volume of oxygen).
2(Pb2NOA) = 2PbO + 2N20, 4- O.
Plumbic nitrate = Plumbic oxide + Nitric peroxide + Oxygen.
ſ º = 2PbO + 2'N'YO, 4- O, |
NO2
(3.) By the action of tin on nitric acid.
Sng + 20IHNO3 = Sn;Olo,5H2O + 5.K.I.O + 10N.O.
Tin -- Nitric acid = Metastannic acid + Water + Nitric peroxide.
[Sng + 20MO, Ho = Sn 305, Holo + 5OH. + 10'NYO,
(4.) By the action of nitryl chloride on argentic nitrite.
NO.Cl + AgNO, AgCl + N2O,
Nitryl Chloride + Argentic nitrite Argentic chloride + Nitric peroxide.
[NO.C1 + NOAgo AgCl + 'N'YO,
Properties.—(a.) Sensible and Physiological.—A brownish, red gas,
very irritating when inhaled. It stains the skin a yellow colour.
(3.) Physical.—Its relative weight (i.e., its weight compared with
hydrogen at the same temperature) diminishes with a rise of tem-
perature. At 275°F. (135°C.) it is 23 times as heavy as hydrogen;
therefore the molecule at this temperature is 46 (23 × 2), and is ex-
pressed by the formula NO, ; but as the temperature is lowered, its
specific gravity increases, and no doubt under such circumstances
N2O, (which at higher temperatures is decomposed into 2NO2) ex-
NITROGEN-COMPOUNDS WITH OXYGEN. 111
presses its molecular state. Actual experiments give the following
results (Deville and Troost):—
At 80:0° F. ( 26-7°C.) Specific Gravity 2-65.
,, 140-3° F. ( 60-2° C.) 3 y 2-08.
,, 177.0° F. ( 80.6° C.) 9 3 1-80.
, 212.1° F. (100-1° C.) 95 1.68.
,, 309.2°F. (154.0° C.) 25 1-58.
,, 361.7° F. (183.2° C.) } } 1:57.
Thus it would seem that the molecule of nitric peroxide is differently
constituted at different temperatures.
Action of heat.—When the gas is perfectly dry, a cold of 0°F.
(–17.8°C.) condenses it into colourless, transparent, prismatic crystals.
These crystals melt at 14°F. (–10°C.), forming a colourless liquid,
which, at 16°F. (–9°C.), becomes yellowish green, and gradually
deepens in color as the temperature rises to 71.6°F. (22.6°C.), when
the liquid boils. The liquid has a specific gravity of 1:451, and cannot
be solidified a second time at a temperature above —22°F. (–30°C.).
By the action of heat on the vapor it becomes gradually darker
until at 104°F. (40°C.) it is almost black. It is decomposed by
electric sparks, and by a temperature above a red heat. The action
of water upon it will be studied under its chemical properties.
(y.) Chemical.—Nitric peroxide reddens litmus. It was long con-
sidered an anhydride, but it always forms, when decomposed by
bases, a mixture of a nitrite and a nitrate.
It does not support the combustion of bodies unless they be burning
energetically when introduced. Chlorine combines with it indirectly
but not directly, to form an oily liquid called chloride of nitryl
(NO.Cl).
When a mixture of the gas and hydrogen is passed over spongy
platinum, the nitric peroxide is decomposed with elevation of tem-
perature, water and ammonia being formed (N20,--7EI2–2NHs--
4H2O). When a mixture of sulphuretted hydrogen and the gas is
similarly treated, water and ammonia are formed, and sulphur is
precipitated (N.O,--7EI.S=2NH4+4B.O.--7S).
Its action on water is remarkable. If a trace of moisture be
present when the gas is first prepared and subjected to the freezing
mixture, it forms a green liquid, having the probable formula of
(N2O3, N2O3.H2O). This liquid turns yellow at 14°F. (–10° C.), and
becomes red at ordinary temperatures. It freezes at—40°F. (–40°C.),
and boils at 82°F. (28°C.). Like the liquid nitric peroxide, it freely
evolves red fumes at ordinary temperatures. But if a very little ice-
cold water be added to the liquid nitric peroxide at 0° F (–17.8 C.),
two liquid layers are immediately formed, the upper layer being the
least coloured, and consisting of nitric acid, and the lower layer, the most
coloured, consisting of nitrous acid and nitrous anhydride.
3N20, -- 2H2O = 3HNO3 + HNO, -- N,0s
Nitric peroxide + Water = Nitric acid + Nitrous acid + Nitrous anhydride.
2N20, -i- OH2 = 3NO, Ho-H NOHo + N,0s.
112 HANDBOOK OF MODERN CHEMISTRY.
If at this low temperature more water be added to the liquid,
nothing but nitrous and nitric acids will remain ;-
N2O, + H2O = HNO, + TINO,
Nitric peroxide + Water F. Nitric acid + Nitrous acid.
[N2O, + OH2 = NO, Ho + NOHo.]
If water be added to the liquid peroxide at ordinary temperatures, the
solution passes through various shades of color, viz., orange, yellow,
green, and blue, finally becoming colorless, an escape of nitric oxide
taking place all the time.
3N2O, + 2 H2O = 4HNO3 + N2O2.
Nitric peroxide + Water - Nitric acid + Nitric oxide.
[3]N2O, + 2OH., - 4NO.Ho + N2O2.]
Thus, it would seem that a variety of decompositions may be effected,
according to the proportions of water mixed with the nitric peroxide,
and the temperature at which the water is added, but that in every
case nitric acid is formed. These reactions may be thus tabulated—
4N20, + H20 = 2HNO, + N,0s + 2N,0s
Nitric acid Nitric Nitrous
anhydride anhydride
Coldo 0°F.(–17.4°C.) | 3N.0, 4-2H,0 = 3HNO, + HNO, + N.0,
Nitric acid Nitrous acid Nitrous
anhydride
3N,0, + 3H,0 = 3HNO, + 3HNO,
Nitric acid Nitrous acid
Ordinary temperatures 3N20, + 2H,0 = 4.HNO, -i- N,0.
Nitric acid Nitric oxide
Action of Acids.-Sulphuric acid absorbs the gas, forming with it a
crystalline compound (2H2SO4,N2O, SO3). Nitric acid dissolves it,
and forms the deep red, green, and blue liquids, called in commerce
“ nitric acid fortissimus.” The color of these liquids is destroyed by
dilution. Hydrochloric acid forms with it several chlorinated com-
pounds. e
Action on the Metals and their Compounds.—Most metals are oxidized
by it. Potassium takes fire in it spontaneously. Iron decomposes it
at a red heat, evolving nitrogen. Potassium, lead, mercury, etc.
form a nitrate with the liquid peroxide, nitric oxide being expelled
(2N2O,--K2=2KNO3 + N.O.). With metallic oxides and hydrates
a nitrate and a nitrite of the metal are formed ; –
Nitric peroxide--Potassic hydrate=Potassic nitrate--Potassic nitrite-i-Water.
[N.0, 4- 20KH = NO.Ko + NOKo + OH..]
Action of Organic Bodies.—In some cases nitric peroxide combines di-
rectly with the organic body; thus C5H10(Amylene) + N2O4–C5H16N2O4.
In other cases it replaces hydrogen, forming nitro—compounds which
REMARKs on THE oxides of NITROGEN. : ; 113
are often explosive. They are produced by the direct action of fuming
nitric acid (mixed with sulphuric acid in order to increase its strength)
on the organic body. The following are illustrations: —
Nitro compounds.
Benzole CeBIs forms CsPIs(NO2) Nitro-benzole.
5 2 , CeBI,2(NO2) Dinitro-benzole.
Napthalene CoEſs ,, C10H1(NO2) Nitro-napthalene.
Glycerine CSEſs0, ,, C, H,3(NO.)0, Nitro-glycerine.
Mannite Cs H10s ,, C.H.,6(NO2)0s Nitro-mannite.
Cellulose Cs H100s , CsPIs 2(NO.)0s Nitro-cellulose.
Starch C12H2001o ,, C12H18(NO2)010 Xyloidin.
The only use of the nitric peroxide is as an agent in the Sulphuric
acid manufacture.
GENERAL REMARKS ON THE OXIDES OF NITROGEN.
Before we proceed to examine the next oxide of nitrogen, it is well
that we should generalise on the facts relative to the oxides of
nitrogen that we have thus far investigated. Note, then—
(1.) That the proportions of oxygen in the series advance in a
regularly ascending order—N2O, N2O3, N2O3, N2O4.
(2.) That the names of the oxides are very confusing.
(3.) That they have all been discovered since the time of Priestley
(1776).
(4.) That none of them have been found in nature in a free state,
and that only one (viz., N.O.s as nitrites) has even been found com-
bined.
(5.) That they may all be prepared by the deoxidation and de-
hydration of nitric acid, and that two of them (viz., N20s and N.O.)
may be prepared by the oxidation of N2O2.
This may be shown thus:–
2 HNO3 —H.0 =N.05 Nitric anhydride.
2 HNOs —H2O —O =N.O., Nitric peroxide.
2 HNOs —H.0 —O2 =N20s Nitrous anhydride.
2 HNO3 —H2O —Os =N2O2 Nitric oxide.
2 HNO3 —H2O —0, - N2O Nitrous oxide.
We may thus summarize the preparation of the nitrogen oxides:—
(i.) N205 is prepared by the action of phosphoric anhydride on
nitric acid.
6 HNO3+P,05–2H3PO,--3N2O3.
(ii.) N2O, is prepared by the action of tin on nitric acid.
20IHNO3+Sns=Sn;010, 5H2O+5.H.0+ 10N,01.
(iii.) N2O3 is prepared by the action of silver on nitric acid.
6HNOs--2Age=4AgNO3 + 3H2O+N20s.
(iv.) N.O., is prepared by the action of copper on nitric acid (Sp. Gr.
1:25).
) 8BIN0s-i-3Cu=30uM206+ 4H20+ N202.
I
114 HANDBOOK OF MODERN CHEMISTRY.
(v.) N2O is prepared by the action of zinc on nitric acid.
10HNO3+4Zn=4ZnN,06+5FI,0+N2O.
(6.) That they are all gases, the first two of the series (viz. N.0
and N.O.) being colorless, and the last two red. One (viz. N.0) is
respirable, and the others are irrespirable.
(7.) That their specific gravities determine their molecular consti-
|
and would
tution. The molecular volume of N2O, is anomalous
be, therefore, more correctly NO; whilst in N2O, the molecule is dif-
ferently constituted at different temperatures.
(8.) By an intense cold three of them may be liquefied and solidi-
fied; viz., N2O, N2O3, and N2O4. N2O, is a permanent gas.
(9.) At high temperatures they may all be decomposed, when
combustible bodies burn in them. -
(10.) Action of Metals.--They are all decomposed by the alkaline
metals, and also by iron and zinc when heated in contact with them.
(11.) Action of Water.—The first two (N2O and N.O.) of the series
are soluble in water, whilst the remaining two (viz., N2O3 and N2O4)
are decomposed by it, and are converted into nitric acid and into
other oxides, viz., N2O4, N2O3, N2O3, and HNO2.
(12.) Action of Acids.-Sulphuric acid is without action upon them.
Sulphuric anhydride unites with N2O3 and N2O, to form the white flakes
of the oil of vitriol leaden chamber. Nitric acid forms dark colored
liquids with N2O3, N2O3, and N2O4.
(13.) Two of them (viz. N.O., and N.O.) are bas/lous in character,
either (a) combining with chlorine to form chlorides (as e.g., N.O.),
or (3) displacing hydrogen in organic compounds (as e.g., N.O.).
(14.) Nitrous oxide is used as an anaesthetic, but the other members
of the series have little use other than the part they play in the
manufacture of oil of vitriol.
(15.) They all set iodine free (like ozone) from potassic iodide.
Nitric Anhydride, N.03–108 (N.03).
Molecular weight (probable), 108. Molecular volume (probable) TT
Melts at 85° F (29.5°C.) Boils at 113° F (45° C.)
History.-First prepared by Deville in 1848.
Preparation. (1.) By passing very dry chlorine over hot argentic
nitrate (Deville).
4AgNO3 + 2012 4AgCl + 2N2O3 + Os.
Argentic + Chlorine Argentic –– Nitrio + Oxygen.
nitrate chloride anhydride
[4INO.Ago-- 2Cl, = 4AgCl + 2N2O3 + O.].
The silver salt must be first heated to about 200°F. (93.5°C.) and
afterwards kept at 150° F (65-6° C.) The products are to be
condensed in a cold receiver.
=
-
NITRIC ACTD, _* 115
(2.) By passing the vapor of chloride of azotyle over argentic
nitrate heated to 140°F. (60° C.)
NO2Cl + AgNO3 = AgCl + N2O3.
Chloride of azotyle + Argentic nitrate = Argentic chloride + Nitric anhydride.
[NO.C1 + NO. Ago = AgCl + N2O3].
(3.) By adding phosphoric anhydride to nitric acid, thereby de-
hydrating it, the mixture being afterwards cooled and distilled.
(Weber.)
Nitric acid + Phosphoric anhydride = Phosphoric acid + Nitric anhydride.
Properties, LA colorless solid, crystallizing in rhombic or in six-
sided prisms. It melts at 85° F (29.5° C.), and boils at 113° F.
(45° C.) It is a very unstable body, and is decomposed by a heat of
122°F. (50° C.). Sometimes it explodes spontaneously. It unites
energetically with water to form nitric acid, the combination being
attended by a great elevation of temperature. A crystalline hydrate
(2N,05, H2O, specific gravity 1-642) is formed by dissolving N.O.s in
strong nitric acid.
Nitric Acid, HNO3=63 (NOAHO).
Molecular weight, 63°. Molecular volume, | | . Specific gravity at
59°F. (15°C.), 1:530. Relative weight (H=1) at 187° F = 29.6.
1 litre of nitric acid vapor weighs 31.5 criths=2'822 grims. In 100 .
parts=N2O3,85-72, H20, 14:28.
Synonyms. Aqua Fortis (Alchymists); Solutive Water (Geber);
Spirit of Nitre (Glauber); Hydric Nitrate; Hydrogen Nitrate (Watts in
Fownes).
History.—Nitric acid was known to the alchymists at a very early
period. Priestley (1777) noticed its formation when electrical sparks
were passed through air : Cavendish (1785) remarked the acidity of
the product when hydrogen was burnt in air, due, as he found, to the
formation of nitric acid, the composition of which was thus deter-
mined. Davy, Guy Lussac, and Thompson determined the proportions
in which nitrogen and oxygen were present in the acid.
Natural History. (a.) In the mineral kingdom it is found as nitres,
soda or cubic nitre being obtained from Chili, and potash or prismatic
nitre from India. These are formed by the rapid oxidation of organic
nitrogenized bodies, such as urine, etc., under the influence of a
tropical heat, and in the presence of soils rich in alkalies. It is also
found as nitrates in many well waters, produced by the oxidation of
azotized animal matters as they percolate in solution through the
soil. Nitrate of ammonia, moreover, is found in rain water, the
116 HANDBOOK OF MODERN CHEMISTRY.
atmospheric electricity effecting the combination of the nitrogen
and oxygen, the nitric acid formed combining with ammonia.
(b.) In the vegetable kingdom.—Nitric acid is not found in the recent
juices of plants, but it occurs in dried leaves (e.g., in those of tobacco),
arising from the decomposition of the alkaloids and the oxidation of
their nitrogen. (c.) In the animal kingdom it is not commonly found
except in the urine after the administration of ammonia.
Preparation. (1.) By the direct union of oxygen and nitrogen.
(a.) By the passage of sparks through a mixture of two volumes of
nitrogen and five volumes of oxygen.
(b.) By burning a mixture of one part of nitrogen and ten parts of
hydrogen in air or oxygen. The water formed will be found to
contain traces of nitric acid.
(2.) By treating nitrous anhydride (N2O3) and nitric peroxide
(N2O) with water (see pages 109 and 112).
(3.) By the slow oxidation of organic matters containing nitrogen
or ammonia in the presence of an alkali.
(4.) Ordinary manufacturing process.-By the decomposition of
potassic or sodic nitrate with strong sulphuric acid. The decomposi-
tion is two-fold:—
(a.) The sulphuric acid displaces half the nitric acid—
H2SO, H- 2NaNO3 NaNO3 + NaHSO -- HINO3.
Sulphuric + Sodic F. Sodic + Eſydric sodic + Nitric
acid nitrate nitrate sulphate acid.
[SO. Ho, + 2NO.Nao = NO.Nao + S0. HoNao + NO. Ho).
(b.) By an increased temperature the hydric sodic sulphate decom-
poses the remaining sodic nitrate, the nitric acid from which distils
OW €I’—
NaNO3 + NaHSO, = Na2SO, -i- HNOs.
Sodic nitrate + Hydric sodic sulphate = Sodic sulphate -- Nitric acid.
[NO-Nao + SO.NaoHo = SO.Nao, -i- NO. Hol.
The sodic nitrate (cubic or Chili nitre) is ordinarily used, as it is
cheaper than potassic nitrate, and yields a larger percentage of nitric
acid (i. e., as 85 to 101:1). The sodic sulphate left in the retort is
used in glass manufacture. The strongest acid (HNO3) is obtained
by distilling the commercial acid with its own bulk of sulphuric acid.
Impurities.—Lower oxides of nitrogen; chlorine and iodine (derived
from the alkaline chlorides and iodides in the nitre); sulphuric
acid, iron, alumina, potash, and soda salts.
Preparation of Pure Acid, Dilute the acid with its own bulk of
water; add one grain of potassic bichromate for every 100 grains of
the strong acid, in order to oxidize any lower oxides of nitrogen
present. Add nitrate of silver to precipitate any chlorine; syphon off
the clear liquid and distil, rejecting the first half of the distillate.
Properties.-(a.) Sensible, When pure, nitric acid is a colorless
liquid, but it is more often found in commerce of a yellow color, from
NITRIC ACID. ſ 117
the presence (by decomposition) of nitrous acid or nitric peroxide.
ſt forms grey fumes when exposed to the air, the acid absorbing
water, and condensing into minute drops. Its taste is powerfully acid.
(3.) Physiological. It is an intensely irritant poison. Sodic car-
bonate or magnesia in water should be given as antidotes.
(y.) Physical. Its specific gravity varies according to its strength (see
Table I. in Appendix). When an acid of any gravity is boiled for some
time, an acid of a definite strength is formed (2HNO3 + 3H2O). This is
the acid of the Pharmacopoeia, and has a specific gravity of 1:42.
Action of Heat.—The strong acid (1-5) boils at 210°F. (98.88°C.),
and an acid of specific gravity 1.42 at 2.48° F (120° C.). At high
temperatures it is decomposed (2HNO3=2|NO2+ H20+O). The strong
acid (specific gravity 1-5) freezes at —40°F. (–40°C.), and an acid of
specific gravity 1-4 at —41°F. (– 40-55° C.), forming in each case a
white buttery mass.
Action of Light.—The acid is decomposed by light into nitric per-
oxide, water and oxygen, the solution becoming more or less colored.
(6.) Chemical. Nitric acid reddens litmus. It is a monobasic acid,
forming salts called nitrates, which have the formula M’NO3. It acts as
a powerful oxidizing agent, owing to the large amount of oxygen it con-
tains (# of its weight), and the ease with which it can part with it.
Thus by its action iodine, phosphorus, Sulphur, selenium, carbon,
boron, and silicon are converted into their highest oxy-acids, whilst
the lower oxides, such as sulphurous, arsenious, and phosphorous
acids, are at once converted into higher oxides.
Action of Acids.-Sulphuric acid has no action upon nitric acid
except dehydration. Hydrochloric acid decomposes it, forming aqua
regia, or nitro-hydrochloric acid (3 of hydrochloric and 1 of nitric
acids), a solution containing chlorine and chloride of azotyle or nitro-
syle (NOCl) (HNO3+3HCl=2H20+ NOCl-H Cls). When aqua regia
is heated, it evolves nitric oxide and chlorine, which latter, in the
nascent state, dissolves gold and platinum (2NOC1-i-2Cl2 +2Au=
N2O2+2AuCl3).
Action on Metals and Ilſetallic Ocides.—It may here be noted that
when sulphuric acid acts on metallic zinc, or when hydrochloric acid
acts on metallic iron or tin, free hydrogen is evolved:
H2SO -- Zn = ZnSO, -- Ho.
2HCl + Fe = FeCls -- Ho.
If sulphuric acid, however, acts on oxide of zinc, or hydrochloric
acid acts on oxide of copper, the hydrogen then is not liberated as free
hydrogen, but in combination with oxygen, as water:-
H.SO, -i- ZnO = ZnSO, + H2O.
2HCl + CuO = CuCl2 + II,0.
When, however, nitric acid acts on metallic zinc or copper, no free
hydrogen is evolved, because the oxygen which is liberated at the
118 HANDBOOK OF MODERN CHEMISTRY.
same time, effects, when in the nascent state, the immediate oxidation
of the hydrogen. The results, however, produced by the action of
nitric acid on the metals vary. It will be noticed that the action of a
dilute acid is more intense than that of a strong acid. On the noble
netals (such as gold, platinum, titanium, and tantalum, etc.) it is
without action. On silver and palladium, if the acid be dilute, and
the liquid kept cold, no gas is evolved, nitrous acid being produced,
which remains in solution—(Ag3 + 3HNO3=2AgNO3 + H2O + HNO2),
On copper and mercury,an acid of specific gravity 1-25 evolves nitric oxide
(N2O2) (3Cu +8EINO3=3CuN.06+4H20+N.O.), but an acid of specific
gravity 1-42 evolves nitric peroxide (N2O), (Cu + 4HNO2=CuM206+
2H2O+N2O1); whilst if the mixture of the nitric acid and the metal be
heated, pure nitrogen will be disengaged (50u + 12HNO3=5Cu N2O6
+ N2 + 6H2O). On zinc (upon which the action of nitric acid is emergetic),
a dilute acid yields nitrous oxide (N2O) (4Zn-i-10HNO3=4ZnN,02-i-
5H20+ N2O), whilst a stronger acid sets free ammonia, which at
once combines with any excess of acid present (4Zn--9HNO3=
4ZnN2O6+3FI2O+H3N). Tin and antimony are oxidized but not dis-
solved by nitric acid. In the case of tin an insoluble stannic oxide
(SnO2) is formed, called putty powder, and nitric peroxide evolved
(Sn+4HNO3=SnO2+2H20+2N2O).
On bismuth, tin and iron the strong acid (Sp. Gr. 1-5) has no action,
but if a little water be added, energetic action at once commences.
If iron, after having been immersed in the strong acid is taken out,
and, without being wiped, is placed in a weak acid, the iron will be
found to have assumed a passive state, that is, the weak acid will
have no action upon it.
Heated with an oacide or a metallic base, nitric acid evolves no gas
but forms salts called nitrates (CuO +2HNO3= H20+Cun.06) all of
which are soluble.
Action on Organic Bodies.—Nitric acid destroys all organic bodies;
it stains all albuminous substances yellow ; when added to morphia,
brucia, or narcotine they are turned red; it oxidizes and bleaches
indigo (C.H.NO), changing it into isatin (C.H.N.O.). Substitution
compounds are often formed by the action of the strong acid on
organic bodies (see page 113).
Tests. (a.) In a free state.
(1.) The production of red fumes by its action on the metals
(N2O2+ air).
(2.) Its power of reddening morphia and brucia.
(3.) In a combined state (as nitrates). 4.
(1.) Add to a nitrate some sulphuric acid to liberate the nitric acid,
and float on the mixture a solution of ferrous sulphate. A part of
the nitric acid will be reduced, the ferrous becoming ferric sulphate,
whilst the remainder of the ferrous sulphate solution will absorb the
lower oxides of nitrogen set free, and the solution become brown at
the junction of the two liquids. (Liebig.)
COMPOUNDS OF NITRO GEN AND THE EIALOIDS. " 119
(2.) Add to a solution of a nitrate, sulphuric acid and a little indigo
solution; the latter will be bleached by the nitric acid liberated by
the action of the sulphuric acid on the salt.
(3.) By adding sulphuric acid to a nitrate and shaking the mixture
up with mercury, N.O., is set free, the quantity indicating the amount
of nitric acid present (Crum’s test modified by Frankland).
(4.) A nitrate placed on red-hot charcoal deflagrates (Chlorates act
similarly).
Uses. (a.) In nature nitric acid is one of the sources of the nitrogen
of plants. It is of no special use to animals. (b.) In chemistry and in
the arts its chief use is as a solvent and an oxidizer. (c.) In medicine
we have in the B.P. the acidum nitricum (specific gravity 1:42, and con-
taining 70 per cent. of HNO3, being in reality 2HNO3,3H2O) and
acidum nitricum dilutum (Sp. Gr. 1:101), containing 17.44 per
cent. of HNO3. The strong acid (Sp. Gr. 1-5) is used as an
escharotic.
CoMPOUNDS OF NITROGEN AND THE HALOIDs.
The combination of Initrogen with the haloids cannot be effected
directly, whilst there is some doubt as to whether any such com-
pounds exist without the presence of hydrogen.
1. Nitrogen and Fluorine.
No compound of nitrogen with fluorine is known without hydrogen
(NH,F).
2. Nitrogen and Chlorine.
Chloride of Nitrogen (Nitrous Chloride).
Of the composition of this body there is considerable doubt, its
analysis being exceedingly difficult, owing to its explosive nature.
Some regard it as NCl3, and others as a compound of NHCl2 and
NCl3. In the former case it is regarded as an ammonia molecule,
where three atoms of hydrogen are replaced by three of chlorine; in
the latter as a double ammonia molecule, where five hydrogens are
replaced by five chlorines, one hydrogen not being disturbed. Pos-
sibly there may be a series of these compounds, such as NH2Cl—
NHCl2–NCl3.
History.-Discovered by Dulong in 1812; investigated by Davy.
Preparation.—By the action of chlorine on a strong solution of
ammonic chloride.
NH,Cl + 3Cl. = 4HCl + NCl3.
Ammonic chloride + Chlorine = Hydrochloric acid + Chloride of nitrogen.
[NH,Cl + 3Cl. = 4 HCl + NCls].
NoTE.—The action of chlorine on an ercess of ammonia is to set
free nitrogen (8NH3+3Cl2=6NH,Cl-i-N.). When ammonia gas
burns in chlorine, hydrochloric acid and nitrogen are formed.
Properties, (a.) Sensible.—An oily liquid (like olive oil) having a
peculiar odor and very irritating to the eyes and nose.
120 HANDBOOK OF MOIDERN CHEMISTRY.
(3.) Physical.—Specific gravity 1.653. It is volatile at ordinary
temperatures, and boils at 160° F (71.1° C.). It does not freeze at
—16.6°F. (–27°C.) It explodes violently at from 200° to 212° F.
(93° to 100° C.)
(y.) Chemical.--The elements in chloride of nitrogen are very feebly
combined. The mere contact of phosphorus, sulphur, arsenic, the
alkalies, or of inflammable bodies generally, such as turpentine, etc.,
cause its immediate explosion. The metals, the mineral acids, alcohol,
and water have no action upon it.
3. Witrogen and Bromine.
It is doubtful whether any compound of these bodies exists.
Millon in 1828 remarked that potassic bromide decomposed nitrous
chloride (NCl3) forming a red liquid having very similar properties to
the chloride of nitrogen. He considered that the Cl3 had been replaced
by Brs.
4. Witrogen and Iodine.
Iodide of Nitrogen.
Of the composition of this body there is much doubt. It was
formerly represented by the formula NIs; Gladstone and Frankland
regard it as NHI., (nitrous hydrodiniodide), and Bunsen as NIs-i-NH3.
Possibly there is a series of these compounds.
Preparation.-By the action of iodine on ammonia.
3NH2 + 2 Ig - NHI, + 2NH.I.
Ammonia + Iodine = Nitrous hydrodiniodide + Ammonic iodide.
[3]NH3 + 21, = NHI. + 2NHI). (Frankland).
NoTE.—Nitrogen is liberated by the action of chlorine and bromine
(but not by the action of iodine) on ammonia.
Properties.—A black powder having an iodine smell and a very
high specific gravity. It is easily decomposed when dry by heat or
by the touch of a feather, fumes of iodine vapor being liberated
(NHI.-N+HI+I). Water dissolves and decomposes it, forming an
ammonic iodate, iodine with a little free nitrogen being evolved.
Sulphuretted hydrogen decomposes it, forming ammonic iodide, hydriodic
acid, and sulphur (NHI. --2H2S=HANI+HI+.S.). It is also
decomposed by solutions of the alkalies and of the alkaline earths,
iodides and iodates being formed.
CoMPOUNDs of NITRogFN, OxygEN, AND CHILORINE.
Nitrous Oxychloride. NOCl=65-5(NOCl).
Molecular weight, 65-5. Molecular volume, . Relative weight,
32.75. Specific gravity, theoretic, 2.2663. 1 litre weighs 32.75
criths=2-9344 grims.
Synonyms.-Chloro-nitrous gas (Frankland); Nitrosyle chloride
(Bloxam); Azotyle chloride.
CHILORO-NITRIC GAS. 121
Preparation. (1.) By mixing together two volumes of nitric oxide
(N.O.) and one volume of chlorine. The three volumes condense to
one volume.
(2.) By heating a mixture of nitric and hydrochloric acid (aqua
regia).
HNO, 4- 3 HCl = NOCl + Cl2 + 2 H2O.
Nitric acid + IIydrochloric acid = Nitrous oxychloride + Chlorine + Water.
[NO.Ho + 3.HCl - NOCl + Cl2 + 20PI.].
Properties.—An orange-colored gas becoming a red liquid at 0° F.
(–18° C.), which boils at 32° F (0°C.) It is decomposed in the
presence of mercury, or by contact with water. If passed into
sulphuric acid cooled to 32° F. (0° C.), crystals of NOHSO, are
deposited (NOCl-i-H.S0,-HC1-i-NOHSO).
Nitrylic Chloride (NO.Cl–81-5) (NO2Cl).
Relative weight (H=1), 40-75. Specific gravity of the liquid, 1:32;
of the vapor, 2-63 (theoretic, 2.819).
Synonyms.- Chloride of Nitryl—Nitric Dioxychloride (Frankland);
Chloropernitric gas (Frankland).
Preparation. (1.) By the action of phosphoric oxytrichloride on
plumbic or argentic nitrate.
3AgNO3 + PC130 = Ag, PO, + 3NO.Cl.
Argentic nitrate + Phosphoric = Argentic + Nitrylic chloride.
oxytrichloride phosphate
[3]NO.Ago + POCl, - POAgos + 3NO.Cl].
(2.) By the action of chlor-hydrosulphuric acid on potassic nitrate.
Properties.—A yellow liquid boiling at 41°F. (5° C) and not
freezing at —24°F. (–31°C.) It is decomposed by water, nitric and
hydrochloric acids being formed (NO.Cl-i-H2O=HCl-i-HNO3).
Chloro-Nitric Gas, NOCl, or N.O.Cl, (NYO,Cl).
Synonyms. – Nitrie dioxy-tetrachloride (Frankland); Nitric ory-
dichloride; Azotyle bichloride.
Preparation.—Formed, together with nitrous oxychloride, by
heating aqua regia.
Nitric acid + Hydrochloric acid = Chloro-nitric gas + Water + Chlorine.
[2NO.Ho + 6HCl = 'NYO.C., + 4OH. H. Cl].
Properties.—Below 19°F. (–7°C.) it is a red liquid, but above
this temperature a yellow gas. It is decomposed by water or by an
alkaline hydrate. It forms with mercury, nitric oxide and mercurous
chloride (4Hg-H N2O2Cl1=2|Hg,Cl2 +N.O.).
122 HANDROOK OF MOIDERN CHEMISTRY.
CHAPTER WI.
PEIOSPEIORUS.
PHosphorus. Compounds of Phosphorus and Oxygen–Suboxide of Phosphorus--
Hypophosphorous acid—Phosphorous anhydride—Phosphorous acid—Phosphoric
anhydride–Metaphosphoric acid—Pyrophosphoric acid—Orthophosphoric acid—
Compounds of Phosphorus and the Haloids—Phosphorous Chloride—Phosphoric
Chloride – Phosphoric Oxy-trichloride — Phosphoric Sulpho-trichloride – The
Iodides of Phosphorus–Phospham—Action of Ammonia on Phosphorus Compounds.
PHOSPHORUS (P = 31).
Atomic weight, 31. Molecular weight (31 × 4), 124. Atomic volume T or
#. Molecular volume ITI. Atomicity pentad (Y) and triad
(") (as in PCls; PH.I; PEI, ; PCls.) Relative weight (H=1), 62.
Specific gravity of vapor, 4.2904. 1 litre of P. vapor weighs (62
criths, not 31 criths) 5:555 grims.
The name phosphorus (pâc and pépw), equivalent to the Latin name
of lucifer, is derived from its property of shining in the dark. The
name had been previously given to various other bodies that were
luminous when heated, viz., Baldwin's phosphorus (calcic nitrate),
Bolognian phosphorus (baric sulphate), Homberg's phosphorus (fused
calcic chloride), etc.
History.-Phosphorus was accidentally discovered by Brandt in
urine during certain alchemical investigations (1669.) He showed
some to a German chemist, Kunkel, who spoke of it to his friend
Eraft. Kraft bought the secret of its preparation from Brandt for
200 dollars. Kunkel (1674) afterwards made it in sufficient quantity
for sale, the material being known as “Kunkel’s phosphorus.”
Boyle and his assistant, Godfrey Hankwitz (1680), also prepared it,
the latter selling it under the name of “English Phosphorus.” The
process was improved by Margraaf (1740). Gahn, in 1768, dis-
covered phosphorus in bones, and Scheele (1769) invented a ready
process for preparing it therefrom, which was afterwards perfected by
Fourcroy, Vauquelin, Nicholas, and Pelletier.
Ancient theories as to its nature.—Phosphorus was believed by the
Stahlians (their theory being in vogue at the time of its discovery)
to be a compound of phlogiston and of the white fumes produced by
its combustion, which were believed by Stahl to be muriatic acid.
Margraaf, of Berlin, in 1740, proved that this was an error, and that
the white flakes were phosphoric acid. The Stahlians then asserted
that phosphorus was a compound of phosphoric acid and phlogiston.
In 1772, Guyton Morveau proved that the phosphoric acid from burn-
PEIOSPHORUS. 123
ing phosphorus was heavier than the phosphorus from which it was
obtained ; after which Lavoisier, in 1774-5, made his famous experi-
ment of burning a known weight of phosphorus in a known quantity
of oxygen, by which he proved phosphoric acid to be a compound of
oxygen and phosphorus. In 1810-12, Davy, Gilbert, Guy Lussac,
and Thénard, established its elementary nature, since which time its
various allotropes have been discovered.
Natural History.— Phosphorus is never met with in nature in an
uncombined state.
(a.) In the mineral kingdom it is found in all the primitive and
volcanic rocks (chiefly as Cas,2PO4), and also in the soils produced
by their disintegration. It occurs as apatite and coprolites (phosphate
of lime), also as wavellite and massive phosphate of alumina, lead,
uranium, etc. (3.) In the vegetable kingdom phosphorus is extracted
from the soil by plants for animal use. It is found in all parts of the
vegetable, but more particularly in the seed.
Quantity of Phosphoric anhydride per cent. present in different substances.
Q/ Q 'A !/ f A)
P30s per cent.
Ash of tobacco stalk 2-73
,, straw (barley, wheat, oats, &c.) . . s & gº º 3:00
,, turnips. . * * * & * - - - * * gº tº 6' 10
,, clover . . tº - e e - - * * - - is e 6:30
,, flax • * e - & Cº. - - - - e - & ge 10-77
, , potatoes & © tº º tº ºr * & * * tº e 11:30
, , Qats . . tº e e G - - * - # tº * - 14-90
,, wheat . . * - * @ - - - - is e ... 16-40
(y.) In the animal Kingdom phosphorus is found in considerable
quantities in brain and in nerve tissue, as though it were essential to
the exercise of the higher functions. It is found in all the secretions
in urinary and in other calculi, in the tartar of the teeth thrown down
from the saliva by the ammonia of the breath, etc.
Proportions of Phosphorus per cent. present in various animal tissues.
Phosphorus per cent.
ſ Dry fibrin . . ... 0-32—0'42.
Mulder. ,, egg albumen .
l ,, blood , . . 0-33.
Lassaigne. Brain normal ... 1:93–1'97.
,, of idiots ... 1:00—l 50.
Courbe. ,, of Sane . . 2:00–2°50.
,, of madmen .. 3:00—4:50.
Bone . . - * ... 16'96 P. = 53 per cent. Ca,P,0,.
Solid matters of urine 2:32 per cent. of alkaline and earthy phosphates.
Preparation.—Phosphorus is the only element in the preparation
of which animal substances are employed.
(1.) Preparation from urine (old methods.)
1st process.-Evaporate the urine to dryness ; mix the residue with
sand and distil. The 'silica liberates the phosphoric acid which the
carbon reduces. (Boyle and Hankwitz.)
124 HANDBOOK OF MODERN CHEMISTRY,
2nd process.-Precipitate the urine with plumbic acetate; mix the
precipitate with one-fourth its weight of charcoal, and distil.
(Grobert.)
(2.) Preparation from native calcic phosphate and from bones.
(New process of Scheele as modified by Vauquelin, Nicholas, etc.)
(a.) Bones (from which the gelatine may be previously extracted)
are heated in an open fire to whiteness, whereby “bone-earth’’
Cas?PO, (P.O.Cao"3) is obtained.
(3.) Three parts of this bone-earth are now digested for several days
with a mixture of 2 parts of strong sulphuric acid (Sp. Gr. 1-55), and
18 to 20 parts of water. An insoluble sulphate of lime and a
soluble monocalcic salt called “Superphosphate ’’ are thus formed:—
Cas2H2O, + 2 H2SO4 = 20aSO4 + Ca2H2PO4.
Tricalcic phosphate + Sulphuric acid = Calcic sulphate + Calcic superphosphate.
(bone ash)
[P.O.Cao", + 2SO. Ho. - 2SO.Cao" + P.O. Ho,Cao"].
(y.) The mixture is now filtered through horsehair to remove the
calcic sulphate.
(8.) The clear filtrate is now evaporated to a syrup, which is then
mixed with one-fourth its weight of charcoal and heated, whereby
water is expelled, and an intimate mixture of charcoal and metaphos-
phate of lime formed:—
Ca2H2PO, - Ca2PO, + 2 H2O.
Calcic superphosphate - Calcic metaphosphate + Water.
[P.O., Ho,Cao” -: P.O.Cao" + 20 H.].
(e.) This mixture is now distilled at a red heat in an earthenware
retort rendered air-tight with borax and sandy clay, when phosphorus
passes over and is collected under hot water :—
3Ca2POs + 10C = Cag2PO, + 10CO + P.
Calcic metaphosphate--Carbon=Tricalcic phosphate--Carbonic oxide-HPhosphorus.
[3H.O.Cao" + 10C = P.O.Cao", + 10CO + P.].
Wohler recommends using sand and charcoal, whereby the whole of the phos-
phorus may be obtained. Thus:-
3Ca2POs -- 180 + 3SiO2 = 3CaSiO2 + 1800 + P6,
Calcic meta- + Carbon + Silica =Calcic silicate-HCarbonic oxide-–Phosphorus.
phosphate
[3B.O.Cao'+ 180 + 3SiO. = 3SiCao" + 18CO + Pa.]
(4.) The phosphorus is purified first by washing it under hot water
containing bleaching powder; then by fusion under ammonia to remove
any acid impurities, and finally under a mixture of Sulphuric acid and
potassic dichromate, whereby any subowide of phosphorus present is
oxidized and changed into soluble phosphoric acid. The pure phos-
phorus is then strained through leather under hot water, and cast
into sticks.
PFIOSPEIORUS. 125
(3) Phosphorus may also be prepared by passing a stream of
hydrochloric acid gas over a mixture of charcoal and heated bone ash.
Ca2PO, 4- 6HCl + 8C = 3CaCl2 + 8CO + 3H, -i- P.
Tricalcic phos. 4-Hydrochloric--Carbon= Calcic + Carbonic-i-Hydrogen-H Phos-
phate acid chloride oxide phorus.
[P.O.Cao", + 6HCl + 8C =3CaCl.-- 8CO + 3H2 + P.].
Varieties. – Phosphorus assumes different allotropic forms, of
which, amongst others, are the following :-
1. Clear transparent variety.—This is a yellow, soft, wax-like body,
tasteless in the solid form, but having a sharp, pungent flavour in
solution. It has the odour of garlic. Its specific gravity varies from
1848 to 1853. It is a non-conductor of heat. It volatilises at 111.2°F.
(44°C.), the fumes in a dark room appearing luminous.
2. White opaque variety (Rose).-This is formed by the action of
light on the above, when kept under water. The white opaque crust
forms most readily when the water contains an abundance of cal-
careous matter. Specific gravity, 1515.
3. Black variety (Thénard) is produced when the common phos-
phorus is melted and suddenly cooled to 32°F. (0°C.).
4. Red variety (Schrötter) is formed by heating yellow phosphorus
for thirty or forty hours in an atmosphere in which it cannot oxidise,
at a temperature of from 460° to 478° F (238° to 248° C.). It is
amorphous, and of a dull red color, without taste, odor, or action on the
body. Its specific gravity is 2:14, and it fuses at 550'4°F. (288°C.)
It is not luminous until heated to its firing point (600-8°F. (316°C.)).
It is insoluble in carbonic bisulphide. It is changed back again to
the common yellow variety by the action of heat in the presence of
air. It is permanent in the air, and gives off no vapor. It is not
fired by contact with iodine.
Properties.—(a.) Sensible.—A solid. The yellow variety may be
prepared in octahedral or dodecahedral crystals by evaporating its
solution in carbonic disulphide in an atmosphere of carbonic anhy-
dride. The red variety is amorphous. The color varies. The
common variety is yellow ; Rose's, white, like porcelain; Thénard's,
black; and Schrötter's, red. The odor of all the varieties, excepting
that of Schrötter, is said to be like garlic. Its taste, except Schrötter's
variety, is acrid. -
(B.) Physiological.—All varieties (except the red phosphorus) are
active poisons, less than half a grain having proved fatal. Its exact
physiological action is doubtful, some considering that its poisonous
action is due to its oxidation internally at the expense of the oxygen
of the blood; whilst others hold that it is a true blood poison, and
remains unaltered by absorption. To get it out of the system by the
stomach-pump, or, if after an interval, by an emetic, administering at
the same time some thick gruel containing chalk or magnesia, the
former to suspend the particles, and the latter to neutralise any acid
126 HANDBOOK OF MODERN CHEMISTRY.
products formed, constitutes the best method of treatment in cases of
poisoning. Above all, the administration of oils or fatty matters must
be avoided. The red variety is not poisonous. The vapours, when
inhaled (as in lucifer-match making), produce disease of the jaw bone.*
(Y.) Physical.–Specific Gravity.—This varies: the specific gravity
of the yellow variety is 1.848 to 1.853; of the white, 1.515; and
of the red, 2:14. The specific gravity of the vapor is 4.303; that
is, its volume is 62 times the weight of the same volume of hy-
drogen at the same temperature and pressure. Theoretically, it should
be only 31 times its weight. Its atom, therefore, is one-half the size
of the hydrogen atom.
Action of Heat.—The yellow variety melts and fires at about 112°F.
(44.6°C.). When melted under a solution of potassic hydrate it may
be cooled to 90°F. (32°C.) without solidifying; but if, whilst in this
state, it be touched under the solution with a solid point, it imme-
diately solidifies, and the temperature rises to 112°F. (44-5°C.). It
volatilizes at Ordinary temperatures in moist air, and at 217° F.
(103°C.) in dry air, giving off an alliaceous odor. It boils or distils
at 554°F. (290° C.), but when boiled in water, phosphorus vapor
comes over along with the watery vapor at 212°F. (100° C.).
If the yellow variety be heated a little above its melting point, and
suddenly cooled, it forms the black or Thénard's phosphorus; this
variety may, however, be changed back again to the yellow form by
fusion and slow cooling. If the yellow variety be heated nearly,but not
quite to its boiling point, and suddenly cooled, it becomes viscous. If the
yellow phosphorus be heated for a long time at from 460°F. (238°C.),
to 480° F. (249°C.), in hydrogen, or in nitrogen, or in any atmosphere
in which it cannot fire, it forms the red variety or “Schrötter's phos-
phorus,” which by a heat of 500°F. (260°C.) may be again reconverted
into the yellow variety. Rose's, or the white phosphorus, at a heat
of 122°F. (50° C.), becomes the ordinary yellow phosphorus.
Action of Light.—When yellow phosphorus is exposed under water
to diffuse daylight, it changes to the white porcelain variety (Rose's).
Sunlight acting on common phosphorus preserved either under water
or in a vacuum, changes it to an orange-yellow color. (Napoli).
Action of Electricity.—Phosphorus is a bad conductor of electricity,
unless it be melted.
Solubility.—The solubility of phosphorus in different liquids is
represented in the following table :-
Solubility of Phosphorus in various Liquids.
Water . . * * to º ... Slight.
Strong Acetic acid . . ... 0-04 per cent.
Alcohol (Sp. Gr. 834) . . 0-4 3 y
Ether (Sp. Gr. 758) .. 0
Olive oil (Sp. Gr. 916) . 1
Turpentine (Sp. Gr. 996) .. 2
Carbon Bisulphide ... 1
* See Woodman's and Tidy's “Forensic Medicine,” p. 73.
•
y
*
9
•0 3 y
5
9 3
0 to 15 times its weight.
PEIOSPHORUS. 127
The solutions, however, differ in strength very materially, accor-
ding to the length of time that the solvent has acted.
Table showing the Solubility of Phosphorus in various Liquids after
remaining in contact with them for different times.
Amount of Phosphorus taken up during
- * Quantity by Quantity by
Liquid. ...” Weight,
1st day. 2nd day. 3rd day. 4th day. 5th day. 6th day.
|
Alcohol . . . . . 1 oz. | = | 400 grS. 0-31 || 0:42 0.54 || 0-96 1 : 5 1.6
Ether . . . . . 1 oz. = | 364 , 2-9 3" () 3- 1 3-3 3-3 3-3
Olive oil . . . . . 1 oz. = | 440 , 1 - 0 1' 3 2' 4 3-0 4 - 0 4 °4
Turpentine . . . 1 oz. | = | 478 , , 3 - 1 4 '8 6'5 8 : 6 10-0 | 12-0
When the hydrogen flame containing phosphorus is examined by
the spectroscope, two green lines are apparent.
(6.) Chemical—Our remarks, for the present, refer to the ordinary
yellow variety only. Phosphorus has an intense affinity for oxygen.
Phosphoric acid is produced by its rapid combustion, and phosphorous
acid by its slow combustion, in dry air or oxygen. (See Analysis of
Air, p. 97.) In moist air the fumes evolved from phosphorus are
luminous in the dark. They are said to consist of ammonic nitrate,
formed by the action of ozonised oxygen on the air, and aqueous
vapor.
This slow combustion of phosphorus is influenced by many circum-
stances:
(1.) Phosphorus is not luminous in pure oxygen at a temperature
below 60°F. (15.6°C.).
(2.) The presence of a diluting gas, such as hydrogen, nitrogen, etc.,
greatly reduces the temperature at which phosphorus becomes
luminous.
(3.) It is essential that moisture should be present.
(4.) The luminosity is greatly promoted by heat, and checked by
cold. It is not luminous in air at 32°F. (0°C.), and but faintly lumi-
nous at from 41° to 43°F. (5° to 6°C.); but above this the luminosity
is in direct ratio to the heat applied.
(5.) The luminosity is increased by rarefaction; whilst on the con-
trary, a pressure of 4 atmospheres entirely checks it.
(6.) The luminosity is stopped by the presence of certain gases and
vapors. In addition to those mentioned in the following table, we
may also name bromine, iodine, nitrous oxide, nitric oxide, vapors
of alcohol and of volatile oils, etc., as interfering with its slow com-
bustion.
128 HANDBOOK OF MODERN CITEMISTRY.
Proportions in which certain Gases stop the slow Combustion of
Phosphorus in air at ordinary Temperatures and Pressures.
Name of the Gas. Proportions in the Temperature when the
e air by volume. luminosity ceases.
F. C.
Sulphuretted hydrogen # 66-0 18.9
Sulphurous acid * - * - Tºt 44 '9 7.2
Chlorine 6 tº e ‘º - - * @ T'; 53-9 12.2
Do. . . *; 65.8 18:8
Ether . . * * * Tºw 65.8 18:8
Olefiant gas . . * * Tºw 65' S 18:8
Phosphoretted hydrogen ºw 65.8 18:8
Naphtha. - tº tº rº, 65.8 18:8
Qil of turpentine * - - - jºi 65.8 18:8
Bisulphide of carbon tº - - e. Merest trace. 97.0 36 - 1
Quantities of Vapour required to check the Luminosity of Phosphorus
in air at elevated Temperatures.
Gas, or Vapour. Proportions in the Temperature at which
air by volume. Oxidation ceases.
F. C.
Olefiant gas # 199.9 93.3
Ether . . } 2] 4 - 1 10 1-2
Do. . . . . . . . . . . # 219.9 104 - 4
Naphtha tº e º 'º º 4 º' s T++* 169: 8 76.6
Turpentine . . * * * & - - Tºg” 185-9 85.5
The oxidation of phosphorus in air, at ordinary temperatures, may be
so rapid that it will take fire, more particularly if the phosphorus be
in a finely divided state. We may note that phosphorus flames do
not spread, owing to the phosphoric acid generated as the product of
combustion, collecting on neighbouring objects. Phosphorus com-
bines with nascent hydrogen to form phosphoretted hydrogen.
Action of Water.—Phosphorus does not form a hydrate with water,
but when preserved for some time under water, it forms phosphorous
acid and phosphoretted hydrogen (P2 + 3H2O = H3PO3 + PHs).
Action of Haloids.—The haloids attack phosphorus instantly. If
iodine and phosphorus be brought into contact, they at once ignite.
Brodie has shown that if a little iodine be added to yellow
phosphorus, melted in an atmosphere of carbonic anhydride, it will
convert an almost unlimited quantity of the yellow into the red
amorphous variety. This result depends on the formation of an iodide
of phosphorus, the phosphorus of which compound is amorphous.
This iodide is decomposed as soon as formed by the yellow phos-
* With a large amount of naphtha and turpentine, phosphorus may be actually
distilled without firing.
PPIOSPHORUS. 129
phorus to make more iodide, which is again decomposed, and so the
action proceeds indefinitely, the whole of the yellow ultimately
becoming the red variety.
Phosphorus combines with sulphur and selenium, and also with the
metals (gold and platinum not excepted) by heat. A platinum dish,
when constantly used for igniting organic substances containing phos-
plates, becomes rough. The presence of phosphorus in iron or copper,
effects considerable alteration in their properties.
Action on Metallic Solutions.—Phosphorus reduces the salts of many
of the metals, such as those of gold, silver, copper, platinum, etc., but
it has no action on the salts of lead, iron, zinc, antimony, arsenic or
manganese.
Action of Acids.-Hydrochloric acid has no action on phosphorus,
either hot or cold. When sulphuric acid, which has no action on phos-
phorus in the cold, is heated, the acid is decomposed (3H2SO,-- P.H
2H3POs (phosphorous acid) + 3SO2). Sulphurous acid is also decomposed
by it; nitric acid oxidises it, phosphoric acid being formed, and the
lower nitrogen oxides evolved (6HNO3 + P. = 2EIsPO, (phosphoric
acid) + 2N2O, -i- N2O3).
Action of Alkalies and Alkaline Earths. – When phosphorus is
heated in contact with the alkalies and alkaline earths, it forms hypo-
phosphites, phosphides, phosphates, etc. If the vapour of phosphorus
be passed over lime heated to redness, a chocolate red powder is
formed which consists of a mixture of calcic phosphide and calcic
pyrophosphate :-
14.P + 14CaO = 2Ca. P.O; + 5Casps.
Phosphorus + Lime = Calcic pyrophosphate + Calcic phosphide.
[14][P + 14CaO= 2P.O.Cao”. + 5.P.Cas].
If phosphorus be boiled with caustic soda or potash, phosphoretted
hydrogen is evolved, and a hypophosphite is formed.
Potassic + Phosphorus + Water = Potassic hypo- + Phosphoretted
hydrate phosphite hydrogen.
3OKH + P, + 3OH2 = 3IPOH.Ko + PHs.
Heated to redness with sodic carbonate, phosphorus liberates carbon.
Phosphorus has no action on dead mucous membrane, unless freely
exposed to the air, when the phosphorus softens, discolors, and in
time dissolves it.
The red variety is not characterised by any of the reactions already
described. It is singularly negative in its chemical properties.
Tests.—1. Its Odor.—This may be recognised in very dilute solutions.
2. Its property of Fuming in Air and Shining in the Dark.—These
effects are only manifest when the phosphorus is examined either in
the dry state, or in solution in water, vinegar, or in the fixed oils, the
effects being intensified by the application of heat. It is not mani-
fest when it is dissolved in ether, carbon disulphide, alcohol, turpentine,
or in the volatile oils, until the solvent has completely evaporated.
R
130 HANDBOOK OF MODERN CHIEMISTRY.
3. Its Faculty of Evolving Ozone, etc., in Damp Air.—This may be
known by—
(a.) A solution of argentic nitrate on white paper becoming black.
(3.) Starch and potassic iodide on white paper becoming blue.
(y). Litmus paper being first reddened and afterwards bleached.
(6.) The protosalts of manganese being discolored.
4. The Color of the Flame and the Products of its Combustion.
5. Its Action on certain Metallic Compounds.
(a.) Solid phosphorus reduces metallic gold, silver, copper, etc.,
from solutions of their salts.
(3.) Argentic Nitrate gives a black precipitate, with a solution of
phosphorus; cupric sulphate a brown precipitate; and mercuric chloride
a yellow precipitate.
6. Its Conversion into Phosphoric Acid.—Boil the phosphorus in a
retort with twelve or fourteen times its weight of dilute nitric acid
(Sp. Gr. 1:200). Evaporate the solution nearly to dryness, and dis-
Solve the residual phosphoric acid in water. To this solution the tests
proper to phosphoric acid must be applied.
Uses.—In Nature phosphorus appears essential to plants and
animals. It is found abundantly in brain tissue, and more parti-
cularly in the sexual organs of both plants and animals. In the Arts
its principal use is for lucifer matches, in the manufacture of which
the phosphorus is mixed with nitre on the Continent, forming “silent
matches,” and with potassic chlorate in England, forming “detonat-
ing matches.”
becoming extensive.
and aphrodisiac.
etc.
almond oil; Pilula Pho
yellow wax.)
The use of the red phosphorus in match-making is
In Medicine phosphorus acts as a nervine tonic
Compounds of AEhosphorus and Oxygen.
It is given in skin diseases, low fevers, phthisis,
(Oleum Phosphoratum, B.P., 12 grs. in 4 fluid ounces of dried
sphori, B.P., phosphorus in balsam of tolu and
Sº, yºu. |wº-ººººº sº."
... }|Po ()
H.PO, or P0H.Ho }º.
º P,0, or P,0, +3H,0 |=2H,PO, or H.PO, or POHHo, | rºom
P#. P.O. or P.O. + H20 |=H.P,0s or HPO, or P0, Ho | º;
Do. do. +2H,0 |=H.P.O., or P,0, Ho, | lº.
ſ !.
Do. do. +3H,0 |=H.P,0, or H.P0, or POHo, |º
acid.
HYPOPEIOSPHORUS ACID. 131
It will be noted from the above table—
1. That there is no anhydride of hypophosphorous acid.
2. That phosphoric anhydride forms three acids by combination
with 1, 2, or 3 molecules of water respectively.
3. That although hypophosphorous acid (H3PO2), phosphorous acid
(H3PO3), and common phosphoric or Orthophosphoric acid (H3PO,)
severally contain 3 atoms of hydrogen in the molecule, nevertheless
they differ as follows : —
In (a) Hypophosphorous acid only 1 hydrogen can be
[replaced by a metal (Monobasic.)
In (ſ3) Phosphorous acid only 2 hydrogens ditto (Bibasic.)
In (y) Phosphoric acid all 3 ditto ditto (Tribasic.)
Suboxide of Phosphorus (P,0).
This compound is supposed to constitute the colored residue left
after the combustion of phosphorus in air. The deposit thus formed
has generally been regarded as a mixture of red phosphorus and a
little phosphoric acid. It is also formed by mixing phosphorus
with phosphorous chloride, exposing the mixture to air, and after-
wards boiling in water. It is a yellow body, becoming red at high
temperatures, and igniting when heated. It is insoluble in water,
without smell or taste, and without acid or alkaline properties.
There is much doubt, however, as to its real nature.
Hypophosphorous Acid, HSPO. (POH. Ho).
The anhydride of this acid has never been obtained.
Preparation.—1. (a.) A baric hypophosphite must be first pre-
pared by boiling phosphorus in a solution of baric hydrate (Rose):—
3.Bah.0, -i- 2P, +6H.0= 3(Ba2H.P.O.) + 2H.P.
Baric hydrate--Phosphorus+ Water =Baric hypophosphite+ Phosphoreted hydrogen.
[3]BaEſos -- 2P, +6OH2= 3P.O.EI, Bao” + 2PH,).
(3) The insoluble baric hypophosphite must be then decomposed
With sulphuric acid, whereby hypophosphorous acid is set free :—
3(Ba2H2PO.) + 3H2SO, - 3DaSO, -- 6H, PO.
Baric hypophosphite + Sulphuric acid = Baric sulphate + Hypophosphorous acid.
[3]?,0.H. Bao" + 3S0. Hoo - 3S0, Bao" + 6POH.Hol.
2. By decomposing plumbic hypophosphite with sulphuretted hy-
drogen:—
(Pb2H.P.O.) + H.S PbS + 2H3PO2.
Plumbic hypophosphite + Sulphuretted = Plumbic sulphide + Hypophosphorous
hydrogen acid.
[P.O.H.Pbo" + SIH, PbS + 2POH. Hol.
Properties.—Hypophosphorous acid may be obtained as a thick
Viscid liquid by careful evaporation under the receiver of an air-pump.
132 FIANDROOK OF MOIDERN CHEMISTRY.
It has a strong acid reaction. When heated it is decomposed, yielding
phosphoric acid and phosphoretted hydrogen (2H, P02–H, PO,--H.P).
It rapidly oxydizes by exposure to air, forming phosphoric acid
(H3PO2+O2=HaBO). It acts as a powerful reducing agent on salts
of gold, mercury, etc.
Hypophosphorous acid may be known from phosphorous acid by
adding cupric sulphate to the free acid and heating the solution to
131° F (55° C). With hypophosphorous acid a reddish black precipi-
tate of cupric hydride (Cu, Ha) is thrown down, which, when heated in
the liquid to 212°F. (100° C.), is decomposed with the deposition of
the metal and the evolution of hydrogen. With phosphorous acid, the
metal is precipitated and hydrogen is evolved, but no Cu,FI., is formed.
Further, hypophosphorous acid reduces the permanganates immedi-
ately, but phosphorous acid only after some time. When hypophos-
phorous acid is treated with zinc and sulphuric acid, it is converted
into phosphoretted hydrogen.
Although the acid contains three atoms of hydrogen, it is never-
theless monobasic. Thus it forms salts as follows:–
(a.) Salts of monads — M'H. PO., e.g., KTH.PO2.
(3.) Salts of dyad metals — M"2H2PO2, e.g., Ba'2H2PO4.
These salts are prepared by boiling phosphorus in an alkaline
solution—
(a.) 3 HKO + P, -- 3 H2O = 3(KH.P.O.) + H.P.;
(3.) 3BaO + 2P, +9FI.0 = 3(Ba2H2PO.) + 2 H.P.
The hypophosphites are used in medicine, as e.g., Calcis hypophosphis
B.P. (Prep. ; by boiling together lime, phosphorus, and water), and
Soda, hypophosphis, B.P. They are commonly used in the form of syrups.
Phosphorous Anhydride, P.O. (P209.)
Synonyms.-Phosphorus Trioxide; Phosphorus Oxide.
Preparation.—(1.) By the slow combustion of phosphorus in dry
alr or 1m oxygen.
(2.) By burning phosphorus in a very limited supply of air.
Properties.—A white, flaky, non-crystalline, inflammable solid,
very volatile, emitting a garlic-like odor. It is highly deliquescent,
heat being evolved at the moment of its combination with water, and
phosphorous acid formed. Phosphorous acid cannot be changed
back to phosphorous anhydride by heat. If phosphorous anhydride
be heated in a sealed tube, phosphoric acid and free phosphorus are
formed (5 P,03–3P.O.5 + P.)
Phosphorous Acid, Hal’O,(POHHo.).
Synonym. – Hydric Phosphite.
Preparation. (1.) By passing moist air over phosphorus.
(2.) By the action of chlorine on melted phosphorus in hot water,
PHOSPEIORIC ANIHYDRIDE. 133
a phosphorous chloride being first formed, which is afterwards
decomposed by the water. Thus—
(a) P. + 3Cl3 = 2PCls.
Phosphorus + Chlorine - Phosphorous chloride.
[P. + 3Cl2 = 2PC1,).
(B.) PCls -- 3 H.O = H, PO, -i- 3HCl.
Phosphorous chloride + Water = Phosphorous acid + Hydrochloric acid.
[PCl, + 3OH. = POHHo. -- 3.HCl).
(3.) By the action on phosphorus of a saturated solution of cupric
sulphate, whereby an insoluble copper phosphide is formed, phos-
phorous and sulphuric acids remaining in solution. The latter is to
be precipitated by baryta water.
(4.) By heating phosphorous chloride with crystallized Oxalic acid.
Properties, (a.) Sensible and Physical.—A thick syrupy liquid,
from which deliquescent crystals may be obtained. It is decom-
posed by heat into phosphoric acid and phosphoretted hydrogen
(4H, P0s–3H, PO, + PHA).
(3.) Chemical.—When phosphorous acid is exposed to the air
phosphoric acid is formed. By the action of phosphorous acid on the
salts of mercury, silver, gold, etc., the metal is reduced. With mer-
curic chloride it first precipitates calomel. It reduces sulphurous acid,
free sulphur being deposited by the secondary action of the H2S on
the SO, (2SO, H-2H20+ 6Hs PO3=2H.S + 6HsPO).
Phosphorous acid is a bibasic acid; one or two hydrogen atoms
being capable of substitution by a metal. Thus—
Salts | Acid M'H.POs as KH.POs.
(with monads) l Normal M.EIPOs as K.HPOs.
Other Salts | Acid M*(H.POs).
(with dyads) l Normal M"HPOs.
It is to be noted, however, that phosphorous acid is tribasic in the
phosphorous ethers, where, as in triethyl phosphorous acid ((C2H3)3POs),
all three hydrogens of the acid are replaced by alcohol radicals; but it
must be remembered that even here only two of the compound
radicals of these compounds, can be replaced by metals.
To distinguish phosphorous from hypophosphorous acid, see page 132.
Phosphoric Anhydride, P.O;(P.O.).
Preparation.—By burning phosphorus in oxygen or in dry air. It
“”ot be prepared by the action of heat on hydrated phosphoric acid.
Properties.—Phosphoric anhydride is a white, flaky, deliquescent
solid, fusible and volatile at a red heat, subliming unchanged, and
greedy of moisture. It hisses when thrown into water, due to the
rapidity of its combination with water, which cannot be again com-
Pletely expelled by heat. Heated with carbon it yields carbonic oxide
and phosphorus.
134 EIANDBOOK OF MODERN CHEMISTRY.
Phosphoric anhydride combines with either one, two, or three
molecules of water, forming three acids as follows : —
(1.) P303+ H2O=2|HPOs =metaphosphoric acid.
(2.) P303+2FI2O=FIP.O. =pyrophosphoric acid.
(3.) P.Os--3H2O=2H3PO,-ortho- or common phosphoric acid.
We must consider these in order.
Metaphosphoric Acid (HPO3=80) (PO.Ho).
Synonyms.-Hydric Metaphosphate; Monohydrogen Phosphate
(Roscoe).
Preparation.—(1.) By dissolving phosphoric anhydride in water
(P.Og-H H2O=2|HPOs).
(2.) By the action of heat on Orthophosphoric acid, whereby
glacial metaphosphoric acid is formed.
Properties.—A colorless solid, very soluble in water. The acid in
solution changes to Orthophosphoric acid slowly at Ordinary tempera-
tures, but rapidly when boiled.
The metaphosphates are formed by the action of heat either on a
dihydric phosphate of a fixed base (NaH2PO4–NaPO3 + H2O), or
on a monohydric phosphate containing one atom of a volatile base
(NH4NaHPO,-NH2+ H20+NaPOs), or on a dihydric pyrophos-
phate (Na2H.P.O. =H2O+2NaPO3).
Tests.-(1.) Argentic nitrate, a white precipitate (AgPO3).
(2.) The acid coagulates albumen.
Pyrophosphoric Acid (H.P.O;=178). (P.O. Ho.).
Synonym.—Tetrahydric Pyrophosphate; Hydrogen Pyrophosphate
(Roscoe).
Preparation.—(1.) By heating orthophosphoric acid to 419°F.
(215° C.)
(2.) By decomposing plumbic pyrophosphate (Pb.P.O.) with
sulphuretted hydrogen :-
Pb.P.O., + 2 H.S 2PbS + H.P.01.
Plumbic pyrophosphate + Sulphuretted = Plumbic sulphide + Pyrophosphoric
hydrogen acid.
[P.O.Pbo". + 2SHg = 2PbS” + P.O.IIol.
Plumbie pyrophosphate may be prepared thus. If the rhombie
crystals of common sodic phosphate (Nag HPO,-- 12H2O) be heated, it
first becomes anhydrous sodic phosphate (Na2HPO,), and afterwards
by further heat sodic pyrophosphate (Na, P.O.), the crystals of which
are acicular. This change results from a combination of two mole-
cules of Na2HPO, and the expulsion therefrom of one molecule of
Water.
Na.HPO, * -
Na,FIPO, | = Na, P.O., + H2O.
Common sodic phosphate = Sodic pyrophosphate + Water.
2POHoNaoa 2- P.O., Nao, + OH.g.
ORTEIOPEIOSPFIORIC ACID. 135
If this sodic pyrophosphate be now dissolved in water, and plumbio
acetate added, a plumbic pyrophosphate will be precipitated [Pb. P.Or
or P.O.Pbo".].
Properties,—Pyrophosphoric acid deposits crystals, when the
solution is evaporated ‘in vacuo’ over Sulphuric acid.
It is a tetrabasic acid. Thus with sodium, we may have all the
hydrogens substituted by the metal.
Tests.-Calcic or baric salts; a white precipitate.
Argentic Nitrate, a white precipitate (Ag, P.O.). If the original
solution be neutral, it will remain neutral after the nitrate of silver
has been added, no free acid being liberated.
Orthophosphoric Acid (H3PO, or H.O.P.O;=98) (POHos).
Synomyms, Tribasic phosphoric acid; Phosphoric acid; Common
phosphoric acid; Trihydric phosphate or Hydric phosphate.
Natural History.—(a.) In the animal kingdom, orthophosphoric
acid is found largely in bones, and in guano, which is the partially
decomposed excrement of sea fowl, and in all parts of the animal as
well as in all excretions and secretions. (3.) In vegetables it is an
essential principle, “superphosphate ’’ constituting one of their most
valuable foods. (y.) In the mineral kingdom it is found as phos-
phorite, apatite, coprolite (so named with the notion that it was
petrified dung), etc. In all cases, however, it is found in combination,
and chiefly with lime and magnesia.
Preparation.—(1.) By dissolving phosphoric anhydride (P.O.) in
water, and boiling the solution.
(2.) By boiling meta- or pyro-phosphoric acids in water.
(3.) By boiling phosphorus with dilute nitric acid, the lower nitro-
gen oxides being evolved. (This is the method of preparing acid
phosphoricum dilutum, B.P., Sp. Gr. 1-08–10 per cent. of P.O;).
(4.) By decomposing bone-ash (Casp,0s) with strong sulphuric
acid, removing the insoluble calcic sulphate, decomposing the residual
acid calcic phosphate with carbonate of ammonia, filtering to separate
the calcic carbonate, evaporating to dryness, igniting to get rid of
ammonia and water, redissolving the residue, and boiling.
(5.) By the combustion of phosphoretted hydrogen in air or oxygen
(PH3+202–HaPO,).
(6.) By decomposing the triplumbic phosphate with sulphuretted
hydrogen (Pbs2PO4-1-3H.S=2H3PO,--3PbS.)
Properties.—Tribasic or common phosphoric acid is a syrupy and
very acid liquid. By evaporation “in vacuo '’ it may be obtained in
crystals. By a heat of 329° to 410° F (160° to 210°C.), it loses
water and forms pyrophosphoric acid (2H3PO, = H.P.O., + H2O),
which, at a red heat, becomes glacial metaphosphoric (H.P.O;=H2O
+2HPOs).
136 FIANDBOOK OF MODERN CHEMISTRY.
Orthophosphoric acid is the common phosphoric acid of common
phosphates.
Orthophosphoric acid is tribasic, and forms three classes of
salts by the substitution of 1, 2, or 3 hydrogens by a metal. Thus,
|With monads. With dyads. Examples.
f J/ . Na'H,PO, Dihydric sodic phos-
MEI,PO, M”2H.PO, phate (superphosphates).
M.H.PO, M”,2HPO, º Common sodic phos-
phate.
2. Neutral Salts . . M, PO, M”,2PO, Na's PO, Trisodic phosphate.
1. Acid Salts
When these salts are heated, they lose water and form other salts.
IFurther, the base need not be necessarily confined to one metal; thus,
in microcosmic salt (the sodic-ammonic hydric phosphate) for example,
we have three different basyls in one compound. Thus—
NaH, NEIPO,4H2O
[PONaon HoHo,4OH...]
Tests.-Reactions of ortho- or common phosphoric acid.
(a.) In a free or combined State in an acid solution.
(1.) Ammonic molybdate, a yellow precipitate, when heated, of
ammonic molybdophosphate, soluble in ammonia.
(b.) In a combined state.
(1.) Lime or baryta water, a white precipitate.
(2.) Ammonia and magnesia sulphate, a white precipitate :-
(Mg"HNPO,6H2O or POAmoMgo",6OH.), insoluble in ammonia,
soluble in acids. This ignited becomes Mg., P.O.
(3.) Argentic nitrate, a yellow precipitate (Ag3RO), the solution,
although previously neutral, becoming acid. Soluble in ammonia and
in nitrio acid.
(4.) Plumbic acetate or mercurous or bismuth nitrate, white precipitates
(Pb,2PO.).
(5.) Whitish yellow precipitates, with uranic nitrate or ferric chloride,
soluble in ammonia and in hydrochloric acid.
Uses.—In nature it plays an important part in animal and vegetable
tissues. -
In the arts it is used in calico printing, and in medicine its use is in-
dicated in such diseases as rickets, etc.
[Ammonia phosphas (NH,) 2HPO, is made by adding ammonia to
phosphoric acid, and allowing the crystals to form. Calcis phosphºs
(Ca,2PO) prepared from bones (os ustum, B.P.) as already described.
Soda phosphas (Na,FIPO, 12H2O), prepared from the acid phosphate
of calcium, by the addition of sodic carbonate (Ca2H.PO,--Na,CO,
=Na,EIPO,--H2O+ CO2+ Cah PO). Ferri phosphas (Fe32PO4) pre-
pared by adding sodic phosphate and acetate to ferrous sulphate
(3FeSO,4-2Na, HPO,4-2NaC.H.O. = Fe,2PO4-3Na2SO4+2C4H2O2).
ORTHOPEIOSPHORIC ACID. 137
Acidum phosphoricum dilutum, prepared by the action of nitric acid on
phosphorus.]
GENERAL REMARKS ON THE ACIDS OF THE OxTDES OF PHOSPHORUS.
It will be convenient here to generalise on the acids of the oxides
of phosphorus.
1. There are three modifications of phosphoric acid known, viz.:-
(a.) Meta- or monohydric or monobasic phosphoric acid—HPOs, or
H2O,P,05.
(3.) Pyro- or tetrahydric or tetrabasic phosphoric acid—H.P.O.,
or 2H2O,P.O.5.
(y.) Ortho- or trihydric or tribasic phosphoric acid—H3PO, or
3H2O,P,0s.
2. These acids may be severally prepared by passing sulphuretted
hydrogen through water containing, in suspension, the corresponding
silver or lead salt. Thus,
Argentic meta- + Sulphuretted = Metaphosphoric + Argentic
phosphate hydrogen acid sulphide.
[2FO. Ago + SH2 - 2PO. Ho + SAge].
Argentic pyro- + Sulphuretted = Pyrophosphoric + Argentic
phosphate hydrogen acid sulphide.
[P.OSAgo, + 2SH, = P.O., Ho, + 2SAge].
(y.) 2Ag3RO, + 3.H.S == 2H.PO, + 3AgeS.
Argentic Ortho- + Sulphuretted = Orthophosphoric + Argentic
phosphate hydrogen acid sulphide.
[2FOAgos + 3SH, - 2POHos + 3SAge].
3. (a.) The solution of P30s in cold water forms:—
Metaphosphoric acid, H2O, P.O; or PO. Ho.
(3.) This solution (other hydrates being present) on boiling be-
COIOle S : —
Pyrophosphoric acid, 2H2O,P,05 or P.O; Ho,
(y.) Whilst on prolonged boiling it yields:–
Orthophosphoric acid, 3EI2O, P.O; or POHos.
4. These acids are distinguished from one another by their reactions
on albumen, on argentic nitrate, and on baric nitrate as follows:–
Aº €Il. On Argentic nitrate. On Baric nitrate.
(a.) Metaphospho- |Coagulates | White gelatinous ppt. (AgPOs), White ppt.
- ric acid
(3.) Pyrophospho- | No action | No ppt. unless rendered alka- | No ppt. unless alka-
ric acid line, when it gives a white line, when it gives
ppt. (Ag, P.O.). a white ppt.
(y.) Orthophospho- | No action | No ppt. unless rendered alka- Ditto ditto.
ric acid line, when it gives a yellow
ppt. (Aga POA).
138 HANDBOOK OF MODERN CEIEMISTRY.
5. These acids form corresponding salts as follows:—
(a.) Metaphosphates, or monophosphates—
/ Na'PO, (PO.Nao).
MPO; fº, #6 jºy
(3.) Pyrophosphates, or tetraphosphates—
M’, P.O ſ Na', P.O; + 10H2O (P.O.Nao, 10OH.).
7 Pb"...P.O., (P.O.Pbo".).
(y.) Orthophosphates, or triphosphates—
NaH2PO, H2O (POHo. Nao,OH,).
Na2HPO, 12H2O (POHoNaoe, 12OH2).
M.PO, ) Na3POslº#29 (PONaos, 12OH2).
** ** ) Na, H, N, HPO,4H2O (PO, Ho, NaoAmo4OH2).
Ca"32PO4 (P.O.Cao's).
Ca", H.2PO, (P20, Ho Cao").
6. All forms of phosphates may be converted into tribasic phos-
phates by fusion with an alkaline hydrate, or carbonate.
7. It will be further noted that if water or ammonia (these being
volatile) enter into the composition of the salts, heat will convert
an Orthophosphate into a pyrophosphate, and a pyrophosphate into a
metaphosphate. This will be better seen as follows:–
(1.) Disodic hydric orthophosphate when heated, becomes Sodic pyrophosphate.
(Na,0), H2O,P,0s (Na,0),P,0s.
(2.) Sodic hydric pyrophosphate }} 5 y Sodic metaphosphate.
Na,0, H20, P20, Na2O,P,0s.
(3.) Sodic ammonic hydric orthophosphate 3 * } } Sodic metaphosphate.
Na,0, (NEIA),0,1120,12,0s Na2O,P,0s.
(Microcosmic salt)
(8.) The reaction of the several salts after the addition of
argentic nitrate is important.
(a.) A solution of metaphosphate of soda (Na2O,P,05 or NaPO3)
is slightly acid. On adding argentic nitrate, a white gelatinous precipi-
tate is thrown down, and the solution becomes neutral, thus—
Sodic metaphosphate + Argentic nitrate = Argentic metaphosphate + Sodic nitrate.
PO.Nao + NO2Ago = PQ. Ago + NO.Nao.
(6.) A solution of sodic pyrophosphate (2Na2O,P,05, or Na, P.O.) is
alkaline. On adding argentic nitrate a white precipitate is thrown down,
and the solution becomes neutral. Thus—
Na,F20, + 4AgNO3 AgP.Or + 4NaNO3.
Sodic pyrophosphate + Argentic nitrate Argentic pyrophosphate + Sodic nitrate.
P20, Naot + 4NO2Ago P2O3Ago, + 4NO2Nao.
(y.) A solution of sodic orthophosphate (NaO,2H2O,P,0s or
Na. HPO,) is alkaline. On adding argentic nitrate a yellow precipitate
is thrown down, and the solution becomes acid. Thus–
Na2HPO, + 3AgNO3 Ag, PO, + 2NaNO3 + HNO3.
Sodic + Argentic Argentic + Sodic + Nitric
orthophosphate nitrate orthophosphate nitrate acid.
POELoNao. -- 3.N.O.Ago = POAgo, + 2NO.Nao + NO:Ho.
=
=
PHOSPEIOROTſS CHILORIDE. 139
(9.) Other varieties of phosphates have been described by Fleit-
mann and Henneberg :—
(a.) By heating together one molecule of sodic pyrophosphate and
two of metaphosphate, a salt is obtained consisting of 2Na3PO4, P.O.5.
(3.) By heating one molecule of pyrophosphate with eight of
metaphosphate, a salt is obtained consisting of 4Na3PO4,3P,05.
Corresponding silver and magnesium compounds have been obtained.
These compounds are very unstable, quickly becoming a mixture of
pyrophosphate and metaphosphate. It would thus seem that the
following phosphates have been prepared, viz.:-
Orthophosphates ... * c & ... 6M2O,2P.O; or 4MAPO.
Pyrophosphates • * * tº tº º ... 6M20,3B.O.; or 3M, P.Or.
Fleitmann and Henneberg's salt (a) 6M20,4IP2O3 or 2M6P4O13.
Do. do. (3) 6M20,5IP.O; or M12 ProQg1.
Metaphosphates ... tº $ & ... 6M2O,6F2O3 or 12MPO3.
Compounds of Phosphorus and the Haloids, etc.
With Chlorine. With Bromine. With Iodine.
Trichloride ... PCl, Tribromide ... PBra Diiodide . . . . PI,
Pentachloride ... PCls | Pentabromide ... PBrs | Triiodide . . . . PIs
Oxytrichloride ... POCl, Oxytribromide ... POBr,
Sulphotrichloride PSC1, Sulphotribromide PSBra
Phosphorous Chloride, PCl3(PCls).
Molecular weight, 137:5. Relative weight, 68-75. Molecular volume,
| | | . Specific gravity of liquid, 1:516; of vapor, 4.79.
Synonyms.-7'richloride or Terchloride of Phosphorus.
Preparation. (1.) By passing phosphorus vapor over heated mer-
curic chloride (corrosive sublimate).
(2.) By the action of chlorine on dry melted phosphorus (P.--3Cl.
= 2PCls).
Properties.—A transparent colorless volatile liquid, soluble in
benzol and in carbonic disulphide. It dissolves phosphorus and also
absorbs chlorine freely, forming PCls. At its boiling point, 165.2°F.,
(74° C.) it absorbs oxygen, forming POCls. It is decomposed by
alcohol, by ether, and by a large excess of water, in the latter case
hydrochloric and phosphorous acids being produced. If hot water
be used the re-action is very violent.
Phosphorous chloride + Water = Hydrochloric acid + Phosphorous acid.
[PCl, + 3OHe = 3|EIC1 + POHHos.]
140 HANDBOOK OF MODERN CHEMISTRY.
Phosphoric Chloride, PCl3(PCl3).
Molecular weight, 208-5. Molecular volume, | | | to –El
Relative weight, 52.1 to 104-25. Specific gravity of vapor at 572° F.
(300° C.) 3-654.
Synonyms.—Pentachloride or Perchloride of Phosphorus.
Preparation.—(1) By the action of chlorine either on dry
phosphorus in an exhausted flask, or on phosphorous chloride
(PCl3+Cl2=PCl3).
(2.) By passing chlorine through a solution, artificially cooled, of
phosphorus in carbonic disulphide. The solution is afterwards eva-
porated to dryness.
Properties.—A white deliquescent crystalline solid, volatile (before
melting) at 212° F (100° C.) It may be fused under pressure at
298° F (148°C.) It burns when passed into a flame, chlorine and
phosphoric anhydride being formed. It combines with ammonia.
When acted on with acids or with alcohols it forms chlorides of the
radicals of the said alcohols and acids. Thus—
C.H.30 or | §H, becomes C.H.C. or | §al
Ethylic Alcohol becomes Ethylic Chloride.
It is decomposed by an excess of water, hydrochloric and phosphoric
acids being formed:—
PCls + 4H2O = 5HCl + H3PO4.
Phosphoric chloride + Water = Hydrochloric acid + Phosphoric acid.
[PCl; + 4OH2 = 5HCl + POHos].
Phosphoric Oxytrichloride, POCl3(POCl3).
Molecular weight, 153:5. , Molecular volume, | | | . Relative weight,
76-75. Specific gravity of liquid, 1:7; of vapour, 5298. Boils
at 280° F (110° C.).
Synonyms.-Phosphoryl Chloride or Trichloride ; Oxychloride of
Phosphorus.
Preparation. (1.) By the slow action of a small quantity of water
on phosphoric chloride (PCl3+ H2O=POCl3+2HCl).
(2.) By passing oxygen through boiling phosphorous chloride
(PCla--O=POCl3). -
(3.) By heating together phosphoric chloride and phosphoric an-
hydride (3PCl3+ P.O;=5|POCl3).
(4.) By heating an acid (such as oxalic or boracic acid) with
phosphoric chloride (Gerhardt) (5 PCls + 2(BH,03) = 3POCl3 +
6HC1-i-B2O3).
Properties.-A volatile limpid fuming liquid, decomposed by water
THE IOIDIDES OF PHOSPHORUS. 141
into hydrochloric and phosphoric acids (POCl3+3H2O= H3PO,--
3.HCl).
The importance of this compound, as well as of the other chlorides
of phosphorus, depends on its action in producing various organic
substitution products.
The bromides and oxybromide of phosphorus correspond to the
chlorine compounds.
Phosphoric Sulphotrichloride, PSC1, (PS"Cls).
Iſolecular weight, 169-5. Specific gravity of liquid, 1-631; of vapor, 5.878.
Boils at 257° F (125° C.).
Synonyms.-Sulphochloride of Phosphorus.
Preparation,-( 1.) By decomposing phosphoric chloride with sul-
phuretted hydrogen (PCl3+SH2=PSC13+2HCl).
(2.) By decomposing phosphoric chloride with antimonious sul-
phide (3PCl3+ Sb2S3=3PSC13+2SbCls).
Properties.—A colorless, fuming liquid. When boiled with sodic
hydrate, it forms sodic chloride and trisodic sulphophosphate; from
this latter the corresponding barium, calcium, and strontium salts
may be prepared by double decomposition. (Wurtz.)
6NaHO –– PSC1, = 3NaCl + NaspSO3 + 3H2O.
Sodic hydrate + Phosphoric = Sodic chloride + Trisodic + Water.
sulphotrichloride sulphophosphate
[60NaH + PSC1, = 3NaCl + PS"Naos -- 3OH.
It is decomposed by water forming phosphoric, hydrochloric, and
hydrosulphuric acids (2PSC13+8H2O=2H3PO, 4-6HCl·H2H.S.)
THE IoDIDEs of PHosphorus.
The Di- or Biniodide of Phosphorus (PIs) is prepared by adding
2 atoms of iodine to 1 atom of phosphorus dissolved in carbonic di-
sulphide, and subsequently cooling the mixture. It forms orange-
coloured prismatic crystals, melting at 230°F. (110° C.), and decom-
posed by water. It has no analogue amongst oxygen, chlorine, or
bromine compounds.
The Triiodide (PIs) is prepared similarly to the diiodide by using
proper atomic proportions of the constituents. It forms dark red deli-
quescent six-sided plates, melting at 130°F, (55° C.).
By heating 100 atoms of phosphorus with 1 of iodine the whole of
the phosphorus may be changed into the red or Schrötter's phosphorus
(see page 128).
Other compounds of oxygen and the halogens with phosphorus
have been described, viz., pyrophosphoryl chloride (P.O3Cl3), phosphorus
bromochloride (PCl, Br.), phosphoryl chlorobromide (POCl, Br), phosphorus
sulphobromochloride (PSC1, Br), etc.
142 HANDROOK OF MODERN CHEMISTRY.
Phospham (HN.Pº).
Preparation.—By saturating phosphorous chloride (cooled by a
freezing mixture) with ammonia gas, a white saline mass (51H3N, PCls),
is obtained. This is now heated in a current of CO, until all the sal-
ammoniac is sublimed. The residue constitutes Phospham. (Gerhardt.)
Properties.-A yellowish-white bulky amorphous powder, termed
phosphide of nitrogen by Rose. Its composition is probably HN3P.
Rose overlooked the presence of hydrogen in the body, inasmuch as
phospham is unaffected by chlorine, and, provided no air be present,
may be heated to redness without change.
ACTION OF AMMONIA on PHOSFEIORUS CoMPOUNDs.
(1.) When anhydrous phosphoric acid (P,05) is heated with am-
monia, phosphamic acid (N.H.P.O.) is formed, (2NH3+P.O;=H20+
N.H.P.O.). When phosphamic acid is heated with water it forms the
acid phosphate of ammonia (N2H4P3O4-i-4II2O=(NH4)30.2H2O.P.,05).
The phosphamate of ammonia, heated in a current of dry ammonia
loses water, and becomes phospham. Thus : —
(NH4)2ON.H.P.O. = 5H2O + 2HN.P.
Phosphamate of Ammonia = Water + Phospham.
(2.) When phosphoric chloride (PCl;) is heated with ammonia, chloro-
phosphamide (N.H.PCl3) is formed, (PC);+2NHa=2HC1-i-N.H., PCl3).
By boiling this body with water it becomes phosphodiamide (N2H3PO);
(N.H.PCl3+ H2O=N2H3PO +3HCl) which by heating becomes mono-
phosphamide (NPO); (N2H3PO=NH3+NPO).
(3.) By the action of ammonia on oxychloride of phosphorus (POCl3)
phosphotriamide is formed (NaH6PO).
(4.) By the action of ammonia on sulphochloride of phosphorus (PSC13)
sulphosphotriamide is formed (NaHSPS).
These amides are derivatives of ammonia salts by the loss of water
molecules.
(NH,),0,2H2O,P,04 – 6H2O = 2NPO, Monophosphamide.
2(NH,).0, H2O, P.O; - 6H.0 = 2N.H.PO, Phosphodiamide.
3(NH4)2O,P,0s — 6H2O = 2Ns HGPO, Phosphotriamide.
(NH4)20,2H2O,P,04 – 4H2O = N.H.P.O., Phosphamic acid.
143
CHAPTER VII.
SULPH.U.R.—SELENIUM TELLURIUM.
SULPHUR.—Compounds of Sulphur with Oxygen. and Hydroxyl—Sulphurous anhy-
dride and acid— Sulphuric anhydride and acid — Hyposulphurous acid —-
Thiosulphuric acid — Dithionic acid — Trithionic acid — Tetrathionic acid –
Pentathionic acid — Compounds of Sulphur and Chlorine — Compounds of
Sulphur, Oxygen and the Haloids—Compounds of Sulphur and Phosphorus.
SELENIUM.–Compounds of Selenium and Oxygen. TELLURIUM.–Compounds of
Tellurium and Oxygen.
SULPHUR (S.).
Atomic weight, 32. Molecular weight, 64. Molecular volume at 1000°C.
|T|, below this, one-third. Atomicity, Hezad (SWO. Hog),
Tetrad (SWO.), Dyad (S"H.). Relative weight, 32. Specific gravity
of solids, various ; of vapor, at 900°F. (4822°C.), 6.617, and at
1904°F. (1040° C.), 2:23; melts at 239°F. (115°C.); boils at
836° F (446°C.).
Synonyms.-Pyrites (rup fire); Brimstone (Brume or Breinse fire,
and Stein a stone); Sulphur (sal salt, and Tup fire.)
History.—Sulphur was known in early times. It is mentioned by
Moses, Homer, and Pliny, and is referred to by Geber as one of the
principles of nature. It was considered by the alchemists to constitute
the impurity of the baser metals. In the middle ages it was regarded
as the principle of fire, and every combustible body was supposed to
contain it.
Natural History.—(a.) In the mineral kingdom sulphur is found (1)
in a free state in many volcanic districts, either in yellow crystals or
in opaque amorphous masses embedded in blue clay and in fissures
in gypsum and celestine (virgin or native sulphur). [When sul-
phuretted hydrogen, steam, and air are passed over calcic carbonate
at 212°F. (100°C.) gypsum is formed, and sulphur deposited.] (2.)
It is found in combination with hydrogen, in certain mineral waters
(Harrogate), and with the metals, as sulphides (FeS2, iron pyrites;
Cu2S.Fe2Ss, copper pyrites; PbS, galena ; ZnS, blende ; Sb2S3, crude anti-
mony; HgS, cinnabar). (3.) It is also found as sulphates, as e.g.,
sulphates of lime (gypsum, CaSO4), baryta (heavy spa, BaSO4), strontia
(celestine; SrSO), magnesia (Epsom salts, MgSO4), and soda (Glauber
salts, Na2SO4).
(3.) In the vegetable kingdom it is present in albumen, gluten, etc.,
and also in the acrid volatile oils, such as essence of mustard (C,EſsNS);
whilst (y.) in the animal kingdom it is found as a constituent of al-
bumen, fibrin, and casein, in muscular tissue, hair, bile, etc.
144 HANDBOOK OF MODERN CHEMISTRY.
Preparation.—(1.) By a rude process of simply melting out the
sulphur from its impurities. -
(2.) By distilling the sulphur in earthenware retorts, and allowing
the distillate to flow into water. This “rough sulphur,” as it is
called, is redistilled in iron retorts, and the sulphur collected either in
cooled brickwork chambers (forming flowers of sulphur), or else as
a liquid which is afterwards cast into rolls (forming roll sulphur.)
(3.) By the distillation of iron or copper pyrites.—The pyrites is
heated either (a) in close vessels, when one-third of the sulphur is
driven off, and magnetic pyrites remain (8 FeS2=Fe,S, +S.), or (3)
in the open air. This is done in the case of copper pyrites as a pre-
liminary stage to copper roasting. The pyrites heaped on brushwood
and fired from a central flue, is kept burning for months, and the
sulphur therefrom collected in pits. The sulphur prepared from
pyrites generally contains a little arsenic. -
(4.) By distilling the spent oxide of iron used in gas purification.
The oxide, by successive revivifications,” becomes charged with from
40 to 60 per cent. of sulphur (2FeS-H H20+ Og=Fe2O3 +OH2+.S.).
> --> --~~
Spent oxide.
(5.) It is also prepared from the tank waste of alkali works.
Varieties.—(1.) Native Sulphur.—This variety occurs naturally, and
may also be obtained by the spontaneous evaporation of a solution of
sulphur in carbonic disulphide. It consists of transparent yellow
crystals (octahedra), which are unaltered by exposure to air. It has
a specific gravity of 2:05. It fuses at 239°F. (115°C.) It is the
most stable of the sulphur allotropes, and is the ultimate condition
which all the other varieties assume.
(2.) Yellow sulphur.—This may be crystallised by fusion (oblique
prisms). It is brownish yellow when first prepared, but changes by
exposure to air to an opaque yellow. This alteration is attended
with a change of form (octahedra) and the evolution of heat. It has a
specific gravity of 1.98. It fuses at 248° F (120° C.).
(3.) Ductile sulphur.—This is prepared by pouring melted sulphur
(800°F.) into cold water. By exposure to air it changes into the
crystalline variety, becoming yellow and brittle, evolving heat during
the alteration. A similar change may be effected by heating the
ductile sulphur to 230°F. (110°C.).
(4.) A Buff. Amorphous Variety.—This constitutes the insoluble re-
sidue that remains after exhausting the flowers of sulphur, or the ductile
variety after prolonged exposure to air, with carbonic disulphide.
(5.) White Variety (milk of sulphur).-This is prepared by precipi-
tating a solution of sulphur in an alkali (an alkaline polysulphide) with
an acid:—
(K.S. 4-2HC1 = 2KCl + H.S + 2S.).
* By revivification the moist ferrous sulphide is changed into ferric hydrate and
sulphur.
SULPH.U.R. 145
A Black Variety has also been described by Magnus, as well as
one of a red color, but of these our knowledge is not complete.
These allotropic forms of sulphur may be thus classified:–

1. 2. - 3. 4. i 5
º - º Amorphous | White amor-
Octahedral. | Prismatic. Ductile. powder. phous variety.
Color . . . . | tºº * Deep amber. Buff. White.
F '...}. Oblique |Plastic amor- Amorphous Amorphous
OTDIl . . . . i. . prisms. phous mass. powder. powder.
Specific grav. 2.05. 1 98. 1-95. 1.95.
• - 239° F. 24 Sº F.
Melting point | (115° C.) (120° C.)
Action of car- Soluble
bonic disul- | Soluble. (changed into Not soluble. | Not soluble. ||Very soluble.
phide . form No. 1).
Properties.-The properties of sulphur differ according to the
variety:
(a.) Sensible and Physiological.—Sulphur is met with in commerce,
either as roll sulphur or as flowers of sulphur. It crystallizes in two
distinct forms, viz., in octahedra and in oblique prisms (dimor-
phous). Ordinary sulphur is yellow, but the colors of its allotropes are
various. Native sulphur is transparent, but all the other forms are
opaque. It has no taste or smell. Its medicinal action is mildly
laxative.
(3) Physical.—The specific gravity of the transparent crystalline variety
is 2-05; of the prismatic 198; of the ductile and the amorphous powder
195. The specific gravity of the vapor at 900°F. (4822°C.) is 6-617,
whilst at 1904°F. (1040°C.) it is 2-222. (Deville.) Thus, at 1904° F.
sulphur vapor becomes dilated to three times the bulk it occupies
at 900°F. This fact is important. We mean by specific gravity the
weight of a body compared with an equal volume of dry air at the
same temperature and pressure. Hence the actual temperature, in
the case of most gases and vapors, is of no consequence. For example,
whether oxygen be compared to air at 60° F., or to air at 600°F., so
long as both oxygen and air be at the same temperature when the
comparison is made, their weights relatively would be as 1-1057 to
1.000. In the case of sulphur vapor, however, its specific gravity at
900°F. is 6:617; that is, it is six and a-half times heavier than air at
900°F., the atom being, therefore, 96 times as heavy as hydrogen.
It follows, therefore, that the atomic weight of sulphur being 32, the
atom would only occupy 4 of a volume. But at 1904°F. its specific
gravity becomes 2.222; that is, the sulphur vapor is about two and
a-quarter times as heavy as air at 1904°F. It is evident, therefore,
that sulphur vapor is only a true gas at this higher temperature, one
atom of sulphur occupying one volume, and being 32 times the weight
of a hydrogen atom.
L
146 HANDBOOK OF MODERN CHEMISTRY.
Action of Heat.—Sulphur is a bad conductor of heat. When held in
the hand it crackles, owing to unequal expansion. It is slightly
volatile at common temperatures, and freely volatile at 2800 F.
(137.8°C). The octahedral variety fires at 239°F. (115° C), and
the prismatic at 248° F. (120° C.). It boils at 836° F (446.6° C).
The action of heat on sulphur is remarkable, and may be examined
under the heads of Fluidity, Color and Form.
(1.) In respect of Fluidity.—At a temperature of from 250° to 280° F.
(121° to 138°C.) sulphur becomes liquid; at 350° F. (170° C.) it be-
comes thick and viscid; and at 500° F (260° C.) it again becomes
liquid.
(2.) In respect of Color.—The sulphur remains yellow to 280° F.
(137.8°C.). At from 280°F, to 350°F (138° to 177° C.) it becomes
orange; at from 350° to 400°F. (177° to 204°C.) it turns a reddish
color; at from 400° to 500°F. (204° to 260° C.) it becomes dark
brown; whilst at 600°F (316°C.) it becomes black.
(3.) In respect of Form.—When sulphur is heated to 239°F. (115° C.)
and cooled slowly, its crystals are right prisms; when heated above
this temperature and cooled slowly, it forms oblique prisms; whilst,
if heated above 500°F. (260° C.), and then cooled rapidly, it assumes
the elastic and amorphous modification.
We may state these facts generally as follows:—When the sulphur
is heated to 280° F (138° C.) it becomes liquid. As the heat is
continued, it gradually becomes thick and viscid, until at 350°F.
(176.7°C.) the liquid becomes so thick that it will not fall out of the
vessel when inverted. It remains at this temperature for some time,
notwithstanding the continuous application of heat. At from 350° to
500°F. its fluidity is restored, and it assumes a dull brown color. If
it be now poured into cold water, the elastic variety is produced. In
the change from the elastic to the common yellow modification, the heat
absorbed at 350°F. (176.7°C.) is evolved. When the melted sulphur
is allowed to cool, it passes through the same stages inversely as when
heated, that is, it first becomes viscous, then fluid, and finally solid.
Sulphur is a non-conductor of electricity, becoming negatively
electrical by friction. All the varieties of sulphur are insoluble in
water, but are soluble in alcohol, chloroform, and ether, and (except-
ing the amorphous modification) in turpentine, chloride of sulphur,
benzene, the fixed oils, and more particularly in carbonic disulphide.
(y.) Chemical.—Sulphur is combustible at from 450° to 500°F. (235°
to 260°C.) burning with a blue flame, and forming SO2. It combines
freely with all the non-metals except nitrogen, and with all the
metals, many of which burn in its vapor. In its chemical relations
it is closely allied to oxygen. Chemically, sulphur may be divided
under two heads:—
(1.) Where it is electro-negative, that is, where it is separated from a
compound at the positive pole of the battery, as in H2S. This form is
soluble in carbonic disulphide.
SULPEIUR. 147
(2) Where it is electro-positive, that is, where it is separated at
the negative pole of the battery, as in SO2 or in S2Cl2. This form
is insoluble in carbonic disulphide.
Concentrated nitric and sulphuric acids act on Sulphur slowly, the former
converting it into sulphuric acid, and the latter into sulphurous acid. It
is changed into sulphuric acid by the action of nitric acid and potassic
chlorate. The alkalies dissolve phosphorus when heated with it, a
mixture of a hyposulphite and a sulphide of the metal being formed.
Uses.—In the arts, sulphur is used in match-making, in preparing
vulcanised caoutchouc, in bleaching, and in the manufacture of gun-
powder and oil of vitriol. In medicine it is used as a laxative, and
in various forms of cutaneous diseases. In the preparation of the
sulphur precipitatum (milk of sulphur), the pharmacopoeia directs 5
parts of sulphur to be boiled in water with three parts of lime. Thus,
a calcium hyposulphite and polysulphide are formed (3CaF2O2+6S2
=2CaSg-H CaS2O3 + 3H2O). The sulphur in the solution is now pre-
cipitated with hydrochloric acid (20aS; + CaS2O3 + 6HCl = 3CaCl2
+3H20+ 6S.). The sulphurous acid set free by the action of the
acid on the hyposulphite decomposes the sulphuretted hydrogen, set
free by the action of the acid on the sulphide (4H2S--2SO2=3S2
+4H2O). “Milk of sulphur,” however, is often precipitated by adding
sulphuric acid instead of hydrochloric acid, and in this way becomes
largely adulterated with calcic sulphate (2CaSg-i-CaS20s-i-3H2SO,
=3CaSO4+ 3EI2O+6S.). This adulteration may be known by a
residue of calcic sulphate being left on ignition.
Sometimes a trace of arsenic is present in the sulphur sublimatum
B. P. (flowers of sulphur) prepared from pyrites.
Compounds of Sulphur with Oxygen and Hydroxyl.

-: * — A as • Constitutional
Aºi. Formula. |+Water" =º * for Name of acid.
Sulph H.S0, SHo, Hyposulphurous acid.*
ll w & tº
. } SO, or S0, +H,0 =H.S0, SOHo, Sulphurous acid.
*ś, SO, or S0, +H,0 =H.S0, S0, Ho, Sulphuric acid.
3. | H.S.0, ſ 5.º. Thiosulphuric acid.
É. H2S,0s l so. Ho Dithionic acid.
#. S0, Ho
s H.S,0s | S” Trithionic acid.
& SO, Ho
SP. S0, Ho
§ ~ H.S,0s §. Tetrathionic acid.
cº) SO, Ho
‘E S0, Ho
.3 S”
#. H.S,0s §. Pentathionic acid.
& U S0, Ho
* This will be considered after sulphuric acid.
148 HANDBOOK OF MODERN CHEMISTRY,
NoTE,-(1.) That the sulphur in these compounds is either hexad,
tetrad, or dyad. -
(2.) That only two anhydrides or oxides have been iso-
lated (viz., SO, and SO3).
Sulphurous Anhydride, SO2(SO4).
Molecular weight, 64. Molecular volume, TTI. Relative weight, 32.
Specific gravity of gas, 2.247; of liquid, 1:38. 1 litre of the gas
weighs 2:217 grims., and 100 cubic inches 69-814 grains.
Synonyms.-Sulphur Dioxide; Volatile Spirits of Sulphur; Phlo-
gisticated Vitriolic Acid.
History.—The irritation produced by burning sulphur is mentioned
by Homer and Pliny. It is said to have caused the death of the
elder Pliny (A.D. 79), in his curious enquiry into the eruption of
Vesuvius. Its properties were studied by Stahl and by Priestley
(1774), who determined its real nature by burning sulphur in pure
oxygen.
Natural History.—It is found in the air of volcanic districts and
in that of towns, in the former case issuing from volcanoes, and in
the latter evolved from burning coal, or from roasting copper pyrites
and other sulphur ores.
Preparation. — (1.) By burning sulphur in air or oxygen
(S+O2=SO2).
(2.) By heating sulphuric acid with metals, as copper or mercury.
Cu + 2DLSO = CuSO4 + SO, + 2 H2O.
Copper + Sulphuric acid = Cupric sulphate + Sulphurous anhydride + Water.
[Cu + 2SO. Hoc = SO2Cuo" + SO, + 20PIs.
(3.) By heating sulphuric acid with carbon or with any organic
matter. The SO2 evolved is mixed with CO2.
2H2SO4 + C = 2SO. + CO, + 2 H2O.
Sulphuric acid + Carbon = Sulphurous anhydride + Carbonic anhydride + Water.
[2SO. Ho, + C = 2SO3 + CO2 +2OH.].
(4.) By heating together sulphur and manganic peroxide.
S. + MnO2 = SO. + MnS.
Sulphur + Manganic peroxide = Sulphurous anhydride + Manganous sulphide.
[S. + MnO2 = SO, + MnS"].
(5.) By heating together dehydrated ferrous sulphate and sulphur
(FeSO,--S.–FeS-2SO.).
The gas must be collected in dry bottles by displacement or over
mercury.
Properties. (a.) Sensible.—A colorless gas having a strong
brimstone odor.
(3) Physiological,—It rapidly destroys life when in a concentrated
form. When very dilute the irritation produced in the first instance
SULPHUROUS ANHYDRIDE. 149
rapidly passes off, the animal becoming tolerant of somewhat large
quantities. One part in 10,000 parts of air is destructive to plant-life.

Proportion
of S0, in Physiological effects and chemical reactions.
10,000 of air.
4:34 Air irrespirable. Acts instantly on iodic acid and starch.
2°00 Air strong both to taste and smell. Acts on starch and iodic acid in
30 seconds.
0-86 Air strong to smell, and irritating. Acts on test paper in 2 minutes.
0 - 1 - Smell perceptible. Acts on test paper after some time.
(y.) Physical.-The gas has a specific gravity of 2:247; 100 cubic
inches weigh 69-814 grains. It is freely soluble in water and in
alcohol. By a pressure of three atmospheres at common temperatures,
or by a cold of —0.4°F. (–18°C.) it becomes a transparent liquid
having a specific gravity of 1:38, boiling at 14° F. (–10° C.) and
solidifying at –105°F.(–76°C.) The solid thus formed is colorless
and transparent, and melts at –1102°F. (–79°C.)
Liquid sulphurous anhydride dissolves bitumen, phosphorus,
sulphur, iodine, etc.
(8.) Chemical.—Sulphurous anhydride first reddens and afterwards
bleaches litmus. It will not support the combustion of a taper.
It is a powerful reducing agent, owing to its tendency to become
oxidized. When a sulphurous acid solution is heated in a sealed tube
to 340° F. (171° C.) it yields free sulphur and sulphuric acid, one
portion of the sulphurous anhydride becoming oxidized at the expense
of another portion (3SO2+2H2O=2H2SO4+S). It reduces nitric
acid (2HNO3+SO2=H2SO4+N2O); also iodic acid, setting free iodine,
and also chromic, arsenic, and permanganic acids,
It is a powerful bleaching agent. It does not, however, destroy
the coloring matter (as in the case of chlorine, the bleaching action of
which is due to oxidation), but merely forms colorless compounds
with the coloring matters. The color of the article bleached with
SO2, may be restored by the action of an alkali or of a stronger acid.
Action on Chlorine.—Sulphurous anhydride combines with chlorine
in equal volumes under the influence of bright sunshine, to form
chlorosulphuric acid or chloride of sulphuryl (SO2Cl2), a colorless liquid
emitting very acrid irritating vapors. This body does not combine
with bases. It is decomposed by water, forming sulphuric and
hydrochloric acids.
NoTE.—The chloride of thionyl (SOCl3) formed by the action of
hypochlorous acid gas on a solution of sulphur in subchloride of
sulphur, is also decomposed by water, sulphurous and hydrochloric
acids being formed. An iodo-sulphuric acid has also been described.
4ction on the Metals.-Sodium and potassium burn in sulphurous
anhydride, forming a mixed oxide and sulphide. A similar result .
150 HANDBOOK OF MODERN CHEMISTRY.
occurs when iron, lead, tin, or zinc are heated in the gas
(SO2+3Zn=ZnS+2ZnO).
! When sulphurous anhydride is passed into a solution of a metallic
hydrate, a sulphite is formed. It is to be noted that—
(a.) If the acid be in excess, an acid sulphite (MHSO5) is formed
RHO +SO3=KHSO4(OKH +SO.-SOHoKo); but that—
(3.) If the hydrate be in excess, a normal or neutral sulphite (M.S.O.)
is formed, 2KHO-H SO2=K2SO4+ H2O(2OKH-I-SO2=SOKo. --OH2).
Passed over metallic perowides, sulphurous anhydride forms sulphates
(PbO2+SO2=PbSO).
In the presence of moisture sulphurous acid decomposes sulphuretted
hydrogen, pentathionic acid being formed (10SO2+ 10H.S=5S.--
8|H2O+2H2S4O6 (pentathionic acid). The sulphur thrown down
during this reaction is electro-positive, and insoluble in carbonic
disulphide.
Sulphurous anhydride is a powerful antiseptic and disinfectant.
Sulphurous Acid (H2SO, or SOHo.)
Water dissolves about 40 or 50 times its bulk of sulphurous anhy-
dride, forming a sulphurous acid solution. This acid, when cooled
below —40°F. (–40°C.), yields a crystalline hydrate (H2SO4, 8H2O),
which fuses at 39.2°F. (4°C.). Sulphurous acid expels carbonic
anhydride from its compounds. It is readily decomposed by heat into
sulphurous anhydride and water, and freely absorbs oxygen from the
air, forming Sulphuric acid. In the presence of nascent hydrogen it
forms sulphuretted hydrogen. It dissolves and is decomposed by
those metals which evolve hydrogen with hydrochloric acid. It is a
dibasic acid, forming two classes of salts, viz., acid and normal
sulphites.
Tests.--(1.) Its brimstone odor.
(2.) Starch and iodic acid. The SO2 reduces the iodic acid, the free
iodine turning the starch blue.
|Uses. In the arts it is employed as a bleaching agent for straw,
wool and hair, nuts, etc., and also as an ‘antichlor’ to get rid of the
excess of chlorine in goods bleached by that gas (SO2+2H20+Cl2=
H2SO4+2HCl). It is also used as an antiseptic, to prevent fer-
mentation, for ‘curing' vegetable and fruit extracts, and as a meat
preservative. Thus beer and wine casks are first sulphured. Its
chief use is in the oil of vitriol manufacture. It is largely employed
as a disinfectant. sº
Sulphuric Anhydride, SOA (SOs).
Molecular weight, 80. Molecular volume, I Tºl. Specific gravity,
1.95. Melts at 65° F. (18.3°C.). Boils at 95° F (35°C.).
Synonyms.-Sulphur trioxide; Sulphuric oxide: Anhydrous sulphuric
acid.
SULPHURIC ACID. 151
Preparation.—(1.) By passing sulphurous anhydride and oxygen
either over heated platinized asbestos (SO2+O=SOs) or through a
tube heated to redness, containing oxide of copper and sesquioxide of
chromium. (Wöhler.)
(2.) By heating a mixture of sulphuric acid and phosphoric anhydride.
Sulphuric acid-- Phosphoric anhydride = Sulphuric anhydride--Metaphosphoric acid.
[SO. Ho. -- P.Og - SOs + 2IPO. Hoj.
(3.) By distilling Nordhausen sulphuric acid into an ice-cold receiver
(H2SO, SO3=H.SO,--SO3).
(4.) By the action of heat on anhydrous sodic bisulphate (disodic
disulphate.)
Na2O,2SOg = NagSO4 + SO4.
Sodic bisulphate. == Sodic sulphate + Sulphuric anhydride.
SO.Nao
| |: = SO2NaO2 + so &
SO.Nao
Properties.-(a.) Sensible and Physical. A white, odorless, asbestos-
like body, capable of being moulded with the fingers. It has a spe-
cific gravity of 1.95. It melts at 65° F. (18-3°C.), and boils at 95° F.
(35° C.). It liquefies by exposure to air, and is decomposed by heat
into oxygen and sulphurous anhydride.
(6.) Chemical. It is not acid to dry litmus. It does not burn the
dry skin. It dissolves sulphur, forming with it definite compounds.
It has a great affinity for moisture, fuming in the air, and hissing when
dropped into water, instantly forming sulphuric acid, which cannot,
after combination, be separated into water and the anhydride. With
ammonia gas it forms ammonic sulphamate.
SULPHURIC ACID, H.so, (SoHo.)
Molecular weight, 98. Molecular volume,
Synonyms.- Vitriolic acid; Oil of Vitriol ; Oil of Sulphur; Vitriol;
Spirit, or Essence of Vitriol ; Dihydric Sulphate ; Protohydrate of Sul-
phuric acid. * -
History.—Probably known to Geber in the 8th century. It is
mentioned by Basil Valentine (15th century), and was fully and
accurately described by Dornoeus in 1570.
Natural History. — (a) In the mineral kingdom it is found in
a free state in the “vinegar springs” of volcanic districts, and
largely in combination with lime, etc. (3.) In the vegetable kingdom
it is found combined with alkalies in the juices of plants ; and (y.) in
the animal kingdom it is found to a small extent free, as in the
salivary secretions of certain animals (Dolium Galea, 2.7 per cent.),
and to a large extent in combination.
Preparation.—(1) Either by the oxidation of sulphur by boiling
152 HANDBOOK OF MODERN CHEMISTRY.
it in aqua regia, or by its exposure to air in the presence of water
(S2+ 3O2+2FI2O=2H2SO4), or by the oxidation of sulphurous acid,
either by exposure to air or oxygen (H.SO,--O=H.SO).
2. By the action of water on sulphuric anhydride (S0, 4-H,0=
H2SO4),
3. By distilling dry ferrous sulphate (green vitriol), prepared by
the oxidation of iron pyrites. This is the old plan still adopted at
Nordhausen in Saxony. (Basil Valentine.) The acid produced by
this process has the formula H.S.O., SO3. Colcothar (Fe2O3) is left in
the retort after the distillation is complete.
4. By passing sulphurous anhydride (SO2), vapors of nitric acid
(HNO3), steam (H2O), and air into a leaden chamber, so arranged as
to ensure their perfect admixture. A shallow layer of water covers
the bottom of the chamber. (Roebuck, 1720.) -
(a.) The sulphurous anhydride is generated by burning crude sulphur
or pyrites (which contains 30 to 35 per cent. of sulphur), or the spent
oacide of gas works (which often contains 40 to 60 per cent. of sulphur).
(ſ3.) The nitric acid is generated by the action of sulphuric acid on
sodic nitrate.
(y.) The steam is derived from a special water boiler.
(8.) The air is provided in due quantity by maintaining a constant
current through the leaden chamber. -
Roughly the changes that occur may be stated as follows:—The
nitric acid oxidizes the sulphurous anhydride, thereby converting it
into sulphuric acid. The nitric acid (HNO3) becomes, by constantly
parting with its oxygen, nitric oxide (N.O.). This nitric oxide im-
mediately takes oxygen from the air, and becomes nitric peroxide
(N2O), which is again capable of converting fresh sulphurous anhy-
dride into sulphuric acid. Thus theoretically a small quantity of
nitric acid vapor in the presence of air, will convert an indefinite
quantity of sulphurous anhydride into sulphuric acid, the N2O4 merely
acting as the carrier of oxygen to the SO2.
The following are the more accurate details of the reaction : —
(a.) The sulphurous acid is first oxidized by the nitric acid, nitric
peroxide being set free.
SO.--2HNO2=H2SO,--N.O.
(3.) In the presence of steam the N2O, becomes nitric acid (HNO3),
and nitric oxide (N2O2), -
3N2O,--2H2O=4HNO3+N202,
(y.) The HNO, thus formed, instantly oxidizes more sulphurous
anhydride, and the N.O. takes oxygen from the air, becoming N.O.
and N.O., which also oxidizes the SO2, N20, being again formed,
This N.O. again becomes N.O., and N20, and so on.
SULPHURIC ACID. 153
If little or no steam be present in the chamber, a white flaky crystal-
line body (N203,2SO42) is formed, produced by the direct combination
of nitrous anhydride or nitric peroxide, with oxygen and sulphurous
anhydride. When this falls into the water at the bottom of the
chamber, it is decomposed, sulphuric acid being produced, and nitric
oxide set free. This latter coming into contact with the air, im-
mediately becomes N2O4, and again forms fresh flakes of this white
crystalline body by combining with sulphurous anhydride. But when
steam is present, this white body is not formed, but the sulphuric acid
is at once produced, and falls as a fine spray into the water.
Properly, nothing should escape from the leaden chamber, except
atmospheric nitrogen. Such theoretical accuracy is not, however, of
practical attainment. To guard against loss and nuisance, the outlet
of the leaden chamber is usually provided with two coke scrubbers.
The first of these is kept moist with sulphuric acid to retain the nitric
oxide, whereby what is called nitrous sulphuric acid is formed, and
from which by heat the nitrous fumes are driven back again into the
leaden chamber. In the second scrubber the coke is moistened with
water, the liquor from which is allowed to flow on to the floor of the
leaden chamber.
When the acid in the chamber has a gravity of from 1:45 to 1-6 it
is drawn off, inasmuch as if it were allowed to become of greater
concentration it would dissolve nitric oxide. This forms chamber acid,
and is used in the Salt cake manufacture. The chamber acid is con-
centrated first of all by evaporation in leaden pans until it has a
gravity of 1:72, beyond which the acid would seriously affect the
lead. This forms the brown acid of commerce, and is used in the
manufacture of superphosphate, and for other rough purposes. It is
afterwards distilled in glass or platinum vessels (the weak distillate
being used for the leaden chamber) until the acid in the retort has a
gravity of 1842. This forms the English oil of vitriol, or O.W.
Varieties.—The anhydride forms four definite compounds with
Water.
(1.) Nordhausen sulphuric acid, or fuming oil of vitriol (H.SO,SO.).
This is prepared by the distillation of green vitriol. Specific gravity,
1:9. It is used for dissolving indigo.
(2.) Oil of vitriol, or true sulphuric acid (H2SO4). This cannot be
prepared by merely boiling down a weak acid, the acid thus obtained
always having the composition H2SO4,4's H.0, or 12SOs, 13H,0. By
exposing this strong acid, however, to a freezing mixture, the acid of
the formula H2SO4 crystallizes out. These crystals melt at 51°F.
(10.5°C.), and boil at 640°F. (470°C.), when the liquid gives off
sulphuric anhydride, the resulting acid solution having the formula
12SOs, 13H2O.
(8.) Glacial sulphuric acid (H.SO, H2O). This is prepared by cooling
an acid of specific gravity 1-78 to 47°F (83°C.), when rhombic crystals
154 EIANDBOOK OF MODERN CEIEMISTRY.
of H2SO4, H2O separate. It boils at 400°F. (205° C.), giving off a
weaker acid.
(4.) Graham's acid (H2SO4.2H2O).-This is prepared by evaporating
a dilute acid ‘in vacuo' at 212°F. (100°C.), until it ceases to lose
weight. Specific gravity, 1-62. It boils at 379°F. (193°C.).
These facts are tabulated by Miller as follows:–

Fusing point. Boiling point. *
Formula. 9 p 3 P Specific
Gravity.
9C. of". oC. oR.
Sulphuric anhydride .. tº tº SO, 18-3 || 65 35 95 1.95
Nordhausen sulphuric acid ... H.S0, SO, 35-0 || 95 52.2 | 126 1:9
True sulphuric acid, Oil of
vitriol e e tº ºn * * H.S0, 10.5 51 || 338 640 I '848
Glacial acid .. tº e ... H.S0, H,0 | 8-3 || 47 | 205 || 400 1.780
Graham's acid .. • * ... H.S04,2H,0 193 379 1:620
IMPURITIES, AND TESTs FOR THE IMPURITIES OF SULPHURIC ACID.
(1.) Compounds of Oxygen and Witrogen (derived from the nitric
acid used in the manufacture).
Tests. – (a.) Turns ferrous sulphate an olive green color. (6.)
Bleaches dilute indigo. -
(2.) Sulphurous Acid (derived from the unoxydised SO2 in the
chamber).
Test.—Sulphuretted hydrogen is set free when zinc is added to the
acid.
(3.) Arsenic (derived from the pyrites).
Test.—(a.) Marsh's test. (3.) Neutralise the acid with potassic
carbonate, acidulate with hydrochloric acid, and pass sulphuretted
hydrogen through the solution, when the arsenic will be precipitated
as a yellow sulphide (orpiment).
(4.) Lead (derived from the leaden chamber).
Test.—Mix the acid with about 10 times its bulk of water, when
the lead sulphate, which is insoluble in a weak acid, will be preci-
pitated. Boil the precipitate in a solution of sodic carbonate; filter;
test one-half of the filtrate with potassic iodide, and the other half
with sulphuretted hydrogen.
(5.) Saline Impurities (derived either from the nitre, or else pur-
posely added to increase the gravity of the acid).
Test.—Evaporate to dryness for residue.
(6.) Carbonaceous Matter (derived from the accidental admixture of
the acid with organic matter).
Test.—The color of the acid.
PURIFICATION OF SULPHURIC ACID.
Dilute 1 part of the acid with 5 parts of water. Pass sulphuretted
hydrogen through the mixture for 5 or 6 hours. Allow the solid
SUILPEIUPIC ACID. 155
impurities to subside, and syphon off the clear liquor. Mix this with
a teaspoonful of common salt, and distil, rejecting the first portion
that passes over.
Properties.-(a.) Sensible.—An oily liquid, without color or smell
when pure, but ordinarily more or less colored, from the presence of
organic matter. It is an intensely corrosive poison. The Nordhausen
acid differs from the other acids by fuming in the air, owing to the
separation of a minute trace of sulphuric anhydride.
(B.) Physical.—The Nordhausen acid has a gravity of 19. Dif-
ferent acids have different gravities, depending on their respective
strengths. (See Table II. in Appendix.)
Action of Heat.—The boiling point of the acids vary. Wordhausen acid
boils at 126° F. (52.2°C.); English acid, at 640°F. (338°C.); the
brown acid, at 435°F (224°C.); and chamber acid, at 348°F. (175-5°C.).
All the acids may be frozen by a cold somewhere about —29°F.
(—34°C.), but they require a temperature considerably above this
for their re-liquefaction.
The acid does not volatilise at the ordinary temperature of the air.
Hence, when a dilute acid is dropped on cloth, it becomes concen-
trated owing to the gradual evaporation of the water. By warming
the cloth before the fire the acid on the fabric may be rendered so
concentrated that it chars the cloth.
When the vapour of sulphuric acid is heated it is dissociated, that
is, partially decomposed, into SOs and H2O.
The specific gravity of the vapor just above the boiling point of the
acid is 2:15, which would represent 2 volumes of H2O and 2 volumes
of SO3 condensed into 3 volumes; but when the heat is increased to
878°F (470° C.), these 3 volumes are found to occupy 4 volumes, the
vapor, at this higher temperature, having a gravity of 1692.
When the acid is dropped upon, or the vapor is passed over red-hot
platinum, steam, Sulphurous anhydride and oxygen are formed. By
the action of water the steam and sulphurous acid may be absorbed,
and the oxygen obtained in a pure state. (See page 57.)
(y.) Chemical.—Sulphuric acid is very acid to litmus. The strong
acid when cold, acts feebly on the metals, but when boiled in contact
with them (excepting in the case of gold, platinum, iridium and
rhodium) it undergoes decomposition, sulphurous anhydride being
evolved, and a sulphate of the metal formed (M” +2H2SO,-M"SO,--
SO2+2H2O). When a weak acid is poured on the more oxidizable
metals (such as zinc, iron, etc.) hydrogen is evolved, and a sulphate
of the metal formed (Zn-i-H2SO=H.--ZnSO).
Sulphuric acid evolves oxygen when added to metallic peroxides,
but with all oxides it forms sulphates. The concentrated acid is also
decomposed when boiled with charcoal or sulphur, sulphurous anhy-
dride being set free.
Its affinity for water is very great. It was found (April, 1870)
156 FIANDBOOK OF MODERN CHEMISTRY.
that 100 grains of acid (Sp. Gr. 1842) freely exposed to the air in a
basin, absorbed 120 grains of water in four days, its bulk being
thereby increased threefold, and its density lowered to 1-340. The
absorption of water, however, by larger quantities is not in like pro-
portion :-1,000 grains of the same acid freely exposed to the air in
a similar manner, only absorbed 232 grains of water in 24 hours,
430 grains in 48 hours, 580 grains in 72 hours, 690 grains in 96
hours, and 770 grains in 120 hours. The acid finally had a specific
gravity of 1:310, which is the point of dilution at which both weak
and strong solutions of the acid arrive when exposed to the air,
Moreover, the charring of organic bodies, such as sugar, produced by
the action of the acid, is due to this affinity for water.
A great rise of temperature, and consequent condensation, occurs
when sulphuric acid is mixed with water. The heat produced is a
little greater when the water is poured into the acid than when the
acid is poured into the water.
Table showing the Heat and Condensation resulting from various Mictures of
Sulphuric Acid and Water. Temperature of Day, 22.22°C. (72°F.).

Sp. Gr. Weight Weight Temperatur Sp. Gr.
; the of . Bulk of of W. Bulk of . e Bulk of fºlk ; É.
Acid used, in Acid used, used, in Water used. iug Fluid sulting
used. | Grains Grains. o F. 9.C. when cold. Fluid.
1-840 3000 3 iij & 3 vi 1000 3 ij & 3 ij 266 | 130 00 3 v 1 - 616
1-840 2000 3 iiss do. do. 252 122 - 20 3 iv 1 : 548
1-840 1000 || 3 j & 3 ij do. do. 210 98-88 3 iij 1 - 390
I '840 §00 3 v do. do. 198 92.22 3 ij & 3 ivss 1.245
1-840 250 3 iiss do. do. 130 54'44 3 ij & 3 iij 1 - 136
1 - 616 || 1616 3 iſ & 3 ij do. do. 119 48° 33 do. 1 - 282
1 : 548 || 1548 do. do. do. 108 42° 22 do. 1 - 246
1 - 390 | 1390 do. do. do. 95 35' 00 do. 1 - 170
1-245 | 1245 do. do. do. 81 27-22 do. 1.074
I 138 || 1138 do. do. do. 78 25° 55 do. 1.055
This table explains the use of the acid in the laboratory as a
dessicating and dehydrating reagent.
Certain organic bodies, such as starch and cellulose, are carbonized
by the strong acid, whilst dilute acids convert them into grape sugar.
The acid coagulates albumen, forming with it, as with other organic
bodies, definite chemical compounds which are insoluble.
Sulphuric acid is a powerful dibasic acid, and displaces other acids,
such as nitric, hydrochloric acids, etc., from their compounds. It
forms two classes of sulphates, viz., an acid sulphate, where one
hydrogen only is replaced by a metal (MHSO), and a normal sulphate,
where both hydrogens are replaced by a metal or metals (MSO, or
M"SO,.) º
Tests.--(1) Taste. The solution is perceptibly sour when it con-
tains 1-1000th part of anhydrous acid.
(2.) Action on Litmus. The reddoning of blue litmus is distinct when
1 part of anhydrous acid is diluted with 6,000 of water,
HYPOSULPHUROUS ACID, 157
(3.) Calcic Chloride gives a copious white precipitate, insoluble in
dilute nitric and hydrochloric acids. A turbidity is distinctly appa-
rent when the solution contains only 0:01.4 per cent. of acid.
(4.) Plumbic Acetate gives a white precipitate, insoluble in dilute
acids.
(5.) Baric Chloride (or baric nitrate) gives a white precipitate,
insoluble in free acids and in caustic alkalies. The turbidity is ap-
parent with a solution consisting of 1 part of acid in 62,500 of water.
The baryta salt must never be added to a neutral or to an alkaline
solution, otherwise carbonic, phosphoric, oxalic acids, etc., may be
precipitated, all of which are, however, soluble in nitric or hydro-
chloric acid. To prove that the precipitate is a baric sulphate, it
must be collected and dried, and mixed with about four times its bulk
of powdered wood charcoal. This mixture is then to be heated to
redness for some time in a platinum crucible. By this means BaSO,
will be reduced to BaS. Add to the cold residue a few drops of dilute
hydrochloric acid, and apply heat, when sulphuretted hydrogen will
be generated, which may be known by its blackening moistened lead
paper.
(6.) Witrate of Strontia gives a white precipitate, partially soluble in
water and in dilute acids.
(7.) If sulphuric acid be gently heated in a test tube with some
pieces of wood, copper, or mercury, etc., Sulphurous anhydride is
evolved, and may be known by its imparting a blue tint to a piece of
starch paper moistened with iodic acid.
(8.) A trace of veratria added to a drop of concentrated acid, produces
first a yellow and afterwards a crimson-red solution.
(9.) Paper is carbonized by the strong acid. If the acid be dilute,
wet a piece of white paper at one spot and heat before a fire. As
Soon as the acid becomes sufficiently concentrated by evaporation, the
paper will turn black.
Uses.—In the arts and manufactures numberless. In medicine the
following preparations are officinal:—Acidum Sulphuricum, B.P.,
Sp. Gr., 184=96.8 per cent. of H2SO4; Acidum Sulphuricum dilutum,
B.P., Sp. Gr., 1394–13-64 per cent. of H2SO4; Acidum Sulphuricum
Aromaticum, B.P., of similar strength to the dilute acid, but containing
ginger and cinnamon.
Hyposulphurous Acid, H.SO3(SHO.).
Synonym.—H.ydrosulphurous Acid.
[NotE.-H...SO, is the true hyposulphurous acid; H.S,0s, which is ordinarily called
hyposulphurous acid, is really thiosulphuric or sulpho-sulphuric acid.
History.--Discovered by Schützenberger.
Preparation. (1) By dissolving zinc in sulphurous acid. (Note:–
No hydrogen is evolved during the reaction).
158 HANDBOOK OF MODERN CHEMISTRY.
H.S.O., + ZnO.
Sulphurous acid + Zinc = Hyposulphurous acid + Zincic oxide.
[SOHo. + Zn = SHog + ZnO).
(2.) By decomposing sodic hyposulphite (NaHSO.) with oxalic acid.
Properties.—The yellow solution of the acid thus formed bleaches
powerfully, its bleaching action depending on its reducing power. It
throws down mercury and silver from their solutions. It rapidly
decomposes by absorbing oxygen.
Thiosulphuric Acid, H.S.O.(SS"OHo. 2).
Synonyms.-Hyposulphurous acid: Sulpho-sulphuric acid; Dithionous
acid.
The free acid has never been obtained. The salts are prepared
either (1) by boiling sulphur with a solution of a sulphite
(Na2SOs--S=Na2S2O3); or (2) by boiling sulphur with an alkaline
hydrate (3Ca(), H20+ 12S=CaS.O., + 2CaSg-H 3H2O). A further quan-
tity of CaS2O, is formed from the CaSs in the latter reaction, by
exposing the solution to the air (CaS5+ 30–CaS2O3-i-S3).
Calcic Thiosulphate (CaS.0,6EI2O) is found in large quantities in
the refuse lime of gas works, and also in the refuse from the ball
soda of the alkali works.
The Sodic Thiosulphate or Hyposulphite, as it is called, is
largely used by the dyer as an antichlor, as well as in photography
and metallurgy, on account of its power of dissolving the insoluble
argentic haloid salts, by forming with them double soluble salts. It is
prepared either (1) by treating a solution of sodic sulphide with sul-
phurous acid; or (2) by digesting together sulphur and sodic sulphite,
or (3) by exposing the calcic sulphide (tank waste or soda waste) of
the gas or alkali works to the air, whereby a calcic hyposulphite is
formed by oxidation, from which ‘hyposulphite of soda may be
prepared by the action of sodic carbonate. The thiosulphates will
not yield the free acid by the action of a stronger acid, on account of
the ease with which they are decomposed into sulphur and sulphurous
acid (H2S2O3=S+ H2SOs).
To distinguish thiosulphuric from sulphurous acid note that—
(1.) On adding an acid to a thiosulphate, sulphur is precipitated,
and sulphurous anhydride is evolved.
(2.) Thiosulphuric acid dissolves argentic chloride, forming argentic
sodic thiosulphite (NaAgS2O3).
(3) A salt of ruthenium, rendered alkaline with ammonia, turns
thiosulphuric acid a deep red color.
The sodic hyposulphite, when heated, first loses water, and is then
decomposed (4Na2S2O3=3Na2SO4+Na2S5).
TRITELIONIC ACID. 1.59
Dithionic Acid, H.S.06=162. (SYO, Hoº).
Synonyms.-H.yposulphuric acid.
Preparation. (a) A manganous dithionate (MnS.0%) is first pre-
pared by passing SO, through cold water containing manganic
peroxide in suspension (MnO2+2SO2=MnS2O6).
(3.) A baric dithionate (Baš.06) is then prepared by acting on the
manganous dithionate with baric sulphide (MnS2O6+BaS=MnS+
BaS2O6).
(y.) Dithionic acid is now liberated by the action of sulphuric acid
(in equivalent proportion) on the baric dithionate (Baš206+ H2SO,
=BaSO, + H2S2O6).
Properties. – The acid, when fully concentrated by evaporation
‘in vacuo,’ has a specific gravity of 1.347, and forms a colorless acid
liquid without odor. If the concentration be attempted beyond this
point, or if heat be applied to the acid solution, it breaks up into
sulphuric acid and sulphurous anhydride (H2S2O5=H2SO4+ SO2).
When exposed to the air, dithionic acid rapidly forms sulphuric acid.
All the dithionates (hyposulphates) are soluble in water, and are
decomposed by heat in the presence of hydrochloric acid, sulphurous
anhydride being evolved without the deposition of any free sulphur.
This distinguishes them from other sulphur compounds.
Trithionic Acid (H2S306=194).
Synonyms.-Dihydric trithionate; Sulphodithionic acid; Sulphuretted
hyposulphuric acid.
History.—Discovered by Langlois.
Preparation of the free acid. (a.) A potassic trithionate (K.S,06)
is first prepared by digesting acid potassic sulphite (KHSOs) with
powdered sulphur. Thus— -
12|KHSO3 + S2 = 4.K.S.O6 + 2K2SOs +6]H2O.
Hydric potassic sulphite--Sulphur = Potassic trithionate--Potassic sulphite-H Water.
- ſ SO. Ko
[12SOHoRo + S. = S + 2SOKoc -i- 60Hz.
4 lso Ko
(3.) On dissolving the crystals of potassic trithionate (K.S.;06) in
water and adding perchloric or hydrofluosilicic acid, the potash is
precipitated, and a solution of the acid obtained.
Properties.—The acid crystallizes in four-sided prisms. It
rapidly decomposes into sulphurous anhydride, sulphurous acid, and
free sulphur (4H2S4O6=6SO2+4H2SOs -- Ss).
The trithiomates are soluble unstable salts, and are easily decomposed
by heat into sulphates, sulphurous anhydride being evolved with the
deposition of free sulphur. They give with mercurous nitrate a black
precipitate, with mercuric nitrate a white precipitate, and with
argentic nitrate a yellow precipitate, which in time becomes black.
160 HANDBOOK OF MODERN CHEMISTRY.
Tetrathionic Acid (H2S4O6 = 226).
Synonyms.-Dihydric Tetrathionate; Disulpho-dithionic acid; Bisul-
phuretted hyposulphuric acid.
: History.—Discovered by Fordos and Gélis.
Preparation of the free acid. (a.) Baric tetrathionate is formed
by adding iodine to baric hyposulphite (thiosulphate) (2BaS2O3 + I,
= Baſe + BaS106).
(3.) Tetrathionic acid is now set free by decomposing baric tetrathio-
nate with its exact equivalent of sulphuric acid.
Properties.—The acid is very unstable. When heated, a solution
of sulphuric acid is formed, sulphurous anhydride is evolved, and free
sulphur is deposited (H2S,06 = H2SO, -- SO3 + S.). The potassic
salt may be recognised by the separation of sulphur when heated with
potassic sulphide (2K2S4O6 + 2K2S = 4.K.S.O3 + Sc). -
Pentathionic Acid (H2S506=258).
Synonyms.-Trisulphodithionic acid; Trisulphuretted hyposulphuric
ocid. w)
History.—Discovered by Wackenroder,
Preparation.—By passing sulphuretted hydrogen through a solu-
tion of sulphurous acid (10SO2 + 10EI2S=2H2S506+ 5S2+8EI2O).
The clear solution is to be concentrated in vacuo over oil of vitriol.
Properties.—The solution thus obtained has a specific gravity of
1-6, and is acid, bitter and tolerably permanent. Concentrated beyond
this gravity it rapidly decomposes. By heat it is resolved into sul-
phuric acid, sulphuretted hydrogen, sulphurous anhydride, and free
sulphur (2H2S4O6=H2SO4+ H2S--4SO2+2S.).
The polythionic acids, as an aid to memory, are represented by
Bloxam as derived from oil of vitriol by successive additions of sul-
phurous anhydride and sulphur : thus
Oil of vitriol H.SO, =H2SO,
Thiosulphuric acid H2SO4+SO. =H2S2O6
Trithionic ,, H2SO4+ SO2 + S =FL:S4O6
Tetrathionic , , H2SO4+SO2+ S2=H2S4O6
Pentathionic , , H2SO4+ SO2+S3–H2S306.
Note the following reactions:
The sulphates with concentrated sulphuric acid (hot or cold) emit
no odor.
The sulphites with dilute sulphuric acid (cold) emit an odor of SO2.
The hyposulphates (dithionates) with dilute sulphuric acid (cold)
emit no odor, but wher. heated emit the odor of SO2.
The thiosulphates (hyposulphites) with dilute sulphuric acid (cold)
emit an odor of SO2, with the deposition of free sulphur,
COMPOUNDS OF SULPHUR, OXYGEN, AND THE HALOIDs. 161
CoMPounds of SULPHUR AND THE HALOIDs.
Compounds of Sulphur and Chlorine.
1. Sulphur chloride tº gº tº * * * tº gº tº S.C.],
2. Sulphur dichloride ... # * * tº gº tº SCI2
3. Sulphur tetrachloride ... * > * e is º SCI, P
Sulphur Chloride (S,C), Or {#)
Molecular weight, 135. Molecular volume, TT . Specific gravity, 1.68;
of vapor, 4.7.
Preparation,-By passing chlorine into melted sulphur and col-
lecting the product in a dry cold receiver.
Properties.—A yellow volatile liquid (Sp. Gr. 1:68), fuming in the
air, and emitting a pungent odor. The specific gravity of the vapor
is 4-7. It is decomposed by water into sulphurous, hydrochloric, and
thiosulphuric acids, and free sulphur (electro-positive). It dissolves
Sulphur freely; hence its use in the manufacture of vulcanised rubber.
It acts powerfully on mercury.
Sulphur Dichloride (SCI.-103).
Preparation.—By saturating the sulphur chloride with chlorine.
Properties.—A deep red liquid. It is decomposed by heat and by
the sun's rays (2SCl2=S2Cl2 + Cl2).
Sulphur Tetrachloride, SCI, (?)
This compound is not known in a free state, and there is some
doubt even as to its existence in combination.
CoMPOUNDs of SULPHUR WITH BROMINE AND IoDINE.
Compounds of sulphur with bromine and iodine similar to the chlorine
compounds are believed to exist. A Sulphur Diiodide (SIs), a body
produced by direct combination, and a Sulphur Subiodide (S.I.) are
the compounds best known.
CoMPOUNDS OF SULPHUR, OxygEN AND THE HALOIDs.
Thionyl Chloride (SOCl3) is an analogous compound to sul-
phurous acid, two of hydroxyl being displaced by two of chlorine
(SOHoa–SOCl3).
Preparation.—By acting on phosphoric chloride with sulphurous
anhydride. (Schiff.)
Properties.—A colorless, pungent liquid of great refractive power;
specific gravity, 1.675; boils at 172.4°F. (78° C.). It is decomposed
by water into sulphurous anhydride and hydrochloric acid. It forms
thiomamide with ammonia.
Sulphuryl Dichloride (SO.C.). Preparation.-By exposing a
mixture of sulphurous anhydride and chlorine to sunlight.
M
162 HANDBOOK OF MODERN CHEMISTRY.
Properties.-A colorless liquid, specific gravity, 1.66; decomposed
by water into sulphuric and hydrochloric acids.
Sulphuryl Dibromide (SO.Br.), a white, crystalline body, Chloro-
sulphuric owide (S.O.C.), a colorless oily liquid, and Sulphuryl
hydroayl chloride (SO3.HCl) have also been described.
COMPOUNDs of SULPHUR AND PHOSPHORUS.
Phosphorus protosulphide ... P.S.
Phosphorus sesquisulphide ... P.S.A.
Phosphorus pentasulphide ... P.Sg.
Phosphorus Protosulphide (P.S) is a yellow, oily liquid, and is
not decomposed by water.
Phosphorus Sesquisulphide (P.S.) is prepared by the action of
sulphuretted hydrogen on phosphorous chloride (2PCls + 3H2S =
P2S3+ 6THCl). It is a yellow crystalline solid, easily decomposed by
Water.
Phosphorus Pentasulphide (P.S.) is a body easily decomposed
by water.
Other compounds, as PAS, PS3, P.S.12, have also been described.
SELENIUM (See).
Atomic weight, 79.5. Molecular weight, 159. Molecular volume, TT .
Relative weight, 79°5. Specific gravity of solid, 4:788; of vapor,
5-68; Atomicity; Hewad (SeviO2H.O.); Tetrad (SeCl); Dyad
(SeH2).
History.—Discovered by Berzelius (1817) in the refuse of a
sulphuric acid factory.
Natural History.-It is found native, but occurs chiefly in com-
bination, as a selenide of copper, iron, silver, etc. It also occurs as an
impurity in native sulphur (seleniferous sulphur).
Preparation.—By the action of a mixture of nitric and sulphuric
acids on the seleniferous deposits of vitriol works, a solution con-
taining selenious and selenic acids is formed. The selenic acid
present in the solution is now to be reduced to selenious acid by the
action of hydrochloric acid (H2SeO4+2HCl=H.SeO3+ H20+Cl2).
From this solution of selenious acid, the selenium may be precipitated
by a current of sulphurous anhydride (2H2SeO3+2H2O+4SO2=
4H2SO4+Sea).
Varieties.--Like sulphur, selenium is found in various allotropic
forms.
(a.) The amorphous form, prepared as described above, consists of
red flakes, which are ductile when melted. It has no taste or smell,
and is a bad conductor of heat and electricity.
SELENIC ACID, 163
(3.) A black vitreous form, prepared by first heating the preceding
amorphous variety to 212° F. (100° C.), and then rapidly cooling.
It has a specific gravity of 4:3. It is insoluble in carbonic disulphide.
(y.) A crystalline form, prepared by heating the vitreous form to
204.8°F. (96° C.) It has a specific gravity of 4-8. Its color is
bluish grey (gexívn, the moon).
Properties.—(a.) Physical. The color of selenium is either red, black,
or bluish grey, according to the variety. Solid selenium has neither
taste nor smell, but the vapor has the odor of putrid horseradish.
It conducts heat and electricity badly, but its electric conductivity is
greatly increased by exposure to direct sunlight. It is insoluble in
water. It fuses readily, and boils below a red heat, giving off a
yellow vapor, which, like that of sulphur, expands anomalously (see
page 145).
(3.) Chemical. Selenium vapor burns with a blue flame, forming
SeO2. By boiling with nitric acid, selenious acid is formed. Selenium
is soluble in sulphuric acid, forming a green solution, from which the
selenium may be thrown down by the addition of water.
CoMPOUNDs of SELENIUM AND OXYGEN, ETC.
Selenious anhydride ... SeO2.
Selenious acid 4 º' ſº ... H. SeO3, or SeOHog.
Selenic acid © o º ... H. SeO4, or SeO3Hos.
Selenious Anhydride (SeO3).
Preparation.—By burning selenium in oxygen, or by boiling it
with nitric acid.
Properties.—A white, deliquescent, crystalline substance, soluble
in water, forming selenious acid (H3SeO3, or SeOHo.). This acid
may also be obtained as a white solid. On adding iron, zinc, sul-
phurous acid, or sulphuretted hydrogen to a solution of selenious acid,
selenium will be precipitated.
Selenic Acid (H2SeO3, or SeO3Hos.)
This acid is not known as an anhydride.
Preparation.—(1.) (a.) A potassic seleniate is first formed by fusing
together nitre and selenium (4RNO,--Sea-2K.SeO,--2N.O.). (3.) A
plumbic seleniate is then prepared by the action of plumbic nitrate on a
solution of potassic seleniate. (y.) On treating plumbic seleniate
with sulphuretted hydrogen, an insoluble plumbic sulphide and a
Solution of selenic acid are formed.
(2.) By the action of chlorine or manganic peroxide on selenious
acid.
Properties.—A colorless, syrupy, hygroscopic liquid, evolving
considerable heat when mixed with water. It may be concentrated
until it has a specific gravity of 2-6. At a temperature of 55.4° E.
(290° C.) it is decomposed into selenious acid, water, and oxygen.
164 HANDBOOK OF MODERN CHEMISTRY.
It has no action on platinum, but it oxidizes the metals generally,
and even dissolves gold. When heated with hydrochloric acid it is
decomposed (H2SeO,--2HCl=H.SeO,--H3O+Cl2).
COMPOUNDS OF SELENIUM AND CHLoRINE.
Selenium forms two chlorides, viz., a monochloride (SeaCl.), a
yellow liquid formed by the direct union of selenium and chlorine,
and a tetrachloride (SeCl), a white crystalline solid, formed by treating
SegCl2 with an excess of chlorine. On its exposure to moisture an
oxychloride (SeOCl3) is formed.
The combinations of selenium with the other haloid elements are
imperfectly understood.
• A carbonic Selenide (CSe2) and two sulphides (SeS2 and SeS) have
been described.
TELLURIUM (Tex).
Atomic weight, 128. Molecular weight, 256. Relative weight, 128.
Specific gravity of solid, 6-2 ; of vapour (at 2,534°F), 9:0. Atomicity,
hea'ad (H.Te01); tetrad (TeCl); dyad (Tel I.).
History.--Discovered by Müller (1782). Its elementary nature
was determined by Klaproth (1798), and the body named by him
Tellurium (Tellus).
Natural History.—It is a very rare substance, but is found both
in a free state, and also combined with bismuth, lead, silver, etc.
Properties.—(a.) Physical. A pinkish-white metallic-looking body,
crystalline (rhombohedral), and very brittle. It fuses between 800°
and 900°F. (426° and 482°C.), and becomes, at a higher temperature,
a yellow gas. It conducts heat and electricity badly. It is insoluble
in water. When taken internally it imparts a peculiar garlic odor to
the breath.
(6.) Chemical. Tellurium burns, when heated in air, with a blue
flame, yielding Te02. It does not form, like the metals, a true basic
oxide. Its solution in sulphuric acid, which is of a purple-red color,
yields a precipitate of tellurium when treated with water.
CoMPOUNDs of TELLURIUM AND OxYGEN, ETC.
Tellurous oxide ... ... Te02.
Tellurous acid tº gº e tº dº e H.Te0s, or Te0Hoc.
Telluric oxide ë e º tº º º Te0s.
Telluric acid tº e º * * * H.Te04, or Te0. Hoz,
Tellurous Oxide (Te02.)
This oxide occurs native as tellurite. It is a white, fusible crystal-
line body. It forms a yellow glass when hot, which becomes white
TELLURIC ACID. 165
on cooling. At a greater heat it sublimes unchanged. It is slightly
soluble in water, forming tellurous acid (H.Te03, or Te0EIoz), which
forms two classes of salts, viz.—neutral (M.Te03), and acid (M'HTeO3),
tellurites.
Telluric Oxide (Te03).
Telluric oxide is a yellow, solid body, insoluble in water and in
acids. It is prepared by the action of heat on telluric acid (HATe04).
Telluric Acid (H.Te04, or Te02Hog).
Telluric acid is prepared by first forming a potassic tellurate by the
fusion of tellurium with nitre. On adding baric chloride to the
solution, and decomposing the baric tellurate formed with sulphuric
acid, a solution of telluric acid is obtained. The solution, after the
baric sulphate has been filtered off, yields crystals having the com-
position H.Te04,2H2O, from which the two molecules of water may be
expelled by heat. It forms salts called tellurates, which are mostly
insoluble.
166 HANDBOOK OF MODERN CHEMISTRY.
CHAPTER VIII.
CARBON.—BORON-SILICON.
CARBON :—Compounds of Carbon and Oxygen—Compounds of Carbon and the
Haloids–Compounds of Carbon with Oxygen and the Haloids—Compounds of
Carbon and Sulphur. BoroN :—Boracic acid—Compounds of Boron with Nitrogen,
the Haloids, and Sulphur. SILICON:—Compounds of Silicon with Oxygen, the
Haloids, Nitrogen, and Sulphur.
CARBON (C=12).
Atomic weight, 12. Atomicity, dyad (CO); tetrad (CO2–CH4). Vapor
density, unknown. *
`-
Synonym.–Charcoal.
History.—Carbon has been known from very early times. Eresius
(300 B.C.) described the method of preparing it from wood, and in
Pliny’s time it constituted the common fuel. In A.D. 1694 the
Florentine academicians burnt the diamond by the sun’s rays. In
1775–6 Lavoisier effected its combustion in oxygen, and in 1809 Davy
burnt graphite in a similar manner. Thus these bodies respectively,
were proved to be pure carbon. Newton, however, had long before
this, asserted that the diamond was a combustible body, on account of
its high refractive power.
Natural History.—(a.) In the mineral kingdom carbon is found in a
free state; (1) as the diamond in sandstone rocks or mica slate. Its
origin is unknown. The ash, consisting of silica and oxide of iron,
left after its perfect combustion, is very minute. (2.) As plumbago,
the ash of which varies from 2 to 5 per cent., and consists of a little
quartz mixed with the oxides of iron and manganese. (3.) As
anthracite, the ash of which varies greatly both in quantity and com-
position. (4.) Carbon is also found associated (a) with hydrogen in
coal, bitumen, jet, shales, naphtha, and in the paraffines, (b) with
oxygen in carbonic anhydride, and (c.) with oaygen and the metals in the
carbonates.
(3.) In the vegetable kingdom, carbon forms about 50 per cent. of dry
vegetable solids. It is supplied to them by the atmospheric carbonic
anhydride which the plant deoxidizes under the influence of Solar
light. Plants are deoxidizing agents, animals are oa'idizing agents.
(y.) In the animal kingdom, all tissues and products are largely made
up of it. Fat contains about 79 per cent.
The chemist roughly proves a body to be of organic origin by the
circumstance that it carbonizes when burnt with a limited supply of air.
Varieties.—(1) Diamond.—The diamond crystallizes in cubes or
in octahedra with convex faces and rounded edges (lenticular). It
CARBON, - 167
cannot be produced artificially. Its specific gravity is 3:4. It is
usually colorless, but is found at times of a yellow, green, blue, and
black tint, the colors being due to mineral matter. It is one of the
hardest bodies known (adamant). It has never been melted. It is a
non-conductor of electricity, but when heated in the voltaic arc, it
swells up and forms a coke-like mass, which conducts electricity
freely. Some diamonds are phosphorescent after exposure to intense
sunlight. It has a high refracting power: at an angle of 24:15 all
light is returned.
It is not affected by the action of nitric acid and potassic chlorate.
A diamond may be known (a) by its hardness (scratching hardened
steel); (3) by its gravity; and (y) by its insolubility in hydrofluoric acid.
(2.) Graphite (ypapo, I write).-Graphite is found both crystalline
(six-sided plates) and in amorphous masses. It has a specific gravity
of 22. It is greyish-black, with a metallic lustre (black lead or
plumbago). It is unctuous to touch, and, although the minute
particles are excessively hard, it nevertheless marks paper when
drawn across it. It is a good conductor of electricity.
When plumbago is acted on with a mixture of nitric acid and
potassic chlorate it forms ‘graphic or graphitic acid, a brown, crystal-
line body, which swells up when heated, forming ‘pyrographitic oxide.”
This latter substance is soluble in nitric acid and potassic chlo-
rate.
(3.) Amorphous carbon.—Amorphous carbon has a specific gravity
varying from 1:6 to 2-0. Its apparent lightness, such as floating on
water, is due to the presence of air in its pores. It is found in various
forms, more or less pure, as e.g., (a.) Coke, the residue of coal after
the gas and volatile matters have been expelled. (3.) The carbon of
gas retorts, a body resembling graphite in some particulars, but differ-
ing in that it does not form “graphic acid '' by the action of nitric
acid and potassic chlorate. (y.) Soot, the condensed smoke deposited
in chimneys. (6.) Lampblack, the unburnt carbon resulting from the
combustion of rich hydro-carbons in a limited supply of air. (e.)
Wood charcoal, the carbon of wood and other vegetable matters. (...)
Animal charcoal (ivory black or bone black), the carbon of bone or other
animal substances. (m.) Tinder.
All these forms, when treated with nitric acid and potassic chlorate,
yield brown compounds that are soluble in water.
It has been conjectured, considering the striking differences in the
properties of these carbon allotropes, that they consist of dissimilar
carbon molecules. The study of their specific heats would suggest
that the charcoal molecule consists of two atoms, the graphite of three,
and the diamond of four. (Specific heat of diamond, 14687; of plum-
bago, '2008; of charcoal, '2415.)
Preparation.—(1) Diamond.—The diamond cannot be prepared
artificially (Action of phosphorus on chloride of carbon 2).
168 HANDBOOK OF MODERN CHIEMISTRY.
(2.) Graphite.—(a.) By submitting the diamond to an intense heat.
(3.) By dissolving carbon in cast iron. On allowing the mixture to
cool slowly, six sided crystalline plates of graphite separate (called
“kish”).
(y.) By dissolving away the iron from cast iron, thus leaving the
insoluble graphitic carbon.
(6.) By submitting the various forms of amorphous carbon to the
heat of the electric arc.
(3.) Amorphous carbon.—(a.) Coke. By heating coal in closed iron
cylinders, an escape being provided for the gaseous and other volatile
matters. The higher the temperature to which the coal is subjected,
the more dense the coke. Coke may also be prepared by burning
the coal in heaps similar to the preparation of wood-charcoal.
(6.) Carbon of gas retorts.--From the decomposition of a portion of
the gas or volatile hydro-carbons by the red hot retort, upon which a
layer of gas carbon slowly deposits. Its appearance varies according
to the temperature at which it is formed.
(y.) Soot.—The condensed smoke of chimneys.
(6.) Lampblack.-By burning certain vegetable matters rich in
carbon, such as resin, tar, etc., in a current of air insufficient for
complete combustion. The hydrogen being the most combustible
portion burns first, and the carbon, for which there is not sufficient
air, is collected in chambers covered with coarse cloth.
(e.) Wood charcoal.—(1.) By the distillation of wood in closed
retorts. Acid fumes are evolved during the process, wood contain-
ing little or no nitrogen, charcoal remaining in the retort. (2.) By
the slow burning of logs of dry wood arranged in heaps, covered,
except round the base of the heap, with turf. In this way, every 100
parts of wood yield about 22 parts of carbon.*
Wood charcoal never consists of pure carbon. The higher the
temperature at which the wood is burnt, the smaller the quantity of
charcoal formed, but the larger the percentage of carbon that it
contains. The “charbon roux’’ of the French consists of wood im-
perfectly burnt by the action of superheated steam.
(...) Animal charcoal. —By burning bones or other animal matter in
closed retorts, when alkaline fumes are evolved, from the nitrogen
present in the animal matters forming ammonia, animal charcoal
remaining in the retort (ivory black).
Properties.— (a) Sensible.—Carbon, in all its forms, is a solid
without taste or Smell, and, excepting the diamond, of a black
color.
* If a piece of wood (C, H10O.) be burnt in the open fire, with free access of air,
carbonic acid and water only are produced; but when burnt in a close vessel, where the
free access of oxygen is prevented, the wood does not truly burn, but simply under-
goes destructive distillation; that is, it becomes changed into simpler and more stable
products, tar, acetic acid, and wood spirit being amongst the products formed.
CARBON. 169
&
(3) Physical.—The diamond is the hardest substance known, al-
though nearly approached in this respect by crystallized boron. The
other varieties of carbon are comparatively soft, although graphite,
which may be easily cut with a saw, is said to wear out the instru-
ments rapidly, owing to the extreme hardness of its minute
particles.
Carbon is dimorphous. It is cubic in the diamond, and size sided in some
varieties of graphite. The other forms of carbon, as well as occasion-
ally graphite, are amorphous. Its specific gravity varies; that of the
diamond ranges from 3:33 to 3-55; of graphite, from 2-0 to 2:35; of
anthracite and coke, from 14 to 2, etc.
Action of heat.—Carbon, in all its forms, is believed to be in-
fusible and involatile. It has been noticed, however, that when the
carbon points from a large battery are brought into contact in an ex-
hausted receiver, a dark cloud appears, and that a black crystalline
body is slowly deposited on the sides of the glass. Further, when
pure powdered carbon is exposed to the intense heat of the voltaic
arc, it forms a coherent mass as if it had been fused. (Despretz.)
The diamond, when heated in the battery, swells up and cakes,
although there is no reason to believe that it is capable of vaporisa-
tion. Finely-divided carbon conducts heat badly. The diamond is a
Inon-conductor. The other varieties, when “en masse,” conduct heat
well, the power of conduction increasing with the density.
Carbon, in all its forms, excepting the diamond, is a conductor of
electricity. Hence the use of graphite in electrotyping.
Carbon is insoluble in every known liquid.
(y.) Chemical.—Carbon in all its forms is combustible in air and
oxygen, yielding as its sole product carbonic anhydride (CO2). The
diamond and graphite are difficult of combustion, but the rest burn
easily. In none of its forms is carbon altered by exposure to weather;
hence many of its uses. -
Action of ozygen.—The action of oxygen on carbon is sometimes,
though rarely, manifested at ordinary temperatures. Thus ferrie
may be changed to ferrous, and mercuric to mercurous salts, by
merely shaking up their solutions with powdered charcoal. At high
temperatures carbon burns in oxygen, and even in carbonic anhy-
dride, in which latter it appropriates one half of the oxygen
(C+CO2=2CO.) Hot charcoal decomposes steam, liberating hydro-
gen, and setting free, according to the temperature, either carbonic
anhydride or carbonic oxide. Its property of combining with oxygen
is made use of in extracting the metals from their oxides, carbonic
anhydride being set free in the case of oxides easily reduced
(2PbO-H C = Pb2+ CO2), and carbonic oxide with those difficult of
reduction (ZnO-HC–Zn-i-CO).
4ction of the haloids.--The direct combination of carbon with the
haloids cannot be effected, but indirect combination, either by the
170 HANDBOOK OF MODERN CHEMISTRY.
substitution of the haloid elements for hydrogen in, or the addition
of the haloid elements to, the hydrocarbons, is of constant occurrence.
Thus ethylene (C.H.) will combine with bromine to form ethylene
dibromide (C2H4Br2), which, by successive substitutions of bromine
for hydrogen, may ultimately be converted into tetrabromethylene
dibromide (C.Brö).
Action on nitrogen.—The direct union of carbon with nitrogen cannot
be effected; but if nitrogen be passed over a mixture of carbon and
potassic carbonate heated to redness, cyanogen (CN) is formed, which
unites with the potassium to form potassic cyanide (K2CO3 + 4C+N2
=2KCN +3CO.)
Action on Sulphur.—Direct union between carbon and sulphur occurs
at a high temperature, carbonic disulphide (CSz) being formed.
Action on hydrogen.—Hydrogen and carbon unite directly at high
temperatures, such as the heat of the voltaic arc, forming acetylene
(C.H.). (Berthollet). During the destructive distillation of organic
bodies numerous hydrocarbons are produced (see Destructive Distil-
lation). -
Action on the metals.--Carbon unites at high temperatures with certain
metals, such as iron, manganese, palladium, iridium, etc., forming
carbides.
Carbon does not combine with phosphorus.
We may note generally, that carbon exhibits a great indisposition
to combine directly with the elements. Hence it is customary to
char the ends of stakes, in order to prevent their decay by the action
of air and moisture when driven into the ground, and to blacklead
metal, so as to prevent its oxidation.
Action of Compounds.--(1.) Water has no action on carbon, except at
a red heat, when hydrogen, together with carbonic oxide or carbonic
anhydride (one or both), are formed (3H20+2C=3H2+ CO+ CO2).
(2.) Acids.—Sulphuric acid has no action on carbon, except when
heated, when the acid is reduced (2H2SO4+C-CO2+2SO2+2H2O).
Nitric acid deflagrates when heated with carbon, the oxides of carbon
and the lower oxides of nitrogen being formed. The action of nitric
acid and potassic chlorate on the various forms of carbon is as fol-
lows:—the diamond is unaffected; graphite is changed into graphic
or graphitic acid (graphitic oxide) (C, H,05), a yellow silky substance,
insoluble in water or in acids, and which, when heated, swells up, and
becomes pyrographitic oxide; the amorphous varieties are soluble,
forming brown solutions. Hydrochloric and hydrofluoric acids have no
action on carbon; phosphoric acid is reduced by it, phosphorus being
set free.
(3.) The fived alkalies and the owides generally do not act on carbon
unless the carbon be heated, when the metals are reduced.
Red-hot carbon decomposes ammonia, forming ammonic cyanide,
hydrogen, and nitrogen.
CARIBON. - 171
Charcoal has certain remarkable physical and chemical properties
of absorbing gases, &c., which we must consider.
(a.) Its power of absorbing aqueous vapor.—Recently ignited charcoal
was found to absorb the following percentages, by weight, of water.
Allen and Pepys.
( pys.) Weight of H,0
per cent. absorbed.
Lignum vitae charcoal ... e - e. e - e. 9-6
Fir charcoal • * g. se tº º • * * e G tº 13-0
Beech charcoal e tº e & e ºs • * * e - © 16-0
Oak charcoal e - - º t e * G - e - e. 16-5
Mahogany charcoal tº º ſº tº tº e tº º º 18.0
(b.) Its power of absorbing gases.—A piece of hard wood charcoal was
found to absorb gases in the following proportions:–
Quantity of gas absorbed.
Ammonia (NH3) tº g tº º “s & 90 times its bulk.
Hydrochloric acid (HCl) ... 85 } }
Sulphurous anhydride (SO2)... 65 7 *
Sulphuretted hydrogen (H2S) 55 5 y
Nitrous oxide (N2O) ... tº º 'º 40 } }
Carbonic acid (CO2) ... e tº - 35 ; 7
Carbonic oxide (CO) .. tº ºn tº 9° 4 } }
Oxygen • * * * * * © ºr tº 9.2 } }
Nitrogen is a - e q & • * * 7-5 } }
Hydrogen ... • * s e tº ºr 1.75 } }
Charcoal made from the shell of the cocoa-nut is said to be the most
absorbent of all varieties.
(c.) Its power of absorbing odors.-The deodorizing property of
charcoal is very marked. Hence its supposed antiseptic properties.
It does not, however, prevent decomposition, but absorbs noxious
gases and then oxidizes them by the oxygen condensed in its pores
(Stenhouse), dissipating their carbon as carbonic acid, and their hy-
drogen as water. The ammonia formed is absorbed by the charcoal.
(d.) Its power of absorbing coloring matters.—The decolorizing
property of charcoal is specially manifested in the case of animal
charcoal or bone-black, possibly because it contains a large proportion
of calcic phosphate, which serves to extend the carbon particles.
Seaweed charcoal has also very considerable decolorizing power.
(e.) Its power of absorbing mineral and other substances.—Thus, if
strychnia or iodine in solution, be shaken up with charcoal, they are
rapidly absorbed. Lime may be abstracted from lime water, and
lead acetate from its solutions by similar treatment. Charcoal is
used by the distiller for the purpose of removing the empyreumatic
oils from spirit.
Uses, (a.) In nature.—Carbon is found as a constituent of every
organic substance. It gives the plant its solidity and its form.
172 -- HANDBOOK OF MODERN CHEMISTRY.
Hence organic chemistry has been defined as the chemistry of carbon
and its compounds.
(b.) In the arts. (a.) Diamonds are used (1) as gems; (2) for glass
cutting; and (3) for lapidary work. The diamond dust commonly used
is the powder of the dark Brazilian diamond.
(3.) Graphite is used (1) for pencils (black lead); (2) for black-leading
to protect iron from rust; (3) for crucibles mixed with clay (blue pots)
on account of its power of resisting high temperatures and sudden
changes; (4) as a lubricator to diminish the friction of machinery, and
(5) as a facing for gunpowder as a protectant.
(y.) Lamp black, owing to its unalterable nature, is used as a
pigment in the manufacture of printing ink, blacking, etc.
(6.) Vegetable or wood charcoal is used as a disinfectant and deodorizer.
Thus, in ventilating sewers, in covering graves, in dissecting rooms and in
hospital wards it is used to prevent offensive smells from putrescent
matter, whilst in respirators it is employed to purify a vitiated air
before it reaches the lungs.
(e.) Animal charcoal is largely used as a decoloriter in sugar-refining,
and in the purification of alkaloids, oils, etc.
(4.) As an absorbent of impurities, we employ animal charcoal for
water filters, whilst in cases of poisoning by various substances, such
as strychnia, etc., the injection of charcoal into the stomach as an
absorbent, constitutes an important method of treatment.
(m.) As a fuel the use of charcoal is important. Coal is of vegetable
origin, the change having been effected by a peculiar decomposition
or fermentation, brought about by the agency of heat and moisture
under great pressure, whereby much of the hydrogen of the wood is
eliminated as marsh gas (CH4), and the owygen as carbonic anhydride
(CO2), the consequent accumulation of the carbon resulting. These
changes are represented in successive steps as follows:–
Carbon. Hydrogen. Oxygen.
(1.) Wood... ... ... 100 12:18 83-07
(2.) Peat ... ... ... 100 9.85 55-67
(3.) Lignite e tº º ſº tº º 100 8:37 42'42
(4.) Bituminous coal dº º º 100 6-12 21:23
(5.) Anthracite ... e & B 100 2-84 1-74
The passage from wood to coal, therefore, consists in the storage of
the carbon and in the elimination of the hydrogen and oxygen. A little
sulphur is also present in coal, derived partly from vegetable albu-
men, and partly existing as FeS2, derived from extraneous sources.
There are also certain Saline and earthy substances present, which
constitute the coal ashes.
The composition of various kinds of coal is shown in the following
table:—
COAL. 173

e ºf Bituminous Wigan ..
Lignite. Coal. Cannel. Anthracite. Coke.
Carbon . . . . . 66'32 78-57 80-06 90-39 96-6
Hydrogen 5-63 5:29 5-53 3-28 0-4
Nitrogen . . 0-56 I '84 2-12 0-83 0- 1
Oxygen .. 22-86 12-88 8-09 2-98 0-8
Sulphur .. 2: 36 0 - 39 1 - 50 0-91 0-3
Ash . . . . 2-27 1-03 2-70 1 : 61 1-8
100.00 100-00 100.00 100 : 00 100-0
The ash of coal varies, however, to a much greater extent than is
stated above. A good coal should not contain more than 5 per cent.
of ash, whilst a bad coal often contains 25 per cent. The following is
the average percentage composition of 40 samples of ash :-
Silica ... * - e. • * > e º º 44'8
Lime tº º tº © tº e * @ 9 gº tº º 9-9
Magnesia... tº tº º * @ 8 e tº tº 2'4
Alumina and ferric oxid 33-7
Sulphuric acid ... & 4 & tº º tº 8’4
Phosphoric acid ... e s o tº tº de ()'8
100-0
The sulphur present in the coal is important, the product of its
combustion being sulphurous acid, a gas very destructive to vegetable
life. Good coal should not contain more than from 1 to 1.5 per cent.
of Sulphur. The coke generally contains about one-half the quantity
of the sulphur present in the coal from which it was prepared.
Amount of Sulphur in different varieties of Coal.

Maximum. Minimum. Average.
Wales 5-07 0-09 36 exps. 1-47
Newcastle. , 2-85 0-06 18 , , 1 24
Derbyshire 1 - 30 0.80 7 ,, 1.01
Lancashire 3° 04 0. 52 28 ,, 1'43
Scotland . . . . l: 57 0-33 8 , 1 11
When coal is heated in close vessels, the volatile ingredients, as well
as the hydrogen, oxygen, and nitrogen present in the coal, are driven
off, either in a free state or combined with more or less carbon, whilst
coke (that is, carbon and earthy matters) remain in the retort. The
composition of coke will be seen in the above table. The more in-
tense the heat to which the coal is subjected, the more dense and the
more incombustible the coke, and the better fitted it becomes for pro-
ducing a steady and intense heat.
Process of burning coal in the open fire.—When the coal is heated it
first softens, then swells up, and finally gives off certain gaseous pro-
174 HANDBOOK OF MODERN CHEMISTRY.
ducts (such as CH, and C.H.), which take fire. If sufficient oxygen
was present, all the carbon would be dissipated as CO2, and all the
hydrogen as H2O. This, however, never happens in a fire grate.
Such gases as CH, and C.H., (marsh and olefiant gases) burn without
Smoke, whilst a large quantity of hydrocarbons, such as benzol, naph-
thalene, etc., which are also formed, catch fire, but the oxygen being
present in insufficient quantity, they undergo only partial combustion.
The unconsumed carbon from these, together with ammonic carbonate
and other products, escape to form the smoke and soot. The hot coke
now left in the grate burns away until all the carbon is consumed,
and the ash or incombustible mineral matter only remains.
When coke is used as a fuel, it does not undergo the first changes
just described. Coke does not swell or soften, and for this reason
cannot choke the draught like coal; and it is less combustible than
coal, from the absence of inflammable hydrocarbons, and conse-
quently burns without smoke.
It will be noted that anthracite or steam coal (stone coal or Welsh
coal), contains more carbon and less hydrogen than ordinary coal. It,
in fact, more nearly approaches the condition of coke. It therefore
emits, when burnt, but little smoke and but little volatile matter, and
consequently but little flame. Its principal use is for furnaces.
Smoke nuisances.—To remedy or reduce to a minimum the escape
of smoke, three things are necessary:
1st. That the fuel should be supplied in small quantities at a
time, and be placed well in front of the fire. (In Jucke's patent
a regular supply of fuel is effected by mechanical means).
2nd. That a strong fire should be constantly maintained.
The fuel should be supplied in small quantities, in order that the
volatile hydrocarbons should not be evolved in too great abundance at
a time; and it should be put in front of the fire, so that before their
escape they may pass over a large surface of glowing embers, whilst
it is important that the fire should be burning briskly, in order that the
gases and vapours may be consumed as fast as they are generated.
3rdly. There should be an adequate supply of air. In certain
smoke preventers (as Hill's patent) hot air is supplied to the
gases as they leave the fire, in order to complete the combustion
of any unburnt portions.
It is clear that the prevention of Smoke depends largely on the
attention of the stoker.
Charcoal is often used as fuel. Its advantage over wood is two-
fold; (1.) That the moisture and volatile matters of the wood have
been got rid of; and (2) that the percentage quantity of carbon is
much greater in the charcoal than in the wood. In the first case
much heat is lost when wood is used for fuel, in the formation of steam
and volatile compounds, which is avoided by using charcoal; and in
the second case, given weights of wood and charcoal being taken, the
CARBONIC OXIDE. 175
charcoal emits twice as much heat as wood. Thus the use of charcoal
prevents loss and also concentrates heat.
(c.) In medicine charcoal has been employed in cases of dyspepsia,
obstinate constipation, and as an application to foul ulcers, carbo
animalis, B.P. (bone-black). The charcoal is purified (carbo animalis
purificatus, B.P.) by digesting the crude charcoal in hydrochloric
acid and water to remove the calcic phosphate. Carbo ligni, B.P.,
(wood charcoal,) is also officinal. It is often administered in the form
of biscuits or lozenges. Its use in various cases of poisoning has
been already noticed.
COMPOUNDS OF CARBON AND OxYGEN.
Carbonic oxide tº dº ſº. tº º ſº © º º tº $ tº CO.
Carbonic anhydride & Cº º • gº tº tº º e CO2.
Carbonic Oxide, CO (CO).
Molecular weight, 28. Molecular volume, ||. Relative weight, 14.
Specific gravity, 0-967.
Synomyms.--Carbon 'monoacide.
History.-Discovered by Priestley when igniting chalk in a gun
barrel. He supposed it to be hydrogen. Its true nature was after-
wards determined (1803) by Cruickshank, Clement, and Desormes.
Natural History. It is never found except as an artificial product,
as e.g. (1.) In the neighbourhood of brick or lime kilns. (2.) In the
gases issuing from iron blast-furnaces (25 to 32 per cent.), from copper
refining furnaces (15 per cent.), as well as from ordinary stoves. Its
escape means waste.
Preparation.—(1.) By burning carbon in a limited supply of air.
(2.) By passing carbonic anhydride over red-hot iron. (Priestley.)
4CO2 + Fes Fe3O4 -- 4CO.
Carbonic anhydride + Iron Magnetic oxide of iron + Carbonic oxide.
[4CO2 + Fes *Y(Fe)YºO, + 4CO].
(3.) By passing carbonic anhydride over red-hot carbon–
CO3 + C = 200.
(4.) By acting on oxalic acid, or upon an oxalate with sulphuric
acid.
C.H.O., -i- H.S0, - CO2 + CO + H2O + H2SO4.
Oxalic acid + Sulphuric = Carbonic + Carbonic oxide + Water + Sulphuric
acid anhydride acid.
{3; + Soho, - co, + Co. 4 of, isoho.
|NOTE.-(1.) The sulphuric acid merely abstracts water from the
oxalic acid.
(2.) By washing the gaseous products with a solution of sodic
hydrate, the CO2 will be dissolved and the CO be left].
=
176 HANDIBOOK OF MODERN CEIEMISTRY.
(5.) By heating potassic ferrocyanide with sulphuric acid.
K.FeC6M 6 -- 6H,SO, + 6H,0 = 2K.S0, -i- FeSO, H- 3N.H.SO, -- 6CO.
Potassie --Sulphuric-i- Water = Potassic + Ferrous + Ammonic --Carbonic
ferrocyanide acid sulphate sulphate Sulphate oxide.
Fe"CºNER, + 6S0, Ho, + 6H,0 = 2SO, Ko, + S0, Feo" +3SO,(NH,0),4-6CO.
(6.) By heating a formate or formic acid with sulphuric acid.
CH.O., -: H2O + CO.
Formic acid - Water + Carbonic oxide.
Properties.—(a.) Sensible.—A colorless gas without odor or taste.
(3) Physiological.—Carbonic oxide is a pure narcotic poison. Its
effects were described by Guyton Morveau in 1802, and by Sir H.
Davy in 1810. Its injurious effects, when injected into the veins,
were discovered by Nysten. Tourdes proved that 1 part of the gas in
7 of air killed rabbits in seven minutes, 1 in 15 in twenty-three
minutes, and 1 in 30 in thirty-seven minutes. Leblanc and Dumas'
experiments show that air containing 1 per cent. of the gas will
kill a dog in one and a-half minutes, and that birds die instantly
in an atmosphere containing 5 per cent.
Dr. Letheby found in his experiments that air containing 0.5 per
cent. Of the gas, kills small birds in about three minutes, whilst an
atmosphere containing 1 per cent. proves fatal in about half the time.
It has been held that the poisonous action of carbonic oxide de-
pends on the formation in the blood of a new and fixed compound of
carbonic oxide and haemoglobin.
(y.) Physical.—Its specific gravity is 0-972; the gas, therefore, is
fourteen times heavier than hydrogen. It has never been condensed.
It is decomposed, when passed through a red-hot tube, into carbon
and carbonic anhydride. (See page 13.)
(3.) Chemical.—Carbonic oxide is an indifferent oxide, and has no
action either on litmus or turmeric. It burns with a pale blue and
very hot flame, carbonic anhydride being the only product. It neither
supports combustion, nor whitens lime water. It explodes with half
its volume of oxygen, forming carbonic anhydride. It has no action
on the metals, except on potassium, which absorbs it when heated
(K.C.O.). It combines with chlorine in sunlight to form phosgene
gas (COCl.). It is slightly soluble in water, 100 volumes dissolving
2.43 volumes at 60°F. It forms potassic formate when heated with
potassic hydrate (KHO+CO=CHKO.). It is absorbed by a solution
of cuprous chloride in hydrochloric acid, forming the compound
CO, Cu2Cl22EI20. On boiling this liquid, the gas is expelled un-
altered.
The carbonic oxide flame is employed in the reverberatory furnace,
where it is made to play over metallic ores, thereby reducing them, the
CO forming CO2 at the expense of the oxygen of the metallic oxide.
CARBONIC ANHYDRIDE. 177
The carbonic oxide is produced by causing the carbonic anhydride
formed at the bottom of the grate to pass through the hot coal in the
grate (CO2+C=2CO). The same thing occurs in an ordinary stove,
the CO2 formed at the bottom of the stove, where there is plenty of
air, becoming CO as it passes through the fire, which burns as soon as
it reaches the surface. Carbonic oxide is present to the extent of 34
per cent. in water gas. This is prepared by first passing steam over
red-hot coke, whereby hydrogen and carbonic oxide are formed
(4H2O + Cº-CO2 + 2CO +4EI2), and afterwards supplying the com-
bustible gases with illuminating properties, by causing them to traverse
red-hot coke saturated with melted resin. The presence of so large
a quantity of carbonic oxide would render the use of water gas very
dangerous. Common coal gas also contains from 4 to 7 per cent. of
carbonic oxide.
Carbonic Anhydride, (CO2=44) (CO2).
Molecular weight, 44. Molecular volume, ſº | | . Relative weight, 22.
Specific gravity, 1529. 100 cubic inches weigh 47-445 grains, and
1 litre 19774 grins.
Synonyms.-Commonly called Carbonic acid; Carbon or Carbonic
Dioxide; Mephitic Air; Gas Sylvestre; Fived Air (Black); Choke Damp.
History.--Carbonic anhydride was known to Paracelsus and Von
Helmont. It was examined by Black in 1757, and called by him
* Fixed Air.” In 1775 Lavoisier, by careful experiments on the
products of the combustion of the diamond, determined its exact
nature and named it carbonic acid.
Natural History. (a.) In the mineral kingdom carbonic anhydride
is found free in the air. It is evolved—
(1.) As a product of respiration in man and animals, Respired air
contains about 4 per cent. of carbonic anhydride.
(2.) As a product of fermentation.—Thus, accidents have arisen from
plunging the head into fermenting vats.
(3.) As a product of lime burning.—Calcic carbonate when heated
evolves carbonic anhydride, leaving caustic lime (CaCOs=CaO + CO2).
By subterranean heat in volcanic districts a similar action takes
place; thus immense quantities of CO2 are given out into the air,
whilst the springs in the neighbourhood become charged with the gas.
(4.) As a product of slow oacidation.—Thus, spring water becomes
impregnated with carbonic acid, from the oxidation of the organic
matter by the oxygen dissolved in the water. If a bottle half full
of water containing organic matter, be kept in a warm room and in a
closed vessel, the oxygen in the bottle will be found after a time to be
more or less completely replaced by a corresponding volume of
carbonic anhydride. So also carbonic anhydride is found in old wells
and cellars, where it is produced by the decay of organic matter and
in Some cases, perhaps, exhaled from the earth.
N
178 HANDBOOK OF MODERN CHEMISTRY.
(5.) A8 a product of the explosion of fire-damp, or carburetted
hydrogen.—The product of the explosion (choke damp) is more often
the cause of deaths than even the explosion itself. -
(6.) As a product of combustion.—All bodies containing carbon yield
by combustion carbonic anhydride. Two ordinary candles produce as
much carbonic anhydride in an equal time as one adult (Angus Smith).
It is also found in a combined state in carbonates, as in limestone,
marble, and chalk. -
(3.) It is not found in any great quantity in the vegetable kingdom,
the special action of the plant being to decompose it, whilst (y) in the
animal kingdom it is found in the exhaled air derived from the
combustion of tissue.
Preparation. (1.) By burning carbon in air or oxygen
(C+O2=CO2).
(2.) By the action of acids on carbonates. If sulphuric acid be
poured on marble, carbonic anhydride is set free, but the action is
Soon arrested by the formation of an insoluble sulphate over the
surface of the marble. Hence we ordinarily employ HCl for the
purpose :-
Calcic carbonate + Hydrochloric = Calcic chloride + Water + Carbonic
acid anhydride.
[COCao" + 2.HCl = CaCl2 + OH, -i- CO2].
It must be collected by displacement.
Properties.—(a.) Sensible. Carbonic anhydride is a colorless gas.
It has no odor when largely diluted with air, but the presence of
above 5 per cent. of CO2 renders the air irritating and pungent.
(3) Physiological. When swallowed, the gas is harmless. Inhaled,
it acts as a narcotic poison.
(1.) The undiluted gas kills instantly by spasm of the glottis.
(2.) When diluted with air, so that the proportion of the gas
present is about 12 or 14 per cent. (as in a room where a chafing dish
has been burnt) it causes giddiness, hurried circulation, fulness in
the head, noises, confusion, perhaps delirium, and finally coma, which
may last a considerable time.
(3.) Air containing 4 or 5 per cent. of carbonic anhydride (such as
air once breathed) causes a sense of oppression with headache,
distress, and perhaps delirium or coma.
(4.) Air containing 3 per cent. of carbonic anhydride cannot be
breathed without great distress, and will probably produce insensibility.
(5.) An atmosphere containing 1 or even 0.5 per cent. of carbonic
anhydride (such as is found in ill-ventilated theatres) is
distressing.
(6.) Its presence in the proportion of 0.1 per cent, may be considered
the boundary line between good and bad air.
These facts show the necessity of good ventilation. Although
CARBONIC ANHYDRIDE. 179
carbonic anhydride is half as heavy again as air, nevertheless the
processes whereby it is produced by raising its temperature render it
specifically lighter. Thus it ascends and accumulates near the ceiling.
The chimney opening only ventilates the lower part of the room.
(y.) Physical. The specific gravity of carbonic anhydride is 1529,
that is, it is 22 times heavier than hydrogen; 100 cubic inches weigh
47.445 grains, and 1 litre 19774 grim. Hence it accumulates on the
floors of caves and caverns (Grotto del Cane). By a pressure of 50
atmospheres at 59° F (15°C.), or by a pressure of 38-5 atmospheres
at 32°F. (0°C.), the gas may be liquefied, the liquid having a gra-
vity of 0.83. It is important to note here, that in liquefying gases
by cold and pressure, an increased pressure is not necessarily equivalent
to a reduced temperature. For in every liquefiable gas there is a tem-
perature at which it cannot be liquefied by any attainable pressure.
This is termed the “critical point,” that is, the point where the gas is
wavering between the gaseous and the liquid state. Thus, if you
heat carbonic anhydride to 88° F. (31.1° C.), no known pressure
(109 atmospheres having been tried) will effect its liquefaction.
Liquid carbonic anhydride does not mix freely with water, but is solu-
ble in spirit, ether, turpentine, carbonic disulphide, etc. If the liquid be
cooled to —70°F. (–56°C.), or if it be allowed to escape into the air,
it instantly freezes into a snow-white solid, the cold produced by its
evaporation in the latter case answering to the artificial cold in the
former. It evaporates without melting, inasmuch as the heat it
requires for its evaporation keeps it as low as —125° F (–87.2° C.),
whilst it melts at —85° F (–65° C). It conducts electricity badly.
The greatest known cold (–148°F., or —100° C.), is produced by
the evaporation of a mixture of solid carbonic anhydride and ether
“in vacuo.”
A heat of 2192°F. (1200° C.) decomposes carbonic anhydride into
oxygen and carbonic oxide, re-combination occurring if the mixture
be allowed to cool slowly. Similarly, the heat of the electric spark
will affect dissociation, the Oxygen set free being said to be in an
ozonised condition.
At ordinary pressure, 1 volume of water absorbs 1 volume of the
gas; at 2 pressures, 2 volumes; at 3 pressures, 3 volumes, etc.; but
on the removal of the extra pressure all the dissolved gas escapes
except the original volume. Thus, by pressure under the earth,
water may be made to take up an extra quantity of gas, whereby it
is rendered effervescent when it comes to the surface.
The rain as it falls dissolves atmospheric carbonic anhydride. This
solution acts on certain rocks, slowly crumbling and disintegrating
them. This process of rock disintegration is assisted by the expansion
of the water in the interstices of the rock during congelation.
Thus soils are formed of the broken down débris (Na,SiO,4-4H2O+
4CO2=HASiO4+4NaHCO3). Further, owing to the solubility of the
180 HANDBOOK OF MODERN CHEMISTRY.
gas in water, the rain brings it to the roots of plants, the solution
dissolving the calcic phosphate which is insoluble in pure water.
(6.) Chemical.—The gaseous, but not the liquid carbonic anhydride,
effects a transient reddening of blue litmus. The pure gas instantly
extinguishes a flame. We may classify the results of dilute carbonic
anhydride as follows:—
An atmosphere containing Action on flame.
16 per cent. of CO2. Flame instantly extinguished.
12 } } 3 y Flame extinguished if not burning vigorously.
10 25 2 3 Taper burns, but the flame considerably dulled.
5 y }} Taper burns readily.
Thus it is evident that a taper may burn in an atmosphere that is
dangerous and even fatai to life.
Potassium burns in carbonic anhydride, setting free carbon (3002--
2K2=2K2CO3 + C). Sodic oxalate is formed when the gas is passed into
melted sodium (2CO2 + Nag-C.Na2O4), and potassic formate, together
with hydric potassic carbonate, when the moist gas is brought into
contact with potassium (2CO2+K. --H2O=ICHCO3 + KHCO3).
Carbonic acid (H2CO3) is not known.
Tests.-A white precipitate with lime or baryta water. Its ready
solubility in a solution of potassic hydrate enables us to separate it
from most other gases.
CoMPOUNDs of CARBON AND THE HALOIDs.
Compounds of Carbon and Chlorine.
Carbonic Tetrachloride e tº º ... CC14.
Carbonic Trichloride ... tº 2 ºn . . CeCl6.
Carbonic Dichloride ... © tº G ... CoCl4.
Carbonic Monochloride & 6 º' ... C. Cl2, or C6Cl6.
These compounds are all prepared by indirect methods.
Carbonic Tetrachloride (CCI,-154).
Synonym.—Bichloride of carbon.
History.—Discovered by Regnault.
Preparation.—(1.) By the action of chlorine on marsh gas (CH4).
(2.) By passing chlorine and carbonic disulphide vapor through a
red-hot tube (CS,4-4Cl2=CC1, +2SCl2). The sulphur chloride may
be dissolved out by a solution of potassic hydrate.
Properties.—A colorless liquid. Specific gravity, I'56. Boils at
172°F (77°C.); freezes at –9°F. (–22.8°C.). It is insoluble in water,
but is soluble in alcohol, and in ether. It freely dissolves fats, resins,
etc. By the action upon it of zinc and hydrochloric acid, chloroform
may be obtained. Its vapor is powerfully anaesthetic.
CARBONIC OXYCHILORIDE. - 181
Carbonic Trichloride (C2Cl6=202).
Synonym.—Sesquichloride of carbon.
History.—Discovered by Faraday.
Preparation.—(1.) By the action of sunlight on a mixture of
Dutch liquid (C.H.Cl2) and chlorine (C,EH,Cl2+4Cl2=C,Cl6+4EICl).
(2.) By passing the vapor of carbonic tetrachloride (CC1,) through
a red-hot tube.
Properties.—A white crystalline solid, having an aromatic camphory
odor. It fuses at 320° F (160° C.), and boils at 360°F. (1822°C.),
when it sublimes unchanged. It is volatile at ordinary temperatures.
It is insoluble in water, but is soluble in ether and in alcohol.
Carbonic Dichloride (CºCl4–164).
Synonym.–Protochloride of carbon.
History.--Discovered by Faraday.
Preparation,-(1.) By passing the vapors of CC1, or C2Cl6 through
a red-hot tube.
(2.) By the action of nascent hydrogen on carbonic trichloride
(C2Cl6).
Properties. A liquid. Specific gravity, 1:19. Boils at 248° F.
(117°C.). It is insoluble in water, but is soluble in alcohol, and in
ether.
Carbonic Monochloride, C2Cl2, or C6Cl6.
Synonyms.— Carbonic subchloride or Herachloride.
Preparation,-(1.) By passing either the vapor of C2Cl, or of
chloroform through a red-hot tube.
(2.) By the action of chlorine on benzene.
Properties, LA white crystalline solid without odor, insoluble in
water, but soluble in ether and hot alcohol. It melts at 438.8° F.
(226°C.), and boils, subliming unchanged at 627.8°F (331°C.),
CoMPOUNDS OF CARBON WITH BROMINE, ETC.
A carbonic tetrabromide (CBra); a carbonic tribromide (C.Brº), pre-
pared by acting on C.Br., with bromine ; and a carbonic dibromide
(C. Bra) prepared by acting on ether or alcohol with bromine, all three
of which are white crystalline bodies, have been described.
By the action of bromine in sunlight on carbonic dichloride
(C,Cl), a carbonic chlorobromide (C,Cl, Br.), a crystalline body, is formed.
No compound of carbon and iodine has been for certain discovered.
COMPOUNDS OF CARBON WITH OxYGEN AND THE HALOIDs.
Carbonic Oxychloride, COCl.
Synonyms, Chlorocarbonic acid; Carbonyl chloride; Phosgene gas.
Preparation,-(1.) By exposing equal volumes of carbonic oxide
182 HANDBOOK OF MODERN CHEMISTRY.
and chlorine to sunlight, the mixture condensing to one-half its
original volume.
(2.) By heating together carbonic tetrachloride and zincic oxide
(2CC1,-i-32n()=3ZnCl2 + COCl.--CO.).
(3.) By the oxidation of chloroform.
Properties.—A colorless pungent gas. It is decomposed by water.
For this reason it fumes in the air, the chlorine combining with the
hydrogen of the moisture (COCl.--H,0=CO.--2HCl). By a cold of
5°F (-15°C.), it forms a liquid which has a specific gravity of
1,432 at 32°F (0°C.), and boils at 46.3°F. (8.2° C).
With ammonia it forms urea and ammonic chloride.
4NH, 4- COCl. = COH, N, + 2NEI,Cl.
Ammonia + Phosgene gas = Urea + Ammonic chloride.
This reaction illustrates the property of phosgene gas in effecting
the displacement of hydrogen and its substitution by carbonic oxide.
The analogous bromine and iodine compounds have not been pre-
pared.
COMPOUNDs of CARBON AND SULPHUR.
Carbonic Disulphide (CS.).
Synonyms.—Bisulphuret or Bisulphide of carbon; Sulphocarbonic acid.
History.-Discovered accidentally by Lampadius in 1796 whilst
distilling iron pyrites. &
Preparation.—(1.) By passing the vapor of sulphur over heated
charcoal (C+S2=CS2).
(2.) By heating together charcoal and iron, or charcoal and copper
pyrites (C+2FeS2=CS2+2FeS).
Properties.-(a.) Sensible.—An ethereal colorless liquid having a
peculiar odor.
(6.) Physiological.—Its action is anaesthetic, and in excess it acts as
a poison. It is used for destroying insects in grain.
(y.) Physical.—Specific gravity of liquid, 1272; of vapor, 2-63. It
boils at 110°F. (43.3°C.), but it cannot be frozen. It refracts light
powerfully. It is volatile at ordinary temperatures.
(8.) Chemical.—It has no action on litmus. It fires at 360° F.
(1822°C.), the products of its combustion being CO., and SO2. It
explodes vehemently when mixed with oxygen. Potassium burns in
the vapor with the liberation of carbon, and the formation of a
potassic sulphide (CS.--2K2–2SK.--C). When the vapor is passed
over many red-hot metallic oxides, it changes them into Sulphides.
When a mixture of the vapor and sulphuretted hydrogen is passed
over hot copper, it yields a sulphide of copper and marsh gas
(CS. +2H.S + Cus-4Cu2S + CHA).
It combines with alkaline hydrates, and with alkaline sulphides to
form sulphocarbonates (M"CSA), which are bodies analogous to the
carbonates, but containing sulphur in the place of oxygen (CaCOs
BORON. - 183
—CaCS). When the sulphocarbonates are boiled with water they
become carbonates. Sulphocarbonic acid (H2CS3) may be prepared by
the action of hydrochloric acid on the salts. It is a yellow oily liquid.
Carbonic disulphide is nearly insoluble in water, but very soluble in
alcohol and in ether. It is a solvent, moreover, of many bodies, such
as sulphur, phosphorus, iodine, the alkaloids, oils, gums, resins, fats,
etc. Hence its use. It is also employed in making thermometers for
registering very low temperatures.
It forms one of the most troublesome impurities of coal gas.
Carbonic Oxysulphide (COS).
This body, which was discovered by Thau, may be regarded as
H2S, where (CO)" has replaced the H2,
Preparation.—(1.) By heating a mixture of sulphur vapor and
carbonic oxide.
(2.) By heating together potassic sulphocyanide and dilute sul-
phuric acid. A hydrosulphocyanic acid is first formed (KCNS+
H2SO4–HCNS+ KHSO4) and afterwards decomposed by the water
into carbonic oxysulphide and ammonia, the latter being absorbed by
the excess of acid (HCNS+ H2O=NH3+COS).
(3.) By heating a mixture of urea and carbonic disulphide.
Properties.—A combustible, aromatic gas, decomposed by heat
into CO and S. It is slightly soluble in water, the solution decom-
posing after a time spontaneously (or immediately if an alkali be
present), into carbonic anhydride and sulphuretted hydrogen. It has
no action upon an acid solution of lead, copper or silver.
BORON (B=11).
Atomic weight, 11. Molecular weight (probable), 22. Triad (BCls—BFs.)
History.—Prepared by Davy (1807), by the action of the galvanic
current on boracic acid. Guy Lussac and Thénard (1808) prepared
it by acting on boric anhydride with potassium. Wohler and Deville
(1857) first prepared the crystalline modification. -
Natural History.—It is never found in nature in a free state. It
occurs as boracic acid in the lagoons of Tuscany, and in combination
with soda as tincal, with magnesia as boracite, and with lime as bora-
calcite, etc.
Warieties. Three varieties have been described, viz., the amor-
phows, the graphoidal, and the crystalline. The graphoidal modification,
however, is probably a compound of AlB2,
Preparation.—(a.) Amorphous boron.
(1.) By fusing together boric oxide and sodium (B20s-- 3Na2
=3Na2O+B2). -
(2.) By the action of boric oxide on potassium, or on potassic boro-
fluoride.
184 HANDBOOK OF MODERN CHEMISTRY.
(6.) Crystalline (diamond) boron. -
By fusing together boric oxide and aluminium (B203+Al2=Al2O3
+B2).
Properties.—The amorphous modification of boron is an olive-
green powder, and burns both in oxygen (forming B2O3) and in
chlorine (forming BCls). It is insoluble in water. When burnt
in air, a trace of boric nitride (BN) is formed. It decomposes hot
sulphuric acid (3H2SO4+B2–B2O3 + 3H20+3SO2), and nitric acid
It also decomposes the alkaline carbonates, sulphates, and nitrates,
setting free carbonic oxide, sulphurous anhydride, and nitric peroxide
respectively.
Crystalline or diamond boron (adamantine boron) which, next to the
diamond, is the hardest substance known, has a specific gravity of
2-68, and when pure is colorless, and a powerful optical refractor. It
is infusible, and is not acted upon by strong acids, but it burns when
heated to redness in chlorine. It forms boric oxide when fused with
potassic sulphate (6KEISO4+B2–B203-1-3K2SO4+3EI,0+ 3SO2).
[Boric or Boracic Acid (HaBOs or BHos). Boracic Anhydride
(B403)].
Preparation and Natural History.—The acid was originally
prepared by Homberg (1702) and by Lemery (1727) by the action
either of dilute sulphuric acid, as suggested by the latter, or of
dehydrated ferrous sulphate, as suggested by the former, on borax
(Na2O,2B2O3 + 10aq called Sedative Salt, and, when in the rough,
Tincal).
The acid is now obtained as follows:–In certain volcanic districts
boracic acid is discharged from the earth in a free and vaporous state,
accompanied by steam jets (suffioni). We know nothing of its actual
origin. For the purpose of condensing these steam jets, brick basins
(lagoons) are erected at the site of the discharge, and are filled with
water from neighbouring springs. A series of these lagoons is con-
structed in a descending line, so that the water may flow from one to
the other. The acid solution which collects in the basins is then eva-
porated down in leaden pans, the suffioni themselves being employed
as the source of heat. The acid is then purified by crystallization.
Properties, (a.) Physical.—The acid has a bitter taste and crystal-
lizes in scales. At 2.48° F. (120°C.) it becomes HBO, or BOHo (meta-
boric acid). At a higher temperature a hygroscopic body (B203) is
formed, which at a greater heat fuses to a clear glass (vitreous boric
acid) which finally volatilizes.
It is soluble in 3 parts by weight of boiling water and in 26 parts
of cold, but its solubility is irregular. It is soluble in spirit, the
solution burning with a green flame,
SILICON OR SILICIUM. 185
(3.) Chemical.—The solution of the acid is faintly acid to litmus,
but if a piece of turmeric paper be dipped into the solution and dried,
it becomes of a brown red color. If this be moistened with an
alkali it changes to an intense blue.
The acid forms salts called borates.
Boric Nitride, BN or BANs.
Preparation.—By heating boron in nitrogen, in air, or in ammonia
gas, or by heating a mixture either of boric oxide and urea, or of
borax and ammonic chloride.
Properties.-A white, infusible, and insoluble powder.
A boric chloride (BC13), a liquid prepared by burning boron in
chlorine; a boric bromide (B.Bra), a liquid also prepared by direct
union; a boric fluoride (BFs), a gas prepared by heating a mixture of
borax, fluor spar, and sulphuric acid, have been described. Moreover,
a boric sulphide (B.S.), a white solid, formed by direct union, is known.
A fluoboric acid (HB023EIF) and a hydrofluoboric acid (HBF4) formed
by the action of water on boric fluoride are also known.
SILICON or SILICIUM (Si-28-5).
Atomicity, tetrad, as in SiCl4,
History.—Silicon was discovered by Davy (1807), when acting on
silicic acid with potassium. Berzelius (1824) obtained it by the action
of potassium on fluosilicic acid.
Natural History.-Silicon has never been found in a free state.
It occurs (a.), in the mineral kingdom, as silica (SiO2); both in a crys-
tallized form, as quartz; and in a non-crystallized form, as flint, chal-
cedony, opal, etc. It also exists abundantly in combination with
metallic oxides. Clays are aluminic silicates. (3.) In the vegetable
kingdom it is found in the stems of cereals; (y) and in the animal
kingdom in teeth, feathers, bones, etc.
Varieties.—Silicon exists in three modifications; (a) amorphows;
(3) graphoidal; and (y) crystalline.
Preparation.—(a.) Amorphous Silicon.
(1.) By heating together potassium and potassic-silico-fluoride
(fluoride of silicon and potassium).
SiR.Fs + 2K2 6|KF + Si.
Potassic silico-fluoride + Potassium = Potassic fluoride + Silicon.
(2.) By heating sodium in the vapor of silicic chloride (SiCl,+
2Naz=Si-H 4NaCl).
(3.) Graphoidal Silicon.—By fusing together aluminium and
amorphous silicon, and afterwards dissolving out the aluminium from
the mixture by boiling hydrochloric acid.
(y.) Adamantine Silicon.
(1.) By fusing amorphous silicon,
=
186 HANDBOOK OF MODERN CHEMISTRY.
(2.) By heating aluminium in a current of silicic chloride vapor
(3SiCl,--2Al2=2Al2Cl6+ 3Si).
Properties.—(a.) Of amorphous silicon. A dark brown powder.
Specific gravity 2-0. Infusible and involatile. It neither conducts heat
nor electricity. It burns when heated in air or oxygen, forming SiO2.
It is not acted on by any solvents except hydrofluoric acid (fluorine
having a great affinity for silicon), forming hydrofluosilicic acid
(Si + 6HF = SiRI2F5 + 2 H2). When fused with potassic hydrate,
hydrogen is evolved, and a potassic silicate formed (Si + 4.KHO =
K4SiO4 + 2 H2). By fusion with aluminium the graphoidal modifica-
tion is produced.
(6.) Of graphoidal silicon. It is found in the form of crystalline
metallic-looking scales, having a specific gravity of 2:49. It conducts
electricity. It does not burn in oxygen. It is not dissolved by hydro-
fluoric acid, but is soluble in a mixture of hydrofluoric and nitric
acids. It is slowly acted upon when fused with potassic hydrate.
(y.) Of adamantine silicon.—Adamantine silicon is even less prone
to oxidation than the graphoidal modification. It resembles crystal-
lized haematite both in color and appearance.
COMPOUNDs of SILICON AND OXYGEN.
Silica (SiO2=60) (SiO2).
Synonyms, Silicon dioacide ; Silicic anhydride.
Natural History.—Silica occurs, in the mineral kingdom, both in
a crystalline and in an amorphous form. Quartz (i.e., rock crystal,
consisting of six-sided crystals terminated by six-sided pyramids),
Amethyst (the purple color of which is due to iron), Cairngorm (a
yellow or brown stone), are illustrations of the crystalline variety;
and Agate, Chalcedony (which in layers of different colors constitutes
Onya), Jasper, Cornelian (the color of which is due to ferric oxide),
Flint, and Opal (where the silica is combined with varying quantities
of water), are illustrations of the amorphous variety.
Sand is very nearly pure silica, its different colors depending on the
presence of various foreign matters. It forms the chief support of
the soil. Plants absorb it freely, as shown by its presence in the
stems of rushes and cereals. This, and its presence in solution in
certain natural waters, as in the Geysers, prove the possibility of its
existing in a soluble form.
All the artificial forms of silica are of the amorphous modification.
Properties.—Pure silica, when en masse, is a hard, colorless, trans-
parent body, but when finely powdered appears white. The crystalline
form has a specific gravity of 2:7, and the amorphous of 2:2. Both
forms are non-volatile, but by oxy-hydrogen heat they fuse to a clear
glass, the crystalline thereby becoming the amorphous modification.
They are insoluble in pure water, and in all acids except hydrofluoric,
SILICIC ACID. 187
The amorphous form is soluble in solutions of the caustic alkalies,
and is slightly soluble in the alkaline carbonates. By heating finely
powdered quartz (but not if it be in lump), it is converted into the
amorphous variety, and becomes soluble in alkalies.
The ordinary vegetable acids (as e.g. tartaric acid), or a weak
acid (such as carbonic acid), precipitate silica from its solutions;
nevertheless, at a high temperature, silica being non-volatile, decomposes
carbonates and even sulphates.
Silica is soluble in fused borax, but not in microcosmic salt.
Silicic Acid.
H. SiO, or 2H2O, SiO2, or SiHo, (tetrabasic acid).
H2SiO3, or H2O, SiO2, or SiOHoe (dibasic acid).
At the moment that silica is liberated from its soluble compounds,
it is soluble in water, silicic acid being thereby formed. This is found
in the two modifications mentioned above.
Preparation.—(1.) If silica be fused with sodic carbonate, car-
bonic acid escapes and a sodic silicate is formed. This salt is alkaline,
and soluble in water. If a few drops of hydrochloric acid (i.e., not
sufficient to render it acid) be added to its solution, it forms a gelatinous
mass, from the separation of hydrated silicic acid. If an excess of
acid, however, be added (i.e., sufficient to render it acid), silicic acid,
together with sodic chloride, are produced, and both remain in
solution :-
Na,SiO, + 4HCl = H, SiO, -- 4NaCl.
Sodic silicate + Hydrochloric acid = Silicic acid + Sodic chloride.
[SiNao, + 4HCl = SiHo, + 4NaCl.
If this solution be dialysed, the sodic chloride, with any excess of
hydrochloric acid, will pass through the dialyser, whilst a pure solu-
tion of silicic acid will remain on the dialyser.
Substances (like sodic chloride) that diffuse rapidly are termed
crystalloids, and those having a low rate of diffusion (such as silicic
acid) are termed colloids.
(2.) It may also be prepared by the action of carbonic anhydride
on a solution of sodic or other soluble silicate. This action is similar
to that which occurs in the natural disintegration of granite.
NaaSiO4 + 4H2O + 4CO2 = H,SiO, -i- 4NaHCOs.
Sodic silicate + Water + Carbonic anhydride = Silicic acid + Hydric sodic
carbonate.
[SiNao, + 4OH2 + 4CO2 = SiHo, + 4COHoNao.]
(3.) By the action of water on silicic fluoride:–
Silicic fluoride + Water = Silicic acid + Hydrofluosilicic acid.
[3SiF, +4OH2= SiHo, + 2 HF, SiF.,.]
188 HANDBOOK OF MODERN CHEMISTRY.
Properties.—The solution of silicic acid may, by cautious evapor-
ation, be concentrated until it contains 14 per cent. of the acid
(HaSiO4). In this state it is a colorless tasteless liquid, and faintly
acid to litmus. By keeping, the acid separates from the water as
a gelatinous mass, which shrinks in drying, and when dry has the
formula SigEI,016 (Si6Oaſſos). If this be heated to 212°F. (100° C.),
it loses water and becomes SigEI,014 (Si6Olofſo). :
If the solution be evaporated in vacuo over sulphuric acid, a lus-
trous glass is formed, containing 78 per cent. of silicic acid (H2O, SiO2).
This is insoluble in water, and but very slightly soluble in hydro-
chloric acid. By further heat the anhydrous acid may be obtained,
which is insoluble both in hydrofluoric acid and in water, but is
soluble in boiling solutions of the caustic alkalies.
CoMPOUNDs of SILICON AND THE HALOIDS, ETC.
Compounds of Silicon and Chlorine.
Silicic tetrachloride ... tº ſº tº tº e & ... SiCl3.
Silicic trichloride © s is tº dº tº © tº ſº ... Si2Cl6.
Silicic hydrotrichloride ... g º e tº º º ... SiHCls.
Silicic Tetrachloride (SiCl3).
Synonym.—Silicic Chloride.
Preparation.—(1) By burning silicon in chlorine.
(2.) By heating carbon and silicic anhydride in a stream of chlorine.
SiO2 + 2C + 2Cl2 = SiCl, + 2CO.
Silicic anhydride + Carbon + Chlorine = Silicon tetrachloride + Carbonic oxide.
[SiO, + 2C + 2Cl2 = SiCl, + 2CO].
Properties. – A transparent, pungent-smelling, colorless, very
volatile liquid. It fumes in the air from the deposition of silica by
the action of the moisture. The specific gravity of the liquid at
32° F (0° C.), is 1.5237, and of the vapor 5'939. It boils at 1382°F.
(59° C.). Water decomposes it into hydrochloric and silicic acids
(SiCl, 4-4OH2=SiHo,+4.HCl).
Silicic Trichloride (Si2Cl3), formed by acting on silicon with
carbon tetrachloride, has been prepared. It is a colorless liquid (Sp.
Gr. 1:58). Its vapor is spontaneously inflammable.
Silicic Hydrotrichloride,-( SiłłCl3) (Silicon chloroform), is prepared
by heating crystallized silicon in a stream of hydrochloric acid (Si-H 3HCl
=SiHCl, 4-H2). It is a fuming liquid, boiling at 96.5° F (36°C.).
The vapor is very inflammable, and explodes when mixed with
oxygen. It is decomposed either (1) by passing it through a red-hot
tube, or (2), at ordinary temperatures by the action of chlorine, or,
(3), by contact with water.
Several Silicic oxychlorides have been prepared.
EIYDROFLUOSILICIC ACID. 189
CoMPOUNDs of SILICON witH BROMINE, IoDINE, ETC.
Silicic Tetrabromide (SiPra) is prepared similarly to the chlorine
compound. It is a colorless, heavy liquid, boiling at 307.4° F.
(153° C.).
Silicic Tribromide (Sig Bro) is also a crystalline substance.
Silicic Tetriodide (Sila) is a crystalline body, prepared by passing
iodine vapor and carbonic anhydride over heated silicon.
Silicic Triiodide (Sig Ig) is also a crystalline solid, prepared by the
action of metallic silver on Siſa.
Silicic Iodoform (SiFIIs), corresponding to silicon chloroform,
has been prepared by passing hydrogen and hydriodic acid over
heated silicon. It is a liquid (Sp. Gr. 3:362), and is decomposed by
Water.
COMPOUNDs of SILICON WITH FLUORINE, ETC.
Silicic Fluoride (SiF4).
Synonym.—Silicie Tetrafluoride.
Preparation.—By heating together silica, calcic fluoride and sul-
phuric acid.
SiO2 + 2CaF2 + 2 H.S.O. = SiF, + 2CaSO, H.O.
Silica + Calcic + Sulphuric = Silicic + Dihydric calcic
fluoride acid fluoride sulphate.
[SiO2 + 2CaF2 + 2SO. Ho, - SiF, + 2SOHo,Cao"].
Properties.—A heavy, colorless, fuming gas. Specific gravity 3-6.
It neither burns nor supports combustion. It may be liquefied by
pressure, and solidified by a cold of —220° F (–140° C.). By the
action of water upon it, silicic and fluosilicic acids are formed.
Silicic fluoride + Water = Silicic acid + Hydrofluosilicic acid.
[3SiF, + 4OH. = SiHo, + 2(2HF, SiF.)].
Many metallic oxides (as lime) absorb it freely.
Hydrofluosilicic Acid (2HF,SiF, or H. SiF6).
Synonym.-Silico fluoric acid,
Preparation.—By the action of water on silicic fluoride. (See last
equation.)
Properties.—The solution is a fuming acid liquid. It does not
attack glass. When heated, silicic fluoride is evolved, and hydro-
fluoric acid, which readily dissolves glass, remains in solution.
Neutralised with bases, a hydro-fluosilicate is formed (2KHO
+2HF,SiF,-2H,0+2KF,SiF.); but if the base be added in excess,
190 HANDBOOK of MoDERN CHEMISTRY.
silica is thrown down, and a metallic fluoride produced (6KHO
+2HF,SiF4–4H2O+6KF+ SiO2). The baric and potassic hydrofluo-
silicates are very insoluble. -
Silicic Nitride (Formula 2) is formed by the direct combination of
silica and nitrogen, at a high temperature. It is a white infusible
body, soluble only in hydrofluoric acid, forming ammonic silico-
fluoride. When heated in carbonic anhydride, it forms ammonic
carbonate. When heated in steam, ammonia is set free. It is not
acted upon by chlorine, nor does heat alone affect it.
Silicic Sulphide (SiS2) (bisulphide of silicon), is prepared either by
direct union, or by passing CS2 vapor over a mixture of charcoal and
silica. It is a white amorphous hygroscopic solid, soluble in water,
by which it is decomposed into silica and hydro-sulphuric acid
(SiS.--2H2O=SiO2+2H2S).
Silico-Formic Acid, or Leukon (\evkóc white) (SiPI2O2) (silicon
formanhydride) is formed by the action of water on silicon chloroform.
It is a white substance, decomposed by the caustic alkalies with the
evolution of hydrogen. It has a powerful reducing action.
Chryseon, or Silicone (Si6H6O47) is an orange-coloured body, inso-
luble in most solvents. It is decomposed by sunlight, and is a
powerful reducing agent.
No compound of carbon and silicon is known.
191
CHAPTER IX.
FIYDROGEN.
HYDROGEN:—Compounds of Hydrogen and Oxygen—Water—Compounds of Hydro-
gen with the Haloids, with Nitrogen, with Phosphorus, with Sulphur and Se-
lenium—Compounds with Carbon, viz., Methane, Ethylene and Acetylene-
Flame—Compound of Hydrogen and Silicon.
HYDROGEN (H = 1).
Atomic weight, 1. Molecular weight, 2. Molecular volume, LI I.
Relative weight, 1. Specific gravity, 0-0693. 100 cubic inches weigh
2:1496 grains, and 1 litre = 1 crith, i.e., weighs 0.0896 grim. 1
grin. at 0° C. and at 760 mm. pressure measures 11:19 litres, and
1 grain at 60° F. and 30 B.P. measures 46-73 cubic inches.
Synonyms.-Inflammable Air or Gas (Cavendish, 1781); Phlogiston
(older chemists); Hydrogen (ijöwp water, and yévvaa, I produce) (Asso-
ciated French Chemists). -
History.-The alchymists described “an inflammable air,” which
was, no doubt, hydrogen. It was studied by Paracelsus in the
sixteenth, and by Hales in the seventeenth century, when engaged
in examining the gas produced by the distillation of coal. Cavendish
(1766) examined it more carefully, and was the first to set it free by
the action of acids on metals. Its properties were afterwards investi-
gated by Watt, Priestley, Volta, and others.
Natural History.-(a.) In the mineral kingdom it is found free in
volcanic gases (to the extent, at times, of 25 per cent.), in firedamp,
and also occluded in meteorites (see page 193). In a combined
state, it forms one-ninth part by weight of water, three-seventeenths
of ammonia, one seventeenth of sulphuretted hydrogen, etc. (6.) In
the vegetable kingdom it is found as a constituent of all tissues, as well
as in the water with which in all cases the tissue is associated; whilst
(y.) In the animal kingdom it is always found in the tissues, and occa-
sionally in a free state in the breath.
Preparation.—(1.) By the electrolysis of water, the hydrogen
being developed at the negative pole.
(2.) By the action of an intense heat on water.
(3.) By the action of sodium and potassium on water at common
temperatures.
2H20 + Nag = 2NaPIO + H2.
Water + Sodium = Sodic hydrate + Hydrogen.
(2OH2 + Nag. = 20 NaH + H2.)
192 HANDBOOK OF MODERN CHEMISTRY.
(4.) By passing steam over certain red hot metals, such as iron.
3Fe + 4H2O = Fe3O4 + 4H2.
Iron + Water Triferric tetroxide + Hydrogen.
(Black or magnetic oxide)
(Fe3 + 4OH, - FesO4 + 4H2.
[NotE.—Metallic platinum cannot be made to decompose water at
any temperature, but if the platinum be intimately associated with
magnesium or with zinc, decomposition of the water may be
effected at ordinary temperatures. Copper decomposes water at a
very high temperature, but if the copper be associated with zinc it
then decomposes it at ordinary temperatures. (Proceedings of R. S.,
1872, pp. 133, 218.])
(5.) By passing steam over red hot coke or charcoal (Deville and
Debray):—
2H2O + C - 2H2 + CO2.
Water + Carbon = Hydrogen + Carbonic anhydride.
[2OH2+ C == 2H2 + CO2].
[NotE.-The CO2 may be removed by lime. If the heat be too
great, CO (and not CO2) is formed, this gas being incapable of re-
moval by lime].
(6.) By the action of hydrochloric or dilute sulphuric acid on zinc
and on certain other metals:—
Zn + 2 HCl = ZnCl2 + H2.
Zinc + Hydrochloric = Zincic Chloride + Hydrogen.
(a.) acid.
[Zn + 2.HCl = ZnCl2 + H2.]
Zn + H2SO, - ZnSO, + Hg.
(3.) Zinc + Sulphuric acid = Zincic sulphate + Hydrogen.
lf. + SO2 Hog = SO2Zno" + H2.]
[NOTE.-(a.) On closing the vessel in which hydrogen is being generated by the
action of dilute sulphuric acid on zinc, the pressure of the gas stops further decom-
position. It has been suggested that, in this case, pressure stops affinity by preventing
the escape of bubbles of hydrogen, the effect of which ordinarily is to displace the
zincic sulphate solution immediately surrounding the zinc. This being stopped, fresh
acid is prevented from coming into contact with the metal. (3.) The hydrogen pre-
pared by the action of acids on metals is not pure, but contains certain compounds of
H and C, which may be removed by passing the gas through wood charcoal, and also
of H and S, and H and As. It may be purified from these latter by passing it through
solutions of caustic potash and argentic nitrate respectively.]
(7.) By boiling zinc in a solution of potassic hydrate, the zinc
displacing the hydrogen:—
2KHO + Zn = Zn]K2O2 + H2.
Potassic hydrate + Zinc = Potassic zincic oxide + Hydrogen.
[2OKH + Zn = Zn]Ko. -- H2.]
(8.) By submitting certain organic substances to destructive distilla-
tion.
HYDROGEN. 193
Properties, (a.) Sensible—When pure, hydrogen is a colorless
gas, without taste or odor,
(3) Physiological,—It has no toxic effects. It may be breathed for
a few seconds (when pure) with impunity, the voice being rendered
peculiarly shrill under its influence. If breathed continuously, death
results from want of oxygen,
(y.) Physical,—Hydrogen is the lightest body known, being 14:47
times lighter than air (Sp. Gr, 0.0693), Sound travels three times
faster in it than in air. It is a permanent gas, that is, no cold or
pressure can effect its condensation. It refracts light more powerfully
than any other gas; compared with air, at the same temperature and
density, its refracting power is six times as great. Hydrogen exhibits
in a remarkable degree the power of diffusion, i.e., a power due to the
constant motion and mutual repulsion of gas particles. If a bottle of
hydrogen be connected vertically, by a narrow glass tube, with a
bottle of oxygen, the oxygen (the heavier gas) being below, the
hydrogen, against the action of gravity, will descend, and the oxygen
will ascend, a complete mixture of the gases in the two bottles re-
sulting. Similarly, if a vessel be divided into two parts by a porous
diaphragm, one-half being filled with one gas and the other half
with another gas, diffusion will take place until the admixture of the
gases is complete. But the rate of diffusion is not alike. Graham's
law is expressed thus:–“ The diffusibility of two gases varies inversely
as the square roots of their densities.” Thus, the density of H = 1 and
of O = 16, therefore the diffusibility of these two gases is as 4 to 1 ;
in other words, the diffusion of four cubic inches of hydrogen will
occupy the same time as the diffusion of one cubic inch of oxygen.
The “diffusiometer” of Graham is a glass tube closed at one end by
some porous material, such as well-dried plaster of Paris. If this be
filled with hydrogen and the open end placed in water, the water
rises rapidly in the tube, because the hydrogen passes through the
porous diaphragm (i. e. diffuses) at a greater rate than the air enters;
i. e., H = 1 and air = 14:47, therefore their relative diffusibility =
v/14:47 to v^T, or as 3.8 to 1; or, for every 1 cubic inch of air
entering the tube, 3.8 cubic inches of hydrogen escape. It will be
seen, therefore, that by this means a mixture of two gases of un-
equal diffusibility may be partially separated (atmolysis).
By the term osmosis, we imply not simply diffusion through small
apertures, but the passage through membranous diaphragms. Here,
adhesion between the membrane and the gas plays its part in the
process, as well as diffusion.
We have remarked that hydrogen is found occluded, that is, ab-
sorbed, in meteoric iron. If hydrogen be passed over a red-hot
plate of platinum, the metal will absorb 3-8 times its own volume of
the gas, whilst palladium will absorb 376 volumes at common tempe-
ratures, 643 volumes at 194°F. (90° C.), and 526 volumes at 473° F.
O
194 FIANDBOOK OF MODERN CHEMISTRY.
(245° C.), the occluded hydrogen being in every case completely
evolved on the application of heat. The absorbed gas possesses
great chemical activity, for if the palladium containing the occluded
hydrogen be placed in a jar of chlorine, or in an iodine solution,
hydrochloric and hydriodic acids will be formed; and, by similar
means, ferric oxide may be changed to ferrous oxide. Graham held
that in this and like cases an alloy of palladium or other metal and
hydrogen (to which, in this state, he gave the name “ hydrogenium ”)
was formed, but of this there is considerable doubt.
The analogy between hydrogen and the metals is well marked, nor
is the fact of its gaseous condition any argument against its metallic
nature.
(6.) Chemical.—Hydrogen has no action on litmus or turmeric. It
will not support combustion, but it burns, when pure, with a per-
fectly colorless flame, any color being probably due to some impurity,
such as a trace of sulphur either in the air or in the gas. Water is
the only product of its combustion (noted by Macquer, 1766). In
burning, it produces a greater heat than an equal bulk of any known
substance; one grain of hydrogen, in combining with eight grains of
Oxygen, produces sufficient heat to raise 62,031 grains of water 19 F.,
or 34,462 grains 1° C.
With oxygen, hydrogen does not combine under ordinary circum-
stances; but by the action of heat, or by spongy platinum, or when
the gases are nascent, combination may be easily effected. [The ex-
plosion resulting from firing the mixed gases depends on the sudden
expansion caused by the heat developed by the combination.]
In the case of the haloids, heat is required to effect the chemical
union of hydrogen with iodine and fluorine, whilst daylight is sufficient
to effect its combination with chlorine and bromine.
With nitrogen, combination may be effected directly, if the gas be
in a nascent state, when ammonia is formed.
With carbon and sulphur, the direct union, and with phosphorus,
selenium, silicon, etc., the indirect union of hydrogen may be effected.
With antimony and arsenic, hydrogen, when nascent, forms gaseous
combinations.
Water dissolves a trace of hydrogen; 100 volumes take up 1.93
volumes of the gas, its solubility being unaffected by the temperature
of the solvent.
The acids have no action upon it, except that nascent hydrogen
reduces nitric acid.
The alkalies are also without action upon it.
With the metals, hydrogen forms but few compounds.
Metallic orides are unaffected by hydrogen, unless they be red hot,
when they are reduced.
Comparing hydrogen with oxygen, we may note their remarkable
chemical dissimilarity; oxygen combines with all the elements (and
WATER. - 195
commonly directly) except with fluorine, whereas the hydrogen com-
pound with fluorine is easily formed and of great stability; moreover,
hydrogen combines directly with none of the elements except with
oxygen, carbon, sulphur, and the haloids (fluorine excepted). The
combining power between oxygen and the metals is intense, whilst
that between hydrogen and the metals is almost nil.
Its proportion in gaseous mixtures may be determined by a eudio-
metric experiment, as already described (page 98).
CoMPOUNDs of HYDROGEN AND OxYGEN.
Water ... - - - tº dº tº e to º ... H.O.
Peroxide of hydrogen ... º º 'º ... H.O.
WATER (H2O or OH2).
Molecular weight, 18; Density, 9; Specific gravity, 1.000.
History.-Water was regarded by the ancients as an element.
Thales (600 B.C.) describes it as the origin of all things; Van Helmont
(1600 A.D.) estimated the quantities present in various animal,
vegetable, and mineral compounds. Priestley (1780) correctly
predicted its composition from noting the moisture formed on firing a
mixture of air and hydrogen. Watt and Cavendish (1781-1783)
confirmed Priestley's predictions by more accurate experiments,
proving its compound nature and the proportions of its constituents.
Lavoisier and Laplace (1783-4) added further confirmatory proofs of
its exact composition.
Natural History.—(a.) In the mineral kingdom it is found as
water, in (a) the atmosphere, also as rain, snow, and hail; and (b)
in seas and rivers. It is estimated that ; of the earth's surface, or
32,000,000 cubic miles is water. It also occurs (c) below the surface
of the earth to a certain depth, thrown up here and there as springs,
and (d) lastly, combined in many minerals as hydrates. (3.) In the
vegetable kingdom, and (y.) also in the animal kingdom, a large per-
centage is water.
Preparation.—Chemically pure water is not found in nature. It
may be prepared by distillation, that is, by vaporizing the water and
condensing the vapor. Filtration removes suspended matters only.
Composition.
By By weight By weight
volumes. (atomic). (percentage).
Hydrogen ... H. = 2 2 11 : 1 1
Oxygen ... O = 1 16 SS-89
H2O= 3 18 100 : 00
The two volumes of hydrogen combining with one volume of oxygen
form two volumes of water gas.
196 HANDBOOK OF MODERN CHEMISTRY.
Proofs of its composition.—These are both analytical and synthetical.
(A.) Analytical. (1.) By the electrolysis of water.
Placing the platinum terminals of a galvanic battery in a weak acid
solution, the acid being added to increase the conductivity of the
Water, hydrogen will be immediately evolved from the negative,
and oxygen from the positive pole. The volume of oxygen evolved
is slightly less than one-half the volume of hydrogen. It should be
exactly one-half, but (1) oxygen is more soluble than hydrogen in
water, and (2) some of the oxygen is ozonized (as may be proved by
its action on iodized starch paper), in which form three volumes are
condensed into two. Allowing for this, the experiment proves that
water is made up of 2 volumes of hydrogen + 1 volume of oaygen.
The same fact might also be demonstrated by passing sparks from
the induction coil through steam, whereby it is decomposed, and
analyzing the products formed.
Oxygen is sixteen times heavier than hydrogen. The bulk of
hydrogen in water being twice that of oxygen, it follows, therefore,
that in 18 parts by weight of water we have 2 parts by weight of
hydrogen + 16 parts by weight of Oaygen.
(2.) That water is made up of oxygen and hydrogen in these pro-
portions by weight may be proved by passing steam over a weighed
quantity of red-hot iron, whereby the water is decomposed, hydrogen
passing over in a free state, and an oxide of iron formed. The
hydrogen may be measured and its weight estimated, whilst the weight
of the oxygen in combination with the iron may also be determined.
(B.) Synthetical. (1.) If two volumes of hydrogen and one volume of
oxygen be fired in a eudiometer by an electric spark, they combine
with explosion, this being due to the energetic and rapid combination
of the gases, attended with sudden expansion and great evolution of
heat. The water gas (H2O) formed will measure (when compared
under identical conditions and at such a temperature that the water is
in a state of gas) two-thirds the bulk of the original gas, or, in other
words, three volumes of the mixed gases will be found to form two
volumes of steam. (Cavendish.) (See page 34.)
It may further be noted that combination in these proportions is
constant. If oxygen and hydrogen be mixed in arbitrary proportions
and exploded, combination always occurs in the proportion of two
volumes of hydrogen with one volume of oxygen, whilst the gas
added in excess, remains unaltered after explosion. -
(2.) If a stream of pure hydrogen be passed over a weighed
quantity of hot and well-dried cupric oxide, the hydrogen will deprive
the copper of its oxygen, and steam will be formed. If the water be
collected and weighed, and the weight of the reduced copper be also
estimated (loss=0), we shall be able to determine the relative
weights of oxygen and hydrogen present in the water formed.
(Dulong and Berzelius, Dumas and Boussingault).
WATER. 197
(3.) Water is the only product of the combustion of hydrogen in air
or oxygen. And, moreover, whenever combustible bodies containing
hydrogen, such as tallow, oil, coal gas, etc., burn with flame, water
is always found as one product of the combustion.
It may here be noted that enormous heat is evolved by the union of
hydrogen and oxygen. Thus, the oxy-hydrogen jet supplies us with
a heat almost unsurpassed by chemical means.
Properties.-(a.) Sensible.—Water (when pure) is usually said to
have neither color, taste, nor smell. As regards its color, we note that
when a layer of six feet is examined by transmitted light, it appears
of a blue tint, and in still greater bulk, as seen in the Swiss lakes, of
a bluish green tint. The presence of organic matter, however, even
in minute quantity, imparts a brownish tinge to the water, so much
so, that the tint-depth may be taken as a rough indication of the
amount of organic matter present in solution.
As regards its odor, although this cannot be detected by man,
animals smell it at long distances, as shown in the case of horses and
camels in the desert.
Physical.—(3.) The specific gravity of water at 39.2°F. (4°C.), (its
point of maximum density) is regarded as 1.000, and is the standard
of comparison for solids and liquids.
Water may exist in the solid, liquid or gaseous state. The change
from the solid into the liquid, or from the liquid into the gaseous
state, involves the absorption of heat.
As to its weight—
1 cub. in, of water weighs (62°F. or 16.7°C.) 252.456 grs., Sp. Gr. 1,000
,, of ice ,, (32°F. or 0°C.) 235.000 grs., Sp. Gr. 0.91674
,, of steam , (212°F. or 100° C.) 0-1932 gr., Sp. Gr. 0.623 (0-0693×9)
52'4
35-0
Water is therefore about 825 times heavier than air. A cubic foot
weighs about 1000 ozs. avoird. (actually 997 ozs.); one gallon, 70,000
grains, or about 10 lbs. avoird, ; 1 litre (at 4°C.), 1000 grammes, or
1 kilogramme.
Water is practically incompressible. Every atmosphere contracts
it about fifty-one-millionths of its bulk, or a presssure of 30,000 lbs.
will force 14 volumes into 13. (Regnault.)
The action of heat.—At all temperatures, water evaporates. At
32°F. (0°C.) it freezes. If this frozen water be heated it melts, but
until the whole of the ice be melted the liquid remains at 32°F.
(0°C.), notwithstanding the application of heat. After the ice is
melted, its temperature gradually rises as the heat is continued up to
212°F. (100°C.), when the water boils, whilst if the heat be applied
long enough, the water will entirely boil away.
I.—We say, then, water freezes or becomes solid at 32°F. or 0°C.
But the exact temperature of freezing is influenced by a variety of
circumstances. The melting point of ice is more constant than the
Jreezing point of water; hence, the former is usually employed in
198 HANIDBOOK OF MODERN CIIPMISTRY.
graduating thermometers. The circumstances influencing the tem-
perature of freezing are as follows:—
(a.) The presence of atmospheric air. In closed vessels, at perfect
rest and out of contact with air, the temperature of water may be
lowered to 14°F. (–10°C.) without solidification, but if the water at
this temperature be shaken, it instantly freezes, the temperature
immediately rising to 32°F. (0°C.).
(3.) In closed vessels, air being present, or in very narrow tubes,
water may be cooled to 5°F. (– 15°C.) without its becoming frozen,
solidification occurring on the slightest motion being imparted to the
liquid.
(y.) If water be surrounded by certain mixtures (such as chloro-
form and sweet almond oil, which may be mixed in such proportions
that the liquid has the same density as water), the water thus
encircled may be cooled, without solidifying, to —4°F. (–20°C.). If,
in this state, however, it be touched with a piece of ice, it instantly
freezes and expands.
(6.) Pressure.—The melting point is lowered 0.0075°C. for every
additional atmosphere. At a pressure, therefore, of 13,000 atmo-
spheres, ice would be converted into water at 0:4°F. (–18°C.) Water
at 39.2°F. (4°C.), enclosed in a perfectly tight vessel where expansion
is impossible, will not freeze although cooled below zero. The ice
crystals are rhombohedric and six-sided prisms.
II. On heating ice at 32°F. (0°C.), we note that the application of
heat does not raise the temperature until the whole of the ice is
melted. Thus, ice at 32°F. (0°C.) uses up heat to become water at
32°F. (0°C.). The amount of heat thus used up by a given amount
of ice is called the latent heat of water. A pound of water at 32°F.
(0°C.) mixed with a pound of water at 175° F (79.44°C.) will have
32 + 175
2
32° F (0°C.), mixed with a pound of water 175°F. (79.44°C.) will
have a temperature of 32°F., but the ice will have melted, 143 degrees F.
having been required for this purpose. Note, therefore,
175 – 143 = 32; temperature of liquid _*** – 32° F.
We regard, therefore, 143° F. (79.4°C.) as the latent heat of water;
in other words, 143°F. (79.4°C.) is the heat, unrecognisable by a
thermometer, absorbed by 1 lb. of ice in becoming water.
[For explanation of thermal unit, or unit of heat, vide page 37.]
III.-Ice presents a peculiar phenomenon termed “Regelation.”
Two pieces of ice, on being Squeezed together, cohere. This cohesion
(“regelation”) is probably due to a certain portion of the ice be-
coming melted at the points of contact, owing to the melting point
being lowered by the pressure, Instantly, however, that the pressure
is removed, the Water solidifies.
a mean temperature of =103.5° F., whilst a pound of ice at
WATER. 199
IV. After a sufficiency of heat has been applied, the water boils.
Water evaporates (that is, gives off vapor) at all temperatures. The
vapor thus given off has a certain “elastic power,” or “tension.”
Air also has an “elastic power,” or “tension,” which is capable of
supporting 760 mm., or nearly 30 inches of mercury; in other words,
air has an elastic power capable of exerting a pressure of 15lbs. on
every square inch. When the tension or pressure of the vapor given
off by the water under the action of heat, balances the tension or
pressure of the atmosphere, the water is said to boil. This occurs at
212° F (100° C).
W. Various circumstances influence the temperature at which
water boils.
(a.) Boiling, we have said, is the “temperature at which the pres-
sure or the tension of the water-vapor balances the pressure of the
atmosphere;” thus inasmuch as the pressure of the atmosphere con-
stantly varies, it follows that the boiling-point of water must also
vary. It is only when the barometer is at 760 mm. (that is, the
mean height of the barometer at the sea-level) that water boils at
100° C., the boiling point being reduced 1° C. for every 27 mm. that
the barometer falls. If water be placed under the exhausted receiver
of an air-pump it may be made to boil even at common temperatures.
On Mont Blanc (417 mm. pressure), water boils at 1832°F. (84°C.).
It will be seen, therefore, that by noting the temperature at which
water boils, by means of what are called hypsometric thermometers, we
may infer, approximately, the elevation. For every 590 feet the boil-
ing point is lowered about 1°F. (19 C.) for every 1,062 feet.
The following table gives the tension of aqueous vapor at different
temperatures. It will be noted that at 212°F. (100° C.), the vapor
tension of water is equal to the pressure of the atmosphere (760 mm.).
Hence water boils at 212°F. (100°C.):—
Tension of the vapor of water (Regnault.)

Temperature. Tension in Mm. Temperature. Tension in Mm.
- of Mercury. of Mercury.
oR. oC. oR. oC.
— 4 –20 0-927 104 40 - 54-906
+ 14 —10 2 : 09.3 122 50 91-982
32 0 4 - 600 140 60 148-791
41 + 5 6-534 15S 70 233- 0.93
50 10 9. 165 176 80 354-280
59 15 12. 699 194 90 525-450
68 20 17.391 212 100 760-000
86 30 31'548
The above diagram will show the importance when graduating
thermometers, of accurately noting the barometric pressure at the
time of graduation.
Further, by increasing the atmospheric pressure the temperature at
200 h HANDDOOIK OF MODERN CHEMISTRY.
which water boils will also be increased. With one atmosphere (i.e.,
760 mm. pressure) we have seen that water boils at 212°F. (100° C.);
with two atmospheres it requires a heat of 249°F. (120.6° C); with
three atmospheres, of 273° F (133.9°C.); with ten atmospheres, of
356-5°F. (180.3°C.); with twenty atmospheres, of 415.4°F. (213°C.);
and so on.
(3.) The boiling point varies with the purity of the liquid :—
A saturated solution of sodic carbonate boils at 104.6°C, or 220-2° F.
5 y 2 3 ,, sodic chloride 5 y 108.4° C. or 227-0° F.
y 3 2 3 ,, potassic nitrate 2 3 115.9°C, or 240-6° F.
5 y } } ,, sodic nitrate 5 3 121.0° C. or 249.8° F.
} } y 5 ,, potassic carbonate ,, 133-0° C. or 271.4° F.
5 y 2 y 2 ) calcic chloride } } 179.5° C. Ol' 355.1° F.
(y.) The boiling point depends on the depth of the bulk heated. A
column 32 feet deep would not completely boil—that is, give off vapor
from the bottom of the vessel—at a lower temperature than 249.8° F.
(121° C.)
(3.) The boiling point varies with the vessel in which the water is
boiled. The adhesion of water for glass is greater than the adhesion
of water for metal. This adhesion must be overcome ; and hence, in
the case of very clean glass, the adhesion between the glass and the
water particles may raise the boiling point 1 or 2 degrees.
(e.) In boiling, the cohesion of the particles of water for one
another has also to be overcome by heat. The presence of gases in
solution lowers the boiling point by destroying this attraction of the
water particles, and, conversely, the absence of dissolved gases
heightens the boiling point.
WI. The latent heat of steam is said to be 997° F., or 537°C. (i.e.,
537 thermal units), that is, the heat required to boil away 1 lb. of
water at 212° F (160° C.), will raise 5:371bs. of water from 32° to
212°F. (=180 degrees F.), [or from 0° to 100°C. (=100 degrees C.)];
or if the steam from 1 lb. of water be conveyed into 5' 37 lbs. of Water
at 32° F (0°C), it will raise it to 212° F (100° C.).
(180 × 5-37 = 996-66, or 100 x 5.87 = 537), -
VII. If a drop of water be placed on a red-hot platinum dish, it
assumes what is called the spheroidal condition ; that is, the spheroid
rests on a cushion of its own vapor, which, being a bad conductor of
heat, prevents the spheroid of water boiling. The temperature of
the spheroid has been ascertained to be about 194°F. (90° C), and
the space between the spheroid and the dish to be about 0.15 to
0°25 mm, - -
VIII, On subjecting water to the action of intense cold, it gra-
dually contracts to 39.2°F. (4°C.). This temperature is what is
called “ the marimum density of water.” [We should note that the
presence of soluble salts lowers the maximum density, so that in sea-
water it is below 32°F. (0°C.)] At this point of maximum density
WATER, 201
a given bulk of water weighs more than at any other temperature.
Hence 1 c.c. of water, at 39.2°F., or 4°C., is taken as representing
a gramme weight. Below 39.2°F. (4°C.) water expands rapidly, so
that ice floats on water, owing to its less specific gravity. (1 Volume
of water at 0°C. becomes 1-09082 volume of ice). Thus water-pipes
break, rocks disintegrate, and rivers and lakes freeze only on the
surface, the ice easily melting as the warm weather returns. At
39.2°F. (4°C.) convection in (i.e., the circulation of) rivers and lakes
C68.SéS.
When water is heated from 39.2°F. (4°C.) it expands; 1 volume
of water at 39.2°F. (4° C), becoming 1:04.312 volumes at 212°F.
(100° C.).
We may here note that aqueous vapour is very opaque to heat.
Thus the moisture of the air prevents radiation from the earth.
Water is a simple refractor of light, its refracting power increasing
as it is cooled, this increase of refraction not being interfered with by
its expansion below 39.2°F. (4° C). (Arago and Fresnel.)
Water as a neutral solvent is unsurpassed. Solution is generally
a purely physical act, neither heat nor change of property resulting.
The act of liquefaction (i.e., the passage from a solid to a liquid) is
usually accompanied by cold (i.e., the absorption of heat).
I. Solubility of solids in water.—The rapidity with which a solid dis-
solves depends—(1) on whether the solid be in lump, or finely.
powdered; and (2), on the motion imparted to the mixture. In the
first case, powdering the body increases the surface upon which the
water acts; and in the second, motion removes the saturated solution
surrounding the solid, thus bringing fresh and unsaturated portions
of the solvent into contact with the material. If such motion be not
imparted to the menstruum during the period of action, solution is
slow and only proceeds by “liquid diffusion ” (a process analogous to
“gaseous diffusion ”), i.e., the passage of a solution of one salt into a solution
of a second salt contrary to gravity. This diffusive power varies with
different bodies. It is rapid with potassic chloride, and with most
crystalline bodies, but slow with gelatine and with most jelly-like
bodies. Bodies that diffuse rapidly are called “crystalloids,” and
bodies that diffuse slowly or not at all, “colloids.” This diffusion of
certain bodies and non-diffusion of others takes place equally well
if a membrane separates the two liquids (Dialysis), the rapidity with
which one liquid passes through the membrane into the second, in no
way necessarily representing the rate at which the second passes
through and into the first. *
In describing the solubility of solids, it is usual to state the number
of parts of anhydrous salt taken up by 100 parts of water at a given
temperature.
Ordinarily the solubility of a body increases, as the temperature
increases. If a boiling solution of a salt be allowed to cool, exposed
202 HANDBOOK OF MODERN CHIEMISTRY.
to the air, a certain portion of the salt crystallizes out and the clear
solution, at normal temperatures, is termed “a saturated solution,”
i. e., a solution which at that temperature can dissolve no more of the
salt; but if it be allowed to cool out of contact with air, a larger quan-
tity of the salt is then held in solution, and this is termed “a super-
Saturated solution,” from which, however, the excess of solid matter
may often be separated by slight physical disturbances, such as
motion, dust, or dropping into the solution a minute fragment of the
salt.
A saturated solution of one salt will often dissolve an appreciable
amount of a second salt.
The influence of temperature on solubility is not constant.
(1.) The solubility, for instance, of potassic chloride is directly as
the temperature, but the solubility of potassic chlorate increases far
more rapidly than the temperature.
(2.) The solubility of some bodies, such as sodic chloride, is the same
at all temperatures.
(3.) The solubility, in some cases, decreases as the water is heated.
Thus lime, is twice as soluble in water at 32°F. (0°C.) as it is in
water at 212°F. (100° C.). One part of strontic sulphate requires
7,000 parts of water at 57.2°F. (14°C.) and 9600 parts at 212°F.
(100° C.) for complete solution.
(4.) Occasionally the maximum solubility of substances is at a tem-
perature a little above the common temperature, and decreases if the
temperature be raised. Thus at 32°F. (0°C) 1 part of calcic sulphate
is soluble in 488 parts of water, but at 95° F. (35°C.) 1 part is soluble
in 393 of water. This is the point of maximum solubility of calcic
sulphate in water, and from this point its solubility decreases, for, at
212°F. (100°C.) 1 part requires 460 of water for solution.
Water, when “super-heated,” i. e., heated under pressure, possesses
greatly increased solvent powers. Thus, at 300°F. (149°C.) water
dissolves glass. Possibly the solution of silica in the Geyser springs,
may be accounted for by the action of water, superheated by internal
pressure.
II. Solubility of liquids in water.—By this is implied the miscibility
or the blending of liquids. Water mixes with alcohol. If the water
be in excess the water is regarded as the solvent, but the alcohol if it
be in excess.
III. Solubility of gases. – All gases are more or less soluble in
water—i.e., are more or less absorbed by water—but all gases are not
equally soluble.
The “coefficient of solubility,” or ‘absorption coefficient,’ as it is called,
is the volume of gas absorbed by one volume of water at 59° F.
(15° C.)
The following table exhibits the absorption or solution of various
gaSeS.
WATER. 203
Wol. dissolved by one. Wol. dissolved by one
Gas at 59°F. (B.P. 30). vol. of water at 59° F. vol. of water at 32° F.
(15° C.) and 30 B.P. (0°C.) and 30 B.P.
Hydrogen tº a tº e is tº •019.3 •0193
Nitrogen . . tº e m e tº º - •0148 •0203
Carbonic oxide .. * * is tº •0243 •0328
Oxygen . . s & tº tº tº tº • 0299 '0411
Marsh gas & ſº * & $ ſº •0391 •0545
Olefiant gas tº e s & & 4 •1615 • 2563
Nitrous oxide .. • 4 tº e •7780 1 - 3052
Carbonic acid 1*0000 1-7967
Chlorine . . tº e * * 2- 56.80 tº-
Sulphuretted hydrogen . . 3.2326 4.3706
Sulphurous acid .. e - 43-5640 68-8610
Hydrochloric acid 457-8000 505-8000
Ammonia. . 782-7000 1148 0000
[NotE.—The absorption coefficient is often stated as the volume of
gas at 0°C. and 766 mm. absorbed by 1 c.c. of liquid at 0°C. and
766 mm.] -
The solubility of a gas in water (and, indeed, in all other solvents)
is influenced by certain circumstances.
(1.) The temperature of the solvent.—The general law may be thus
stated:—The volume of gas dissolved increases as the temperature of the
solvent decreases. But note—
(a.) In the case of hydrogen, the solubility remains the same for
all temperatures.
(3.) The law is only true so long as the solvent remains liquid, for
directly the liquid freezes, the dissolved gases are usually liberated.
But exceptions to this rule are found in the case of condensible gases,
such as carbonic anhydride, and in the case of those gases such as
chlorine, which form definite chemical compounds with water.
When the solvent is boiled, the dissolved gas is, as a rule, entirely
evolved. In the case, however, of those gases that are very soluble
(such as hydrochloric acid gas), mere boiling never effects the entire
expulsion of the gas. The solution having become of a certain
strength, remains constant, evaporation to dryness being the only
means of effecting the complete removal of the remainder.
(2.) The degree of pressure.—In the case of the moderately soluble, but
not in the case of the very soluble gases, Dalton and Henry's law holds
good, that “the volume of gas absorbed, varies directly with the pressure.”
With a pressure, e.g., of one atmosphere, one volume of water at 0°C.
dissolves 1:18 volumes of CO2; with # atmosphere, *—) 0.59
volume; with 2 atmospheres, (1:18 × 2–) 2.36 volumes, etc.
By placing a solution of gas in a vacuum, its almost entire removal
from the solvent may be effected. It may be noted, moreover, that a
similar withdrawal may often be effected by exposing the solution of
one gas to an atmosphere of a second gas.
204 HANDBook of MODERN CHEMISTRY.
We have now to consider the action of solvents on a mixture of
gases.—Good drinking water should be well aerated, i.e., should
contain a certain quantity of dissolved gas. Every gallon of water
should yield 7 to 8 cubic inches of gas, or about 4 cubic inches of
nitrogen, 2 cubic inches of oxygen, and 1 cubic inch of carbonic
anhydride. These gases are dissolved by the water from the air.
But air is a mixture of 1 part of oxygen to 4 parts of nitrogen (exactly
as 21 to 79), whereas the dissolved gas is in the proportion of 1 of
oxygen to 2 of nitrogen. How is it, then, that the ratio of the gases
dissolved by the water, is not the same as that in which they are
present in the air 2 .
In a mixed gas the solution of the several constituents does not
depend on the general pressure, but on the pressure everted by each gas
‘per se.” For example, to take a simple case: If we act with water on
a mixture of one volume of oxygen and three volumes of nitrogen
under a pressure of four atmospheres, we shall find that the oxygen
dissolved, will be that quantity that the water can absorb under one
atmosphere (i.e., the 4th of four atmospheres); and the nitrogen,
the quantity the water can absorb under a pressure of three atmo-
spheres (i.e., #ths of four atmospheres). So with air, 4th of which
is oxygen and #ths nitrogen, the pressure of the whole being
one atmosphere. The quantity of each gas dissolved will be found
by multiplying the proportion of the gas in the mixture, by its
co-efficient of solubility; thus—
0.0299 (coefficient of absorption of oxygen) X+ (proportion of oxygen in air)=0.00598
0-0148 ( do. do. of nitrogen) × ( do. of nitrogen do.) =0.01184
0.01782
Therefore, of every 0-01782 volumes of air dissolved by water,
0.00598 will be oxygen and 0.01184 nitrogen ; that is, in about the
proportion of two of mitrogen to one of oxygen. Thus, the air
dissolved by water is richer in oxygen than the atmosphere. This
oxygen is present in the water, not only for the support of water-
animal life, but for its own self-purification, whereby harmful
products are changed into harmless products by oxidation. The
carbonic acid, too, plays its part in rock disintegration and in soil-
formation,
Water dissolves the haloid elements, and is slowly decomposed by
them with the evolution of oxygen (H20+Cl2=2|HCl·HO). On the
combustible solids (carbon, etc.) it has little or no action unless it be
heated, when it is decomposed (C+ H2O=CO+ H2). On oxygen,
nitrogen, and hydrogen, its action is simply solution. The metals
are attacked differently by it. (a.) Some, as the alkaline metals
decompose it at ordinary temperatures; (3) others, as magnesium,
decompose it if the water be boiling; (y) others, as iron, 2&ng, etc.,
WATER. - 205
decompose it when the metals are red hot; whilst (8) gold and
platinum require to be raised to a white heat in order to effect its
decomposition.
(y.) Chemical.—Water is without action either on litmus or turmeric.
Chemically, it is an indifferent oxide. It unites with bodies in several
ways to form hydrates. Thus— -
(1.) It unites with the anhydrides to form acids, heat being evolved
at the time of combination (SO,--H.0=H.S.O.). This water molecule
cannot be afterwards separated from the anhydride, merely by the
action of heat. Sulphuric acid, moreover, has a great affinity for water,
and hence one of its common laboratory uses.
(2.) It unites with bases to form hydrates, heat being evolved at the
time of combination. In some cases the water molecule cannot be
driven off by heat (e.g., KHO), whilst in other cases a red heat will
effect its expulsion (e.g., CaFI2O2=CaO + H2O).
(3.) It unites with certain bodies as water of crystallization, i.e., water
connected with the shape and color of the crystal. This water
of crystallization may be expelled at a temperature of 212°F.
(100°C.), certain changes resulting. Thus, if blue sulphate of copper
(CuSO4, 5H2O) be heated to 212°F. (100°C.), it loses four of its water
molecules, becoming CuSO4, H2O, whilst at the same time it loses both
shape and color. So again the pink hydrated chloride of cobalt
(CoCl2 + 6aq) forms when heated the blue anhydrous chloride (CoCl2),
which again becomes hydrous and pink on exposure to air (sympathetic
ink). Similar changes of color are well marked in the magnesie-
platino-cyanide, which is green, red, yellow, or white, according to the
quantity of water of crystallization it contains. Some salts (as e.g.,
NaCl) contain no water of crystallization, whilst in many others (as
e.g., sodic sulphate, borax, etc.), the number of water molecules may
be made to vary, different crystalline shapes resulting.
In some cases (as e.g., sodic carbonate), bodies part with their
water of crystallization at ordinary temperatures (effloresce); whilst in
many others (as e.g., potassic carbonate) they take in more water on
exposure, and melt (deliquésee). Thus calcic chloride is used in the
laboratory as a desiccating agent.
(4.) It unites in certain cases as water of constitution, or water of halhy-
dration, i.e., as water associated with the chemical properties of bodies.
Thus, a Crystal of magnesic sulphate contains 7 molecules of water
(MgSO4,7BI2O). If this be heated to 212°F. (100° C.), 6 molecules
(water of crystallization) are driven off, and the salt is represented
by the formula MgSO4, H.O. No heat, however, short of 410°F.
(210°C.) will effect the removal of this last water molecule, and when
the salt is heated to this temperature, it begins to decompose. It is
clear, therefore, that this last water molecule is bound to the salt by
a closer attraction than the other six molecules, and is termed
“water of constitution.”
206 HANDBOOK OF MODERN CEIEMISTRY.
|
This constitutional molecule of water may often be replaced by
another salt, whereby a double salt is formed. Thus, MgSO, H.O
+6H2O may be made to form MgSO, K2SO,--6H2O, where K.SO,
replaces the molecule of constitutional water.
In order to express these two forms of water in a salt, the water of
constitution is often written in chemical symbol, and the water of
crystallization as aq (aqua), thus, MgSO, H20+6aq.
(5.) Water may possibly exist in many organic bodies, such as
sugar, starch, gum, etc., in a molecular form.
Varieties of Water.
I. Common Water.-(a.) Rain Water.—This is the purest form of
water ; but even in the country, and much more in towns in the
neighbourbood of factories, it is always more or less contaminated
with the various impurities present in the air. The rain always con-
tains more or less sodic chloride, organic matter, ammonia, nitric
acid, etc. If rain water has been allowed to come into contact with
lead, it is certain to dissolve a small quantity of the metal.
The rain collected after a long continuance of wet, is the nearest
approach we know of to pure natural water.
(b.) Spring and Well Water.—The total solids present in these may
vary from 5 to 200 grains per gallon, their quantity and character
being largely dependent on the chemical nature of the soil through
which the water percolates. Calcic and magnesic carbonates and
sulphates, with sodic chloride, are the salts most commonly present.
The presence of nitrites or an excess of nitrates and chlorides, fre-
quently found in the shallow well waters of towns, usually indicate
sewage pollution, the two first being the oxidized products of animal
nitrogenized substances (ammonia and albuminoid bodies), and the
last being derived from the common salt used as food.
Sodic carbonate is commonly found in those well waters (as in the
deep wells of London) that have percolated through a bed of chalk.
The organic matter in the water of wells and springs is usually very
small. Carbonic acid is the chief and very often the only gas present
in such waters. Its origin is, probably, either the subterranean de-
composition of carbonates, or the oxidation of the carbon of organic
matter. It serves to hold the earthy carbonates in Solution. A
spring-water will often exhibit a slight turbidity after standing, due
to the carbonic acid escaping by the exposure of the water to air,
and the consequent precipitation of a part, and often as much as one-
third, of the total calcic or magnesic carbonate.
The temperature of spring-water varies from ice-cold to 167°F.
(75°C.), as in the case of some of the Carlsbad springs. The deep
springs are usually the hottest.
(c.) Lake and Marsh Water usually contain more or less organic
VARIETIES OF WATER. 207
matter. Lake water is of excessively variable composition, being
sometimes very pure (as e.g., Loch Katrine), but at other times loaded
with saline matter.
(d.) River Water.—Its composition depends much on the nature of
the soil through which the river passes, and also on the extent of
motion, the nature of the bed of the river, and the exposure the water
undergoes. River water may be regarded as a mixture of rain, spring,
and lake water. It differs from spring water generally, by being less
clear (spring water undergoing natural filtration), and less sparkling
(the carbonic acid present being in smaller quantity), and usually
containing less solid matter. The organic matter present is derived
from surface drainage and sewage; but this, after a sufficient run,
if well diluted, is in a great measure got rid of, owing to the self-
purifying action of the river.
II. Mineral Waters, i. e., a spring water containing some medici-
nal ingredient. The names given to mineral waters depend on the
predominating ingredient present; thus—
(a.) Acidulous Waters, from carbonic acid, which may be present in
quantities varying from 30 to 200 cubic inches per gallon (Seltzer,
Ilkeston, Spa, Pyrmont, etc.).
(b.) Aperient Saline Waters, from the presence of sulphates:—
(1.) Magnesic sulphate (Epsom, Ileamington, etc.).
(2.) Sodic sulphate (Cheltenham, Scarborough, etc.).
(c.) Calcareous Waters, from calcic sulphate, or from calcic carbon-
ate held in solution by carbonic acid (Matlock, Bath, Bristol, etc.).
(d.) Chalybeate Waters, from the presence of carbonate of iron held
in solution by free carbonic acid (Pyrmont, Tunbridge, etc.). On
exposure to air, Fe2O3, H2O is precipitated (2FeCOs + 0 + H2O =
Fe2O3, H20+ 2CO2)
(e.) Brine, from the presence of sodic chloride, bromide, and iodide
(Middlewich, Shirleywich, Droitwich, etc.).
(f) Alkaline Waters, from the presence of sodic carbonate and bi-
carbonate (Ems, Vichy, Malvern, etc.).
(g.) Siliceous Waters, from the presence of silica (Geysers).
(h.) Sulphuretted or Hepatie Waters (Harrogate, Aix-la-Chapelle,
etc.).
(...) Sulphurous Waters (Springs in the neighbourhood of volcanoes).
(j.) Boracic Waters (Lagoons of Tuscany).
III. Sea-Water.—Sea-water contains a large quantity of sodie
and magnesic chlorides, to which its bitter saline taste is due, and to
the hygroscopic character of which salts, the non-drying of clothes
wetted with sea-water is to be attributed.
The following two analyses of sea-water may be quoted:—
208 HANDBook of MODERN CHEMISTRY.
British Channel Mediterranean
(Schweizer). (Usiglio).
Specific Gravity tº e * , * * 1027-4 (at 16°C.) | 1025-8 (at 21° C.)
Water . . gº º tº º tº G tº º 963-74372 962. 345
Sodic chloride . . tº tº tº tº tº b 28° 0'5948 29' 4 24
Potassic chloride, . tº º tº º & ſº 0.76552 0. 505
Magnesic chloride * * tº º tº ſº 3' 66658 3 - 219
25 bromide tº º * * is tº 0 ()2929 0. 556
,, Sulphate * * is tº & 4 2:29578 2.477
Calcic sulphate . . tº º $ tº tº tº 1 * 4 ()662 1.357
,, carbonate . . tº ºt tº ſº tº $ 0.03301 0-114
Iodine . . tº ºn tº tº ſº § tº ſº tº traces.
Ammonia. . tº ſº tº ſo gº tº tº tº traces.
Ferric oxide tº º is ſº tº wº s & e is 0 003
1000 : 00000 1000-000
The sea is the receptacle for the solid matters discharged by rivers,
and dissolved by them from the earth. Their abstraction again from
the sea and their return to the soil is effected by fish and marine
plants.
IV. Water for Drinking Purposes.—It is important to deter-
TOIIlê-
(1.) Its hardness.—The terms “hard” and “soft,” refer to the soap-
destroying power of a water. Soap is an alkaline stearate. The ad-
dition to it of lime and magnesia decompose it, forming a calcic or
magnesic stearate. Hence the reason why it is difficult to obtain
“a lather ” with hard water, (i.e., a water containing lime and mag-
nesian salts), viz., because a certain quantity of the soap is re-
quired to decompose the calcic and magnesian salts before a lather
can be obtained, whilst, conversely, a lather is at once formed with a
soft water, because of the absence of calcic and magnesic salts. Two
kinds of hardness are usually described—(a.) Temporary hardness,
i.e., hardness due to calcic or magnesic carbonates. These salts are
almost insoluble in pure water, but are freely soluble in water con-
taining carbonic acid (possibly as bicarbonates). On boiling, the
carbonic acid is expelled and the carbonates are precipitated. Hence
temporary hardness is that hardness which may be got rid of by
boiling the water. (3) Permanent hardness, i.e., hardness due to calcic
and magnesia sulphates, etc. This is not got rid of by boiling. By the
terms “total * or “initial hardness '' we imply both the temporary and
permanent hardness of a water.
In expressing the hardness of a water in degrees, it is to be under-
stood that every degree, theoretically, represents 1 grain of calcic car-
bonate or its equivalent in soap-destroying power, in 1 gallon of water.
(2.) Its action on lead.—A water that acts freely on lead is not fitted
for a town supply. -
(3.) Presence of organic matter, which if of animal origin renders
water unwholsome.
HYDRIC PEROXIDE. - 209
Hydric Peroxide (H.O.) {3}.
Molecular weight (probable), 36.
Synonyms.-Peroride of Hydrogen; Hydric Dioxide ; Hydroxyl :
Oxygenated Water.
History.-Discovered by Thénard in 1818, and examined by
Brodie and by Schönbein in 1850.
Preparation.—(1) Peroxide of barium (prepared by heating
caustic baryta (BaO) in a current of oxygen) is first mixed into a
paste with water (BaO2,6H20 being formed), and then added to
dilute hydrochloric acid, surrounded by a freezing mixture.
BaO26 EI2O + 2TBICI - H2O2 + 6H2O + BaCl2
Hydrated baric + Hydrochloric = Hydric peroxide + Water + Baric chloride.
peroxide acid
| Op.” q OH - |
ſ {5Bacon, 2BC = | 3# +6OH.4. BaCl.
By decomposing the BaCl, with dilute sulphuric acid, HCl will be
set free. The process then may be repeated until the liquid is of the
required strength. Finally, the hydrochloric acid may be removed by
argentic sulphate, and the sulphuric acid by baryta water.
(2.) By passing carbonic anhydride through a mixture of water
and baric peroxide—
BaO2 + CO2 + H2O == BaCOs + H2O2.
Baric peroxide–HCarbonic anhydride + Water = Baric carbonate + Hydric peroxide.
O // - rf OH.
| | 5Ba” + CO2 + OH2 = COBao" + | OH.
(Similarly, it may be prepared by adding BaO2 to dilute hydrofluoric
acid, a baric fluoride being precipitated; or by adding potassic per-
oxide to a tartaric acid solution, a potassic tartrate being precipitated.)
Properties, (a.) Sensible and physiological. A colorless and when
concentrated a syrupy liquid, having a slight chlorous odor. It
whitens the skin. It has a powerfully metallic, astringent taste, whiten-
ing and deadening the sensibility of the tongue, and rendering the
saliva thick and viscid.
(3) Physical. Specific gravity, 1453. A temperature of 70° F.
(21.1° C.) effects its slow decomposition, which becomes violent at
212°F. (100° C.), when the liquid evolves 475 times its volume of
oxygen. It does not freeze at —22°F. (–30°C.). It mixes with
water in all proportions.
(y.) Chemical. Its reaction is neutral, but it bleaches litmus.
In contact with ozone, water is produced, and common oxygen set
free. There is very little doubt but that the body described (page
63), as antozone is simply hydric peroxide, its antagonistic action
to ozone being at once apparent by the following equation,
(H2O2 + Og = H2O + 20.). It forms water when acted on with
nascent hydrogen (H.O., +Zn-i-H...SO,-ZnSO,--2H,0). It slowly
P
210 THANIDBOOK OF MODERN CHIEMISTRY.
decomposes, evolving oxygen, leaving common water. (This action
is retarded by the presence of acids, and hastened by alkalies.) Its
decomposition may be effected by powdered metals, such as gold,
silver, platinum, etc., the metals themselves undergoing no change
during the process (see Catalysis). As a chemical agent it has both
oxidizing and reducing properties:–
(1.) Oa'idizing. It bleaches litmus and indigo. It rapidly changes
Selenium, arsenicum, etc., into their highest oxides. It converts
arsenious and sulphurous acids into arsenic and sulphuric acids; sul-
phide into sulphate of lead; the protoxides of iron, cobalt, calcium,
etc., into peroxides, etc., etc.
(2.) Reducing. Mixed with the protoxides of silver, mercury, gold,
etc., it not only loses its own oxygen but effects the reduction of the
oxide (Ag30+2H2O3=Age-H H20+ O.). Similarly it reduces the per-
oxides of manganese, lead, etc. (MnO2+ H2O2=MnO-H H20+O2).
and also chromic and permanganic acids (2GrO3 + 3H2O3=Cr2O3 +
3H2O+ 3O2), it being at the same time itself reduced.
It is to be noted that in all these cases the action is retarded by the
presence of an acid, and aided by the presence of a free alkali.
Tests.--(1.) It liberates iodine from potassic iodide. (H2O2+2KI
=2KHO +I.)
(2.) When added to a solution of guiacum mixed with blood cor-
puscles, it turns it of a blue color. (Schönbein.)
(3.) If chromic anhydride (CrO3) be added to a solution of hydric
peroxide, an unstable perchromic oxide is first formed, Cr.03 being
the ultimate product. This compound is of a blue color and is soluble
in ether, by which means its removal from the solution may be
effected. This constitutes a very delicate test for hydroxyl.
Uses.—It has been used in medicine externally as a lotion and in-
ternally for diabetes and oxaluria. It constitutes the golden hair dye
of the shops, the dyeing action being in reality a bleaching (oxidiz-
ing) action.
COMPOUNDS OF FIYDROGEN AND THE EIALOID ELEMENTs.
Hydrochloric Acid (HCl) (Anhydrous).
Molecular weight, 36-5. Molecular volume, ITT . Relative weight,
1825. Specific gravity, 1:27.
Synonyms.-Spirit of Salts; Marine acid; Muriatic acid; Chloride
of Hydrogen : Chlorhydric acid.
History.—Probably known to Geber in the eighth century. The
process of obtaining it from sulphuric acid and salt was first described
by Glauber. Priestley (1772) was the first who obtained it as a gas.
Its real nature was suspected by Scheele (1774), but it was believed
by Berthollet and others to be an element, until Davy established the
truth of Scheele's suspicions.
Natural History.—It is not found either in the animal or in
FIYIDROCHLORIC ACID. 211
the vegetable kingdom. It is found in the gases issuing from vol-
canoes and in the springs and rivers in their vicinity. It is found
in the air over the sea, and in the neighbourhood of alkali works, etc.
Preparation.—(1.) By the direct combination of equal volumes of
hydrogen and chlorine by heat, light or electricity. (Combination of
these gases does not take place in the dark ; in diffuse daylight com-
bination is slow, whilst in sunlight the action is often accompanied by
explosion.)
(2.) By burning hydrogen in chlorine.
(3.) By the action of dilute sulphuric acid on chlorides.
(a.) Prepared by this method in the laboratory in glass retorts at a
low temperature, the reaction is as follows:—
H2SO, H- NaCl NaHSO, + EIC].
Sulphuric acid + Sodic chloride Hydric sodic sulphate + Hydrochloric acid.
[SO. Hoc -- NaCl SO2HoNao + HCI.]
(3.) Prepared commercially in iron retorts at a high temperature, the
following reaction occurs :—
H2SO4 + 2NaCl = Na2SO4 + 2EIC).
Sulphuric acid + Sodic chloride = Sodic sulphate + Hydrochloric acid.
[SO. Hoa -- 2NaCl = SO.Nao. -- 2HC].
(4.) By passing steam and chlorine through a red hot porcelain
tube (2H2O+2Cl2=4HC1-i-O.)
Properties, (a.) Sensible and physiological.—A colorless, pungent
Smelling gas, having a strong acid taste. It is poisonous to animal
life, and very destructive to vegetation, even when diluted with 25,000
parts of air.
(b.) Physical.—Specific gravity 1-27; 100 cub. in. (at 60°F. and 30
Bar. Pr.) weigh 39:23 grains, and 1 litre (0° C. and 760 mm.) 1.6352
grim. At a pressure of forty atmospheres at 50°F. (10°C.) it forms a
colorless liquid, having a specific gravity of 1:27, less refracting than
water, a solvent of bitumen, and with a very feeble action on litmus.
It has never been frozen.
The gas may be decomposed by electricity.
(c.) Chemical. Hydrochloric acid gas reddens litmus. It neither
supports the combustion of a taper nor is itself combustible. Sodium
and potassium burn in it. It acts on the metals, evolving hydrogen.
It fumes in the air owing to its affinity for water, which absorbs from
480 to 500 times its bulk, The liquefied hydrochloric acid (anhydrous)
dissolves solid litmus without reddening it, and, unlike the solution of
the gas, is without action on iron, zinc, lime, etc., or even on the car-
bonates.
=
Hydrochloric Acid (Solution).
Preparation.—By dissolving the gas in water.
Properties.-(a) Physical. The liquid is colorless if pure, but
more often it is slightly yellow. It fumes in the air. A solution
212 HANDBOOK OF MODERN CHEMISTRY.
containing more than 20 per cent of the acid, evolves when heated
hydrochloric acid gas; but if it contains less than 20 per cent. it then
merely gives off water. A 20 per cent. acid distils unchanged. By
electrolysis it may be split up into its constituent gases.
Its specific gravity varies with its strength. (See Table III. in
Appendix.)
(3.) Chemical. A weak solution of the acid turns blue litmus red.
Its action on the metals varies; some metals are freely dissolved by
the cold acid with the evolution of hydrogen (K, Na, Ba, Fe, Zn, etc.);
—others are only acted on by the boiling acid (Sn, Cu);—others are
only slightly acted upon (Sb, Pb, Ag, Bi, etc.), whilst some are per-
fectly unaffected, either by the cold or by the boiling acid (Au, Pt, etc.).
If, however, free chlorine be present in the acid solution, both gold
and platinum are rapidly dissolved by it. On the metallic owides it
commonly forms water and a chloride of the metal corresponding to
the oxide acted upon (Fe2O3+6HCl=Fe2Cl6+3H2O), or if such
compound does not exist, to one containing less chlorine than its equi-
valent oxygen (PbO2+4HCl=PbCl,+2H,0+C.).
IMPURITIES.
(1.) Sulphurous acid, derived from the deoxidation of the sulphuric
acid either by the organic matter of the salt, or by the metal of the
still.
Test.— The evolution of sulphuretted hydrogen when zinc is added
to the pure acid.
(2.) Sulphuric acid, which may be known by a soluble baryta salt
producing a white precipitate of BaSO4.
(3.) Free chlorine, which imparts a greenish yellow tint to the acid
solution, may be known by its odor, and by the solution dissolving a
little piece of gold leaf.
(4.) Iodine and bromine are sometimes present, derived from impuri-
ties in the common salt.
(5.) Arsenious chloride, derived from the sulphuric acid, may be
known by the acid giving a yellow precipitate with sulphuretted
hydrogen.
(6.) Stannic chloride (mentioned by Gmelin) will be thrown down as
a yellow precipitate, gradually becoming brown on passing sulphuretted
hydrogen through the acid.
(7.) Plumbie chloride (Vogel) may be present, derived from the
lead in the sulphuric acid, as well as possibly from other sources.
(8.) Ferric chloride (Rose and Graham) may be recognised by
neutralising the acid with sodic carbonate and afterwards adding
tincture of galls or potassic ferrocyanide. With the former a violet,
and with the latter a blue precipitate will be obtained.
(9.) Other salts may be recognised by evaporating the acid to
dryness, and examining the residue.
HYDROBROMIC ACID. 213
(10.) Organic matter. This is often the cause of the dark color
of the acid. It may be known by evaporating the acid to dryness,
and noting whether the residue becomes charred by the continued
application of heat.
PREPARATION OF PURE HYDROCHLORIC ACID.
It will at all times be found easier to make a pure acid than to
purify a bad one. The following method is recommended :—Dilute
one part of good sulphuric acid with six parts of water, and pass a
stream of well washed sulphuretted hydrogen through it for some
hours. After allowing it to stand undisturbed for five or six days,
so that any precipitate may settle, syphon off the supernatant acid,
and having added a teaspoonful of common salt, concentrate by heat
to the original bulk.
Fill a large retort half full of good salt, and add to it the sulphuric
acid thus prepared. The retort should have fitted to it a glass tube,
of such a length and shape that it may pass into a pint bottle half
full of distilled water, the end of the tube dipping about of an inch
under the water. The bottle is to be fitted with a second tube, con-
nected with a second bottle of water, so that any acid vapors that
escape from the water of the first bottle may be absorbed by the
water of the second. The acid thus obtained will generally be found
pure, but should be carefully tested before using, both by passing
sulphuretted hydrogen through it, as well as by boiling with copper,
the purity of which has been already proved by analysis.
Characters of pure hydrochloric acid:—
(1.) The absence of color (freedom from organic matter).
(2.) The absence of residue on evaporation to dryness (freedom
from metallic salts, etc.).
(3.) No precipitate on the addition of an excess of ammonia (free-
dom from iron).
(4.) No precipitate with sulphuretted hydrogen (freedom from
arsenic, sulphurous acid).
(5.) No precipitate in a dilute solution with baric chloride (freedom
from Sulphuric acid).
Hydrobromic Acid (H.Br.) (Anhydrous).
Molecular weight, 81. Relative weight, 40-5. Molecular volume, [T].
Specific gravity, 2.75.
Synonym.—Hydric Bromide.
History.—Discovered by Balard in 1826.
Preparation.—By the direct union of hydrogen and bromine
vapor :—
(1.) By burning hydrogen in a mixture of air and bromine vapor.
Also by combining hydrogen and bromine vapor by means of electric
214 HANDBOOK OF MODERN CHEMISTRY.
sparks, or by the contact of heated platinum, or by passage through
a red hot tube (H, + Br. = 2EIBr). -
(2.) By heating potassic or sodic bromide with phosphoric acid.
[N.B.-If sulphuric acid be used instead of phosphoric acid the liberated hydro-
bromic acid both decomposes and is decomposed by the sulphuric acid, sulphurous acid
and bromine being liberated (2HBr + H.S0, - Br, + S0, 4-2H,0)].
3KBr + HapC), = R3PO, + 3HBr.
Potassic bromide + Phosphoric acid = Potassic phosphate + Hydrobromic acid.
[3]KBr + POELos = POKos + 3HBr.]
(3.) By distilling together bromine water and phosphorus. (In
this reaction a phosphorous tribromide (PBra) is first formed).
6H2O + 3Bro -- P. 6HBr + 2(H2PHO).
Water + Bromine + Phosphorus Hydrobromic acid + Phosphorous acid.
|60H2 + 3 Bro -- P. 6HBr + 2POHHo.),
A solution of the gas may be prepared—
(4.) By passing sulphuretted hydrogen through bromine water—
=
Sulphuretted hydrogen. + Bromine = Hydrobromic acid + Sulphur.
[2SH, + 2Brz = 4 HBr + Sc).
Properties.—(a.) Sensible and Physiological. Hydrobromic acid is
a colorless gas, having a pungent odor and an acrid acid taste. It is
irrespirable, producing, even when very dilute, intense pulmonic
irritation.
(3.) Physical. Specific gravity 2-75. It is not decomposed by heat.
It may be condensed at — 92.2° F. ( – 69°C.) to a liquid, and at a
still lower temperature to a solid. It is freely soluble in water (see
below).
(y.) Chemical. It reddens litmus. It neither burns nor supports
combustion. It fumes in the air with the liberation of a trace of
bromine. Most metals are acted upon by it;-thus potassium
instantly decomposes it with the liberation of hydrogen. Like hydro-
chloric acid it is decomposed by metallic peroxides, and by high
oxygen acids. It is also decomposed by chlorine (2EIBr + Cl3 =
2HCl + Bro).
Hydrobromic Acid (HBrOH,0),) (Solution).
This is a solution of the gas in water. The strongest solution
HBr,5PI.0 (containing 48:17 of HBr) has a specific gravity of 1:49,
and boils at 258-8° F (126° C.). It may be distilled without change.
It fumes when exposed to the air.
Hydriodic Acid (HI) (Anhydrous).
Molecular weight, 128. Relative weight, 64. Specific gravity 4'4. Mole.
cular volume IT .
Synonym.—Hydric Iodide,
EIYDRIODIC ACID, 215
History.--Discovered by Guy Lussac and Davy in 1814.
Preparation.—(N.B.-Compare the similarity in the preparation of
hydriodic and hydrobromic acids.)
(1.) By the direct union of hydrogen and iodine vapor by their passage
over spongy platinum, or through a red hot tube (H2+Ig=2HI).
(2.) By heating together potassic iodide (or any other iodide) and
phosphoric acid :—
3KI + H.P.O. = 3BI + K3IPO4.
Potassic iodide + Phosphoric acid = Hydriodic acid + Potassic phosphate.
[3]{I + POHos = 3HI + POKos.
(3.) By distilling together iodine, water and phosphorus. (In this
reaction a phosphorous triiodide (PIs) is first formed):—
Water + Iodine + Phosphorus = Hydriodic acid + Phosphorous acid.
[6OH2 + 3I. -- Pe = 6HI + 2POHHog.]
(4.) By heating a mixture of phosphorus, iodine, potassic iodide
and water. This reaction occurs in two stages:—
(a) Phosphoric acid and hydriodic acid are formed—
8H2O + 5T2 + P. 1 OEII + 2H3PO4.
Water + Iodine + Phosphorus Hydriodic acid + Phosphoric acid.
[80 H2 + 5Is H- P2 10 EII + 2POHos.]
(3.) The potassic iodide is then acted upon by the phosphoric acid,
whereby a further quantity of HI is formed :—
4 KI + 2 HSPO4 4 HI + 2K2HPO,.
Potassic iodide + Phosphoric acid Hydriodic acid + Hydric potassic phosphate.
[4KI + 2POHos 4 HI + 2POHokoe.]
A solution of the gas may be prepared as follows:–
(5.) By passing sulphuretted hydrogen through iodine suspended
in water—
=
=
2H.S + 2 Ic = 4HI + Se.
Sulphuretted hydrogen + Iodine = Hydriodic acid + Sulphur.
[2SH, + 2I. == 4HI + Sg.]
On distillation pure hydriodic acid may be obtained.
Properties.-(a.) Sensible and Physiological. Hydriodic acid is a
colorless gas, having a strong odor and taste. It is quite irrespirable.
(3.) Physical. Specific gravity 4:4. It may be liquefied by pressure;
by a cold of —60°F. (–51°C.) it solidifies to an ice-like mass. It
is decomposed by heat and electricity. It is very soluble in water.
(y.) Chemical. Hydriodic acid reddens litmus. It neither burns nor
supports combustion. It is decomposed by chlorine, by bromine and
by sulphurous acid, iodine being set free ((a.) 2EII+ Cl2=2|HCl-HI.
(3.) 4HI+SO2=2H2O+ S-i-2I2). The gas fumes in the air, the
atmospheric oxygen slowly effecting its complete decomposition
(4HI+O2=2H20+2I.). For this reason hydriodic acid is a powerful
reducing agent, even to the conversion of sulphuric acid into sulphu-
retted hydrogen (H2SO4+8HI=HAS+4H20+ 4Is). It is decomposed
216 HANDBOOK OF MODERN CHEMISTRY.
by most metals, hydrogen being set free (2HI+2Hg=HgI,4-H,).
With most oxides and other salts it forms iodides.
Hydriodic Acid (HI(H2O),) (Solution).
This is a solution of the gas in water. The strongest solution
(2HI, 11H2O) has a specific gravity of 17, and distils unchanged at
261° F (127°C.). It dissolves iodine, and is decomposed by atmo-
spheric oxygen, the iodine being deposited in fine crystals. The re-
actions of the gas given above apply equally to its reactions in
solution.
Hydrofluoric Acid (HF) (Anhydrous).
Molecular weight, 20. Molecular volume, IT |. Relative weight, 10.
Specific gravity of vapor 0.689; of liquid at 55° F (12.8° C.), 0.987.
Synonym.—Hydric fluoride.
History.—Discovered by Scheele (1772). Examined and described
by Guy Lussac and Thénard in 1810.
Properties. — (a.) Physical. The anhydrous acid is a colorless
fuming liquid, which boils at about 65° F. (18.3°C.), and has a
specific gravity of 0.987 at 55° F (12.8° C.). It does not solidify
at –30°F. (–34.5°C.). This anhydrous liquid acid is said to have no
action on glass or on the metals, except on sodium and potassium. It
chars organic substances, burns the skin, and explodes when mixed
with oil of turpentine.
Hydrofluoric Acid (HF(H2O),) (Solution).
This consists of a solution of the anhydrous acid in water, with
which it combines with intense avidity.
Preparation.—By heating together calcic fluoride and sulphuric
acid in a lead or platinum retort, and condensing the distillate in a
receiver surrounded by a freezing mixture.
Calcic fluoride + Sulphuric acid = Hydrofluoric acid + Calcic sulphate.
Car', + SO2Hoa = 2HF —H. SO.Cao".
Properties.—(a.) Physical. A colorless, strongly corrosive liquid.
The concentrated acid has a specific gravity of 1:060, which by suffi-
cient dilution to form the acid H.F,2H20, rises to a specific gravity
of 1:150, but decreases by further dilution. The acid HF,2H2O boils
at 248° F (120° C.), and distils unchanged.
(3.) Chemical.-The acid fumes in the air from its affinity for water.
It reddens litmus. It acts powerfully on all organic substances,
explodes when mixed with turpentine, and dissolves most metals
(except Au, Pt, Ag, Hg, Pb, and Mg) evolving hydrogen, and form-
ing metallic oxides. It dissolves glass, forming a fluoride of silicon
IMIDOGEN–THE IMIDES. 217
(SiF.), and must therefore be preserved in gutta-percha bottles. It
is not decomposed by chlorine.
Test.—Its corrosive action on glass.
GENERAL REVIEW OF THE COMPOUNDS OF HYDROGEN AND THE
HALOIDS.
(1.) Constitution.—They are all formed by the combination of
1 volume of hydrogen and 1 volume of the haloid element combined
without condensation.
(2.) Natural History.-None have been found in nature in a
free state, except hydrochloric acid, a trace of which has been
noted in the atmosphere in the neighbourhood of volcanoes.
(3.) Preparation.—HCl and HF are prepared by the action of
H2SO, on a chloride or fluoride. HBr and HI are prepared by the
action of phosphorus on the haloid element in the presence of
water, a teriodide (PIs), or a terbromide (PBr3) being first formed,
which is afterwards decomposed by the water—
#, + 3H.0 = #, + H.PH0.
(4.) Properties.—(a.) Sensible and physiological. They are all
colorless gases, having pungent odors, and producing excessive
irritation when breathed. (3.) Physical. Their specific gravities vary.
They may all be condensed by cold and pressure, and decom-
posed by heat and electricity. They are all soluble in water, forming
the liquid acid. (y.) Chemical. They are all acid to litmus, are non-
combustible and non-supporters of combustion, are decomposed by
nitric acid, are attacked by metallic peroxides, and combine with
bases to form salts.
COMPOUNDs of HYDROGEN AND NITROGEN.
Theoretically there are four compounds of nitrogen and hydrogen,
viz.:-
Imidogen (Laurent) NEI.
Amidogen (Kane and Dumas) NH2.
Ammonia (all chemists) NH3.
Ammonium (Berzelius) NH4.
Only one of these compounds, however, viz., ammonia, has been
obtained in a free state.
Imidogen (NH)—The Imides.
The imaginary radical Imidogen is supposed to exist in certain con-
jugate bodies, termed by Laurent “The Imides.” They are not a
numerous class, and are obtained by the action of heat on certain acid
salts of ammonia, two molecules of water being thereby liberated.
Thus CiołII.O2, NH represents camphor imide, and is formed by
abstracting two molecules of water from the bicamphorate of am-
monia (NH4HClo B1,04).
218 HANDBOOK OF MODERN CHEMISTRY.
Amidogen (NH,)—The Amides.
Amidogen is regarded as the radical of a compound, where one
hydrogen atom of ammonia has been replaced by a metal or by a
compound radical. Thus, if potassium be heated in dry ammonia-
gas, hydrogen is liberated, and potassic amide KHAN is formed ; or
if ammonic oxalate [(NH4)2C2O.J be heated, two water molecules are
evolved, and oxamide (NH2). C.O., is left.
Two views have been entertained as to the constitution of the
amides. Some regard them (1) as compounds of amidogen (NH2)
with a metal or a compound radical, and others (2) as an ammonia,
where a metal or a compound group has been substituted for a hydro-
gen atom. .
Ammonia, NH3.
*-m-sº
Molecular weight 17. Molecular volume | | | . Relative weight 8-5.
Specific gravity, 0-59. Melting point –103°F. (—75° C.). Boiling
Point, —37° F. ( —38°C.).
Synonyms.-Volatile Alkali; Spirit of Urine; Spirit of Hartshorn;
Alkaline Air (Priestley). -
History.-Mentioned by Pliny. It was first described accurately
by Black (1756), and afterwards experimented upon by Priestley
(1790). -
Natural History.—It is found (a.) In the mineral kingdom in air
(1 in 28 million volumes (Wille)), in water and in the soil; and (3.)
in the organic kingdoms in various secretions, as in the urine, etc.
Preparation.—(1.) By the action of nascent hydrogen on nitrogen ;
as, e.g.—
(a.) By decomposing water containing air in solution by means of
a battery or with certain metals, such as iron, zinc, etc.
[Iron in rusting decomposes the moisture of the air, the free hydrogen of which
combines with atmospheric nitrogen. Hence in all rust a certain amount of ammonia
is to be found.]
(3.) By liberating hydrogen in the presence of nitrates or nitric
acid (HNO3+4EI2=NH3+ H20+2H2O) by such means as the follow-
Ing:—
(i.) By acting on a solution of a nitrate with metallic aluminium
and caustic soda. (Schultze).
(ii.) By acting on a solution of a nitrate with zinc and hydrochloric
acid or dilute sulphuric acid (HNO3+4EI2=NH3+3H2O).
(iii.) If nitric oxide be passed over a mixture of lime and potassic
hydrate, calcic and potassic nitrates are formed together with ammonia.
Similarly if nitric oxide and hydrogen be passed over warm platinised
asbestos, water and ammonia are found.
(2.) By the decomposition of organic matters containing nitrogen.
AMMONIA. 219
•º
This may be—
(a.) Spontaneous, as when organic matter decays; or
(3.) The result of destructive distillation; as e.g., by heating horn,
coal, etc., in closed retorts. Thus, most of the commercial ammonia
salts are derived from the ammoniacal liquor produced during the
distillation of coal.
(NotE.—The nitrogen of all nitrogenised bodies (provided it be not present as a
nitrate or cyanide) is evolved as ammonia when heated with the hydrated alkalies.)
(y.) By acting on ammoniacal salts with an alkali or alkaline
earth.
2NH4C1 + CaO= CaCl2 + 2NH3 + OH2.
Ammonic chloride + Lime = Calcic chloride + Ammonia + Water.
Properties.—(a.) Sensible and physiological. A colorless gas, having
a pungent odor, and an acrid taste. When the concentrated gas is
inhaled it is poisonous, but when dilute its action is stimulating.
(3.) Physical. The specific gravity of ammonia gas is 0-59. By a
cold of —40°F. ( —40 °C.), or by a pressure of 6 atmospheres at
50° F (10°C.), or of 8-5 atmospheres at 68°F. (20° C.), the gas is
condensed into a clear, mobile, highly refractive, liquid, which boils
at —37°F. ( —38°C.). The liquid ammonia dissolves sulphur,
phosphorus, iodine, and the alkaline metals, forming with these last
a blue solution, from which the metal is deposited unchanged when
the ammonia is evaporated. At a cold of —103° F. ( —75° C.),
the liquid ammonia freezes to an ice-like solid, having a greater
specific gravity than the liquid.
In “Carré's ice making apparatus” liquid ammonia is first formed
by condensing ammonia gas into a liquid in a strong iron vessel,
which liquid, in again becoming a gas, absorbs so much heat that
it freezes the water with which the liquid ammonia is surrounded.
Ammonia gas may be decomposed either by electric sparks or by
passing it through a hot porcelain tube. In each case the volume of
gas formed is double the original volume operated on. Ammonia gas
is very readily absorbed by clayey and peaty soils, by most porous
bodies, by water (more freely indeed than any other gas), and by
alcohol. No definite combination of water and ammonia is believed
to occur, the absorption being a merely physical act of solution.
(y.) Chemical. Ammonia has an alkaline reaction ; turmeric is turned
brown by it, and red litmus blue, but the changes are not perma-
nent (volatile alkali). It is not a supporter of combustion, and is
very feebly combustible, burning under favorable conditions with a
greenish yellow flame, water and free nitrogen forming the products.
Action of oaygen. When 3 to 4 parts of ammonia gas are mixed with
1 part of oxygen it explodes, water, nitrogen, and traces of nitric acid
being formed. If ozonized air be mixed with ammonia gas, white
clouds of ammonic nitrite are formed from the ammonia becoming
oxidised to nitrous acid (4NH3 + 3O2 = 2(NH4,NO2) + 2.H2O).
220 FIANDEOOK OF MOIDERN CFIEMISTRY.
This oxidation of ammonia may also be effected by a hot platinum
wire introduced into a mixture of the gas and air. In the presence
of a strong base, the oxidation of ammonia to nitric acid, and its
Subsequent combination with the base, constitutes a process termed
nitrification (2NHs -- K.0 + 402 = 2ENO, + 3H2O).
Action of the haloids.-Ammonia is decomposed by chlorine with
the formation of the hydrogen acid (8NH3 + 3Cl2 = 6NH4C1 + N2).
With acids, ammonia forms salts. Thus when the volatile hydro-
chloric acid is brought near ammonia, white fumes of ammonic
chloride are produced, a reaction constituting a test for the presence
of the alkali. Neither the alkalics, nor the combustible solids have any
action upon it.
Action on metallic salts.-Ammonia combines with various metallic
salts, at times apparently taking the place of their water of crystallisa-
tion, but not necessarily analogous, so far as the relationship between
the number of the molecules is concerned. Thus, cupric sulphate has
the formula CuSO4,5EI2O, and ammoniated cupric sulphate the formula
CuSO4,4H4N, H2O. Hence ammonia frequently acts on metallic salts
differently to potassic or sodic hydrate. (a.) If the ammonia be
in insufficient quantity to neutralise the acid, a basic salt may be precipi-
tated (4CuSO4+ 6H3N +7H2O=3(HAN),SO,--CuSO4,3CuO,4H2O); or
(3.) If it be added in eaccess a precipitate may be formed either of
the hydrated metallic oxide, together with an ammonic salt
(2Fe23S0, -ī- 12H9N + 9PI,0=6(HAN),SO, + 2Fe2O3,3H2O), or of a
combination of ammonia with the precipitated oxide [as e.g., uranic
oxide, forming (HAN),0,2U20s], or of a double salt of the metal and
ammonium, as e.g., the ammonic magnesic phosphate (H4N), Mg2F20s,
12H2O), or various ammoniated salts may be formed, such as the
ammoniated cupric sulphate, or various substitution products may
result, where one or more atoms of hydrogen are replaced by a metal
or by an electro-positive radical. Thus:–
Potass-amine NH.K.
Tri-chlor-amine NCla (?).
Tri-zinc-amine NZns.
Platin-amine N.H.Pt”
Ethyl-amine NH2(C.H.).
Di-ethyl-amine NH (C2H3)2.
Tri-ethyl-amine N(C.Hs)a.
Acet-amine NH,(C.H.,0).
Sulpho-amine N.H.,(SO2)".
Solution of Ammonia (Liquor Ammoniae).-This is merely a solu-
tion of the gas in Water.
At 32°F. (0°C.) water absorbs 1050 vols. of NH3.
At 59° F (15° C.) , * } 727 , , , ,
At 77° F. (25°C.) , ,, 586 , , , , , ,
When these solutions are boiled the whole of the ammonia is
evolved.
GASEOUs PHOSPHORETTED HYDROGEN. 221
The specific gravity of the solution of ammonia varies with its
strength. (See Table IV. in Appendix.)
Ammonia solution is a colorless, alkaline liquid, having a very
caustic taste, and blistering the skin. It freezes at —40°F. (–40°C.)
The gas is evolved at ordinary temperatures. The solution dissolves
many salts (as AgCl) and oxides (CuO, ZnO, Ag,0) that are insoluble
in water.
If the liquid be pure it should on evaporation leave no residue.
The impurities of a solution of ammonia are—
(a.) Carbonic acid.—Test: White precipitate with lime water.
(6.) Chlorine.—Test : White precipitate on adding argentic nitrate
to the solution neutralised with nitric acid.
(y.) Sulphuric acid.—Test : White precipitate on adding baric
nitrate to a solution neutralised with nitric acid.
(3.) Lime—Test : White precipitate with ammonic oxalate.
(e.) Lead or copper (derived from the apparatus, or from the solution
having been kept in glass containing lead).-Test : Brown or black
precipitate with sulphuretted hydrogen.
Ammonium (NH4).
This compound metal has never been isolated. Its possible
existence has been inferred by the close relationship of the ammonium
salts to those of sodium and potassium, and also by the production of
an amalgam having the metallic lustre of ordinary amalgams, under
circumstances where its formation is theoretically possible. This amal-
gam rapidly decomposes into mercury, ammonia and hydrogen.
The amalgam may be prepared as follows:–
(1.) By placing a globule of mercury connected with the negative
pole of a battery on a piece of moistened sal ammoniac (NH4Cl)
placed on a piece of platinum foil, and connected with the positive pole.
(2.) By pouring a little potassic amalgam into a saturated solution
of sal-ammoniac, when the amalgam rapidly swells up, potassic
chloride being formed at the same time.
CoMPOUNDs of HYDROGEN WITH PHosphorus.
1. Gaseous phosphoretted hydrogen PHs (PH3).
2. Liquid phosphoretted hydrogen...P.H., or P.H., (P.H.).
3. Solid phosphoretted hydrogen ...P.H or P.H., | #} (?)
None of these can be easily prepared by direct union.
Gaseous Phosphoretted Hydrogen, PHs (PHs.)
Molecular weight, 34. Molecular volume, ITI. Relative weight, 17.
Specific gravity, 1:19. -
Synonyms.-Phosphamine (from its analogy to ammonia); Phos-
phorous Trihydride.
222 HANDBOOK OF MODERN CHEMISTRY.
History.-Discovered by Guigembre (1783), whilst distilling potash
With Spirit that had been used for anatomical preparations. It was
afterwards studied by Davy (1812), who devised other methods for
its preparation, and also by Dumas, Rose, etc. -
Natural History.—Evolved during the decomposition of phos.
phorised organic bodies (odor of fish).
ºperation-do By heating phosphorous or hypophosphorous
a ClCIS.
(a.) 4H.PO, - PH, + 3HAPO4.
Phosphorous acid = Phosphoretted -- Phosphoric acid.
hydrogen
[4]2OHEIo, - PH, + 3POHos].
(3.) 2H3PO. = PH, + H.PO4.
Hypophosphorous Phosphoretted Phosphoric
81.01 hydrogen acid.
[2POH, Ho = PH, + POHo.).
(2.) By boiling phosphorus in a strong solution of an alkali or an
alkaline earth.
3KHO + P, H- 3II.O 3KPH2O2 + PHs.
Potassic + Phosphorus + Water = Sodic hypo- + Phosphoretted
hydrate phosphite hydrogen.
[3OKH + P., H- 3OHe 3POBANao + PH,).
[N.B.-(a.) Free hydrogen is also evolved by the action of an excess of free alkali
on the hypophosphite, a phosphate being formed as well as the liquid P.H.,.
(3.) If alcohol be used instead of water the non-inflammable form is generated.]
(3.) By decomposing calcic phosphide (prepared by passing phos-
phorus vapor over red hot lime) with water.
(4.) By the action either of water or potassic hydrate on phos-
phoric iodide.
(a.) PH, I = HI + PHs.
(3.) PH, I + KHO = PH2 + KI + H2O.
[N.B.-This PH, is not inflammable.]
(5.) Possibly it is produced in very small quantities by the action
of nascent hydrogen on phosphorus.
Properties.—(a.) Sensible and physical. A colorless, stinking gas.
Specific gravity 1:19. It may be liquefied by pressure, and is decom-
posed by heat and electricity. Water absorbs from one-fourth to
one-fiftieth of its volume.
(3.) Chemical. Although in constitution analogous to ammonia, it
has no alkaline reaction, but is, on the contrary, feebly acid to blue
litmus. Nevertheless its analogy to ammonia is shown by its com-
bining with certain acids, such as hydriodic and hydrobromic acids,
forming with them the crystalline compounds phosphoric iodide (PH, I)
and phosphoric bromide (PH, Br). Both of these compounds are de
composed by water. The gas as ordinarily prepared is spontaneously
inflammable; but this is not the case with the pure gas. This spon-
F
soliD PHOSPHoRETTED HYDROGEN. 223
taneous inflammability depends on the presence of a trace of the
vapor of liquid phosphoretted hydrogen (PH2), one part of which in
500 of PH, is sufficient to confer this property upon it. (1.) The pure
non-inflammable gas may be rendered inflammable (a.) by mixing it with a
little PH2 vapor; or (ſ3.) by bubbling it through nitric acid contain-
ng nitrous acid in solution, Twº oth part of its bulk of nitrous anhy-
dride being sufficient for this purpose. Or again, (2,) The spontaneously
inflammable gas may be rendered non-inflammable (a) by passing it over
charcoal; or (3) by exposing it to sunlight, or (y) by passing it through
hydrochloric acid; in both of which latter cases the liquid phosphoretted
hydrogen is decomposed into solid and gaseous phosphoretted hydro-
gen (5 PH2=P, H+ 3PEIs), or (3) by exposing the gas to a freezing
mixture, whereby the vapor of the liquid phosphoretted hydrogen is
condensed, or lastly (e) by mixing it with certain vapors, such as
those of ether, turpentine, alcohol, etc. When the impure gas is
ignited it produces wreaths of white smoke, due to the formation of
phosphoric anhydride. The gas explodes when mixed with oxygen.
The haloids, sulphurous acid and some of the metals decompose it. It
is mostly decomposed when passed into metallic solutions, phosphides
of the metals being precipitated (3CuSO4+2PH3=3|H2SO4+ P2Cus).
In the case of gold and silver salts the metals are reduced, phos
phoric acid remaining in solution,
Liquid Phosphoretted Hydrogen, P.H., {#.
Preparation.—By passing phosphoretted hydrogen (prepared by
the action of water on calcic phosphide) through a freezing
mixture.
Properties.—A light yellow liquid, boiling at 95° F (35° C.), not
solidifying at —4°F. ( —20° C.), very inflammable, and decomposed
by Sunlight into solid and gaseous phosphoretted hydrogen (5IP2H4–
6PHs + P.H.). It fires on exposure to air. The presence of this
body in gaseous phosphoretted hydrogen confers on it the property
of spontaneous inflammability (Thénard.) A similar effect is pro-
duced by its admixture with hydrogen, with carbonic oxide, or
with other combustible gases. -
Solid Phosphoretted Hydrogen, P.H., {##,
Preparation.—By the action of sunlight or of hydrochloric acid
on liquid phosphoretted hydrogen, or by the action of hydrochloric
acid on calcic phosphide. -
Properties.—A yellow solid, firing at 302°F. (150° C.), insoluble
in water or in alcohol, but soluble in a solution of potassic hydrate,
gaseous phosphoretted hydrogen being evolved.
224 HANDBOOK OF MODERN CHEMISTRY,
COMPOUNDS OF HYDROGEN AND SULPHUR.
Sulphuretted hydrogen tº tº º dº º q * * * H.S.
Persulphuretted hydrogen ... & tº * * * H.S., (?).
Sulphuretted Hydrogen, H.S (SH.).
Molecular weight, 84. Molecular volume, TTI. Relative weight, 17.
Specific gravity, 1' 1912.
Synonyms.-Dihydric sulphide; Hepatic air; Hydrogen mono-
sulphide; Sulphidic acid; Hydrosulphuric acid.
History.—Discovered by Scheele (1777).
Natural History. — (a) In the mineral kingdom, sulphuretted
hydrogen is found in the gases issuing from volcanoes, often to the
extent of 25 per cent.
It is found in certain mineral waters, as, e.g., in those of Harrogate,
Aix-la-Chapelle, etc., and in the sea-water near the mouths of rivers.
The water on the west coast of Africa is stated to contain 6 cubic
inches of sulphuretted hydrogen per gallon, the smell of the gas
being noticeable 27 miles out at sea. In these cases the conditions of
its formation are the presence in the water of organic matter and of
sulphates, the former being oxidized by the oxygen of the latter,
until a sulphide is formed (CaSO4 – 0, - CaS). When this sul-
phide is acted on by the carbonic acid in the water, sulphuretted
hydrogen is set free (CaS + H2O + CO2 = CaCO3 + H2S). The
unpleasant taste of many aerated waters is due to their having been
manufactured with water containing organic matter and sulphates,
whereby a sulphide is formed, which is decomposed by the carbonic
acid present in large excess.
Its presence in sewer-gas results from the putrefaction of organic
matters containing sulphur, as well as by the process already
described. In the neighbourhood of sulphate of ammonia works, it
may often be detected in the air, for in distilling coal (as well as in
the destructive distillation of all organic matters containing sulphur)
large quantities of the gas are generated, which, combining with the
ammonia, collect in the ammoniacal liquor. It is also set free in
quenching the coke at the gas works, the hydrogen of the decomposed
water combining with the sulphur of the fuel. Large quantities of
H2S are also evolved in the last part of the process of tar distillation.
It may be worth noting here that if present in a room it may be
entirely removed by setting free a trace of chlorine.
(3.) In the vegetable kingdom it is unknown, whilst (y) in the animal
kingdom it is found in intestinal flatus, and in decomposing animal
matters.
Preparation.—(1) By the direct union of hydrogen and sulphur.
(a.) By heating together sulphur and hydrogen; or (3) by passing
hydrogen into boiling sulphur; or (y) by burning hydrogen in
SULPEIURETTED HIY DROGEN. 225
sulphur vapor or sulphur vapor in hydrogen; or (3) by passing steam
and sulphur vapor through a tube filled with red hot pumice stone.
(2.) By decomposing a metallic sulphide with an acid; e.g. :—
(a.) Dilute sulphuric acid on ferrous sulphide—
H2SO4 + FeS - FeSO, + H.S.
Sulphuric acid + Ferrous sulphide = Ferrous sulphate + Sulphuretted hydrogen.
[SO. Ho, + FeS" = S0. Feo" + SH..]
(3.) Dilute hydrochloric acid on antimonious sulphide :-
6HCl + Sb2S, = 2SbCls + 3H2S.
Hydrochloric + Antimonious sulphide = Antimonious chloride + Sulphuretted
acid hydrogen.
Properties.-(a.) Sensible and physiological. Sulphuretted hydrogen
is a colorless gas, having the odor of rotten eggs. Physiologically,
it acts as a narcotic, and is very poisonous; 1 part in 1,500 will kill
birds; 1 in 1,000, dogs; 1 in 250, horses. (Dupuytren and Thénard.)
(6.) Physical. Its specific gravity is 1:1912. 100 cubic inches weigh
38 grains, and 1 litre 1.5.1991 grims. By a pressure of seventeen
atmospheres, or by a cold of —101°F. (–74° C.), it may be con-
densed into a colorless liquid, which boils at –79-6° F. (–62°C.),
and freezes at –122.8° F. (–86° C.). It is decomposed both by heat
and electricity. Water freely absorbs it; at 32°F. (0°C.), it dissolves
4:37 times its bulk of the gas; at 59°F. (15°C.) 3:23 times, and at
75° F. (24°C.) 2-66 times.
(y.) Chemical. Sulphuretted hydrogen reddens litmus feebly. It
is a combustible gas. If the supply of air be free, water, Sulphurous
acid, with a little sulphuric acid (if the air be moist), are formed. If
the supply of air be limited, sulphur is deposited. It will be noted,
therefore, that any sulphuretted hydrogen evolved in manufacturing
operations, may be effectually removed by passing the gas through
the furnace.
Mixed with oaygen in the proportion of 1 part of H.S to 1-5 of O,
it explodes on the application of heat. By the action of the haloid
elements, sulphuretted hydrogen is immediately decomposed, the ha-
loid appropriating the hydrogen and liberating sulphur (SH3+Cl3 =
2HCl-HS). Oxy-acids (such as nitric, sulphurous acids, etc.), decompose
it, setting free sulphur. It is absorbed by the alkalies, forming sul-
phides (as K.S.), solutions of which, on being further treated with
sulphuretted hydrogen, form sulphydrates or hydrosulphides (K-S-H
H.S.–2KHS).
Certain metals displace hydrogen from the gas, forming a sulphide.
This occurs in some cases at ordinary temperatures (as e.g., in the case
of Hg, Ag, etc.), (Hg2+H.S=Hg, S-i-Ha). Thus, silver is blackened
by exposure to the air of towns, a silver spoon by the sulphur of an
egg, and silver coins by keeping them with sulphur matches in the
pocket. [The black sulphide thus formed may be removed by strong
Q
226 BANDBOOK OF MODERN CHEMISTRY.
ammonia or by potassic cyanide.] In other cases, heat is required to
effect combination (as e.g., in the case of K, Sn, etc.)
(a.) 2FI.S +R2=2KHS--H2. (3.) H.S +Sn=SnS+ H2.
In this latter case it will be remarked that the volume of hydrogen
evolved is identical with the volume of sulphuretted hydrogen
operated upon. Metallic oacides are changed, by the action of the gas,
into their corresponding sulphides, water being formed simultane-
ously (PbO-i-H2S=PbS+ H2O). A similar action is observed in the
case of the metallic salts (Pb(NO3)2+ H2S=2HNO3 + PbS). Thus,
the lead used for paint becomes black, although the black sulphide
(PbS) formed is, under the influence of air and light, converted into
the white sulphate (PbSOA). The colors of the various sulphides
produced when the gas is passed through metallic solutions are, in
many cases, very characteristic, and constitute important tests. On
wnetallic chlorides the action of the gas is similar to that on oxides.
The solution of sulphuretted hydrogen has a feebly acid reaction. It
rapidly decomposes, becoming turbid, from the atmospheric oxygen
combining with the hydrogen, whereby sulphur (the electro-negative
variety) is precipitated as a white deposit. It is better, therefore, to
make the solution with water that has been well boiled, or has been
previously saturated with the gas.
Uses.—In the laboratory, as a test for the metals.
Tests.-Blackens lead paper.
Persulphuretted Hydrogen (H.S. 2) 'S'. He, or Hss,
Molecular weight, 66 (?). Specific gravity, 1769.
Synonyms.-Persulphide of hydrogen; Hydric persulphides Dihydric
disulphide; Hydrosulphyl (Frankland).
History.—Discovered by Scheele (1777). Its properties were fully
investigated by Berthollet.
Preparation.—Lime and sulphur are first boiled together, whereby
a disulphide of calcium is formed ('S',Ca"). This solution is then
dropped into dilute hydrochloric acid (1 of acid to 2 of water), when
persulphuretted hydrogen is formed:—
Calcic + Hydrochloric = Persulphuretted -- Calcic
disulphide acid hydrogen chloride.
'S',0a" + 2EIC1 - S.H2 + CaCl2.
[NotE.—If the acid be poured into the calcic disulphide solution,
then another reaction occurs, sulphur being precipitated (sulphur
precipitata, P. B.) CaS.--2HCl=CaCl2+H.S +S].
Properties—(a.) Sensible and physiological. A yellowish oily liquid
having a sulphuretted hydrogen odor. Specific gravity, 1769. It is
a very unstable body, and is decomposed by a slight heat into Sul-
COMPOUNDS OF CARBON AND HYDROGEN. 227
phuretted hydrogen and sulphur. It is insoluble in water, but soluble
in ether.
(3) Chemical. Persulphuretted hydrogen is inflammable, and burns
with a blue flame. Its composition is doubtful, but it is believed to
be analogous to hydroxyl (H.O.). It is closely allied to it in certain
of its reactions. Thus, it bleaches litmus. The presence of acids
increase, whilst alkalies decrease its stability. It dissolves free sul-
phur, and is decomposed, like hydroxyl, by the mere contact of certain
metals and metallic peroxides. It is believed to combine with many
vegetable alkaloids.
Seleniuretted Hydrogen, H. Se (SeHº.)
*-*-*
Molecular weight, 81-5. Molecular volume TTI. Relative weight, 40.75.
Specific gravity, 2-8.
Synonyms.-Selenetted hydrogen; Hydroselenic acid; Dihydric selenide;
Selenhydric acid.
History.--Discovered by Berzelius.
Preparation.—( 1.) By passing hydrogen and selenium vapor
through red-hot tubes.
(2.) By the action of acids on selenides :—
FeSe + 2EIC1 — H. Se + FeCle.
Ferrous + Hydrochloric = Seleniuretted + Ferrous
selenide acid hydrogen chloride.
[FeSe” + 2EIC1 – Selig + FeClj.
Properties.-(a) Sensible, physical, and physiological.—A colorless,
offensive smelling gas, producing great irritation and violent nasal
catarrh. Specific gravity, 2-8. Soluble in water.
(6.) Chemical. Inflammable. The solution in water is feebly acid.
When exposed to the air it absorbs oxygen, depositing selenium, Its
reactions are closely allied to those of sulphuretted hydrogen, pre-
cipitating in many cases metallic selenides when passed through
solutions of metallic salts. The alkaline selenides are soluble. The
selenides of zinc and manganese are coloured, but the rest are black.
CoMPOUNDs of CARBON AND HYDROGEN.
These compounds, termed generically hydrocarbons, belong chiefly,
if not entirely, to organic chemistry. Three of these compounds will
be described here, viz., marsh gas, CH4; olefiant gas, C.H., ; and
acetylene, C2H2. These three bodies are, moreover, the starting points
of three series of hydrocarbons, the members of which, as in the case
of other hydrocarbon series, increase by a regular increment, or some
multiple of CH2, such a series being termed an homologous series.
Thus— *
228 HANDBOOK OF MODERN CHEMISTRY.
Marsh Gas Series. Olefiant Gas Series. | Acetylene Series.
(CH2)n+H2. (CH2)n. (CH2)n—Hz.
Methane (marsh gas) CH, Ethylene (olef. gas) C.H., Acetylene . . . . C.H.,
Ethane . . . . . . C.H., | Propylene . . . . C. He Allylene. . . . . . C.H.,
Propane . . . . . . CaFIs | Butylene . . . . C, H, Crotonylene . . . . C. He
Etc. Etc. Etc.
Methane, or Light Carburetted Hydrogen, CH4.
Molecular weight, 16. Molecular volume ITI. Relative weight, 8. Specific
*-*.
gravity, 0:5576.
Synonyms.-Marsh gas : Methane; Methylic hydride (CH, H); Sub-
carburetted hydrogen : Heavy inflammable air; Fire damp ; Pit gas.
History.-First examined by Volta (1778).
Natural History.—Found in stagnant ditches, i.e., wherever
vegetable matter is decomposing out of contact with air, but in
the presence of moisture (marsh gas). It occurs occluded in coal, 100
grains of which will at times yield 200 c.c. of gas, containing nearly
90 per cent. of marsh gas, the remaining 10 per cent. consisting of
nitrogen, oxygen, and carbonic acid. It is evolved from the earth in
many volcanic districts.
Preparation.—(1.) By the decomposition of organic matter (as
sewage) out of contact with air.
(2.) By the dry distillation of coal.
[Probably CH, and C0, were the two gases formed when the hydrogen and oxygen
were separated from the wood during its change into coal].
(3.) By heating acetic acid or an acetate, with sodic or potassic
hydrate :-
ECH3C2O2 + IKEIO - R.COs + CH1.
Potassic acetate + Potassic hydrate = Potassic carbonate + Methane.
[ ſ CH3 - |
| | Coko t ECHO - COKo, + CHA
(4.) By passing a mixture of carbonic disulphide vapor and sul-
phuretted hydrogen (or steam) over red-hot copper :-
Carbonic + Sulphuretted + Copper = Cupric + Methane.
disulphide hydrogen sulphide
[CS." -- 2SH, + 4Cu = 4CuS + CH,).
(5.) By the action of water on zincic methide.
Zn(CHS), + 2 H.0 = 20 H, + ZnO.H.
Zincic methide + Water = Methane + Zincic hydrate.
(6) By the action of nascent hydrogen on chloroform (CHCl), or
on CC), or on CHT3.
Chloroform + Hydrogen = Methane + Hydrochloric acid.
ETHYLENE OR BEAVY CARBURETTED HYDROGEN. 229
Properties.-(a.) Sensible and physiological.—A colorless, odorless,
tasteless gas. It has no injurious action on the body.
(3.) Physical.—Specific gravity, 0:5576. It possesses great powers
of diffusion. It cannot be condensed by cold or pressure. It may,
although with difficulty, be completely decomposed by heat and
electricity, carbon being deposited, and a double volume of hydrogen
evolved. Passed through a red-hot tube, hydrogen, ethylene, acety-
lene, and ethylic hydride are formed. 100 volumes at 32°F. (0°C.)
absorb about 5-4 volumes of the gas.
(y.) Chemical.—It is a very inert gas, and constitutes the first
member of the paraffin series (parum and affinitatis). It has no action
on turmeric or on litmus. It contains more hydrogen than any other
compound of C and H. It burns with a pale illuminating flame, a
white heat or actual flame being required for its ignition, carbonic
anhydride and water constituting, if the supply of air be free, the
products of its combustion, whilst acetylene and other products are
formed if the supply be limited. Exploded with twice its volume
of oxygen, carbonic anhydride and water result, whilst with 1-5 times
its volume, carbonic oxide and water are formed. It explodes even
when mixed with air in the proportion of 1 part of the gas to 17 of
air, the energy of the explosion increasing until the methane consti-
tutes one-seventh of the total volume.
Action of the Haloids.-Iodine and bromine, are without action
upon it. Chlorine does not combine with it in the dark, whilst in Sun-
light the union is intensely energetic, forming, in the presence of
moisture, carbonic anhydride and hydrochloric acid (CEIA-1-4Cl2+
2H2O=CO2+8HCl). If the chlorine be present in great excess the
substitution of chlorine for the hydrogen may be effected, carbonic
tetrachloride, CCl3, or lower derivatives such as CHCls,CEICl2, etc.,
being formed.
Neither sulphur nor phosphorus, acids nor alkalies have any action
on the gas.
Ethylene or Heavy Carburetted Hydrogen C.H., {{#.
Molecular weight, 28. Molecular volume, [T]. Relative weight 14.
Specific gravity 0.978.
Synonyms. – Olefiant gas (Dutch chemists); Ethylene; Elay!
(Berzelius); Etherene (Faraday); Etherin.
History.—Discovered by the associated Dutch chemists (1795).
Afterwards studied by Berthollet.
Natural History.—Present to the extent of 1 to 6 per cent. in
fire damp.
Preparation.—(1.) By the dry distillation of coal and other or-
ganic bodies (resins, fats, oils, etc.) s -
(2.) By the action of sulphuric acid (or other dehydrating agents,
230 HANDBOOK OF MODERN CHEMISTRY.
such as boric anhydride) on alcohol at a temperature of about
329°F. (165° C.) The action occurs in two stages:–
(a.) Sulphovinic acid is first formed—
C.H3(OH) + H2SO, = C, H3, HSO, + H2O.
Alcohol + Sulphuric acid = Sulphovinic acid + Water.
(3.) The sulphovinic acid is afterwards decomposed by heat into
ethylene and sulphuric acid— *
C2H5, HSO, - C.H., + H2SO4.
Sulphovinic acid = Ethylene + Sulphuric acid.
(3.) By the action of nascent hydrogen on acetylene (C.H., + H2=
C2H4).
[NotE.-Acetylene, C.H., is the only hydrocarbon that can be prepared artificially.
From it ethylene, and from ethylene, alcohol can be formed.]
Properties.—(a.) Sensible. A colorless, odorless gas, having an
anaesthetic action.
(3) Physical. Specific gravity 0.978. It may be liquefied by cold
and pressure at –166°F. (–110° C.) (Faraday), but it cannot be
frozen. It is decomposed by a red heat and by electric sparks. If
the heat be not too great, acetylene and hydrogen are formed
(C2H4=C2H2+ H2); at a higher temperature marsh gas is produced,
and one half of the carbon is deposited (C,EIA-CH4+ C), whilst at a
higher temperature still, it suffers complete decomposition (C2H4–
C2-H2H2) Water absorbs about one-eighth its bulk of the gas.
Alcohol, ether, the volatile and fixed oils also dissolve it.
(y.) Chemical. It has no action either on litmus or turmeric. It
burns with an intense white light, constituting one of the chief illu-
minants of coal gas. When mixed with three volumes of oxygen, it
explodes (C.H.4+ 3O2=2CO2+2H2O), water and carbonic anhydride
resulting.
Action of the haloids.—(a.) When olefiant gas is fired with twice its
volume of chlorine, it deposits carbon and forms hydrochloric acid.
(6.) Mixed with its own volume of chlorine and exposed to diffuse
light, it forms an oily body called Dutch liquid, C.H.Cl2 (Dichlor-
ethane; Ethylene chloride). This liquid has a specific gravity of
1.256 at 53-6°F (12°C.), and boils at 1832°F. (84°C.). The forma-
tion of this body is the origin of the name “Olefiant gas.” (y.)
When the gas is mixed with a larger proportion of chlorine, and
exposed to sunlight, the product C2Cl6 may be formed. Bromine, but
not iodine, forms products of a similar kind. An Ethylene iodide,
C.H.I., may be produced by passing ethylene into a mixture of
iodine and absolute alcohol.
Bhosphorus and sulphur have no action upon it.
Fuming sulphuric acid (or SOs) absorbs it, forming (C.H.,2SOs)
ethyl-sulphuric acid. Mixed with an alkaline solution of potassic
permanganate, carbonic, formic, and oxalic acids are produced.
ACETYLENE. 231
* // |H.
Acetylene C2H2 | º
Molecular weight, 26. Molecular volume, | | | | Relative weight, 13.
Specific gravity, 0-92.
º Synonyms.-Ethine ; Klumene.
Preparation.—(1.) By the direct combination of carbon with
hydrogen; as, e.g., by the combustion of the carbon poles from a
powerful battery in an atmosphere of hydrogen.
(2.) By the incomplete combustion of bodies containing carbon and
hydrogen, such, e. g., as methane, vapor of alcohol, etc.
(3.) By the action of an alcoholic solution of potassic hydrate on
bromethylene—
C.H. Br + KHO = C.H., + KBr + H2O.
Bromethylene + Potassic = Acetylene + Potassic + Water.
hydrate bromide
(4.) By the electrolysis of fumaric acid (C.H.(COOH)4=C.H2+
2CO2 + H2).
(5.) By passing a mixture of methane and carbonic oxide through
a red hot tube (CH4+ CO=C.H., H-H2O).
Properties,—(a.) Sensible. A colorless gas, having a geranium
odor. It is very poisonous.
(3.) Physical. Specific gravity 0-92. It has never been condensed.
It is decomposed by an intense heat (such as electric sparks) with the
separation of carbon. By the action upon it of a continuous red heat,
benzene (C6H6) has been formed, together with a liquid hydro-carbon
called styrole (CºHs), and which hitherto had only been obtained from
storax. Acetylene is the most stable of all carbon compounds. It is
soluble in water, the solution answering to the tests.
(y.) Chemical.—It burns with a smoky flame, 1 volume of gas con-
suming 2-5 volumes of oxygen, and forming 2 volumes of CO2. Mixed
with chlorine and exposed to diffuse daylight, it explodes spontane-
ously, with the separation of carbon (C.H2+Cl2=C. --2HCl). It com-
bines with bromine to form acetylene dibromide (C2H4Br2). When
electric sparks are passed through a mixture of nitrogen and acety-
lene, hydrocyanic acid is formed (C,EI, +INo-2CNH). Oxidizing
agents, such as potassic permanganate, convert it into Oxalic acid.
It is absorbed by sulphuric acid, with the production of vinyl-sul-
phuric acid (SO2(C.H.30)Ho). It combines directly with hydrogen
to form olefiant gas (C.H., + H2=C.H.).
Tests.-(a.) With cuprous chloride it forms a red explosive pre-
cipitate of cuproso-vinyl oxide [cuprous acetylide or cuproso-vinylic
ether, (C.Cu, H)2O), 2Cu2Cl2 + 2C, H, 4-H.O = 4HCl + (C,Cu.H.).0.
This body is supposed to have caused explosions in brass and copper
232 HANDBOOK OF MODERN CHEMISTRY.
pipes used for gas. It is immediately decomposed by hydrochloric
acid, acetylene being set free ((C,Cu,H),0+4EICl=2Cu2Cl2 + H20+
2C2H2). By the action of nascent hydrogen it forms ethylene.
(3.) It gives a white explosive precipitate with argentic nitrate,
insoluble in ammonia or in nitric acid.
Coal Gas.
Three classes of products are formed by the dry distillation of
coal—gas, water, and tar, the relative proportions of each depending
much on the temperature to which the coal is subjected. Coal gas is
a compound gas, consisting of illuminants, diluents, and impurities.
The illuminants are, olefiant gas (C2H4), and analogous hydrocarbons
(C3H6, CHs, etc.), and hydrocarbon vapors, such as the vapor of
benzol. The diluents are, hydrogen, marsh gas, and carbonic oxide.
The impurities are, carbonic anhydride, sulphuretted hydrogen, and
other sulphur compounds.
The following table, from Roscoe, represents the composition of
coal gas, prepared respectively from cannel and from common coal.
In estimating the illuminating power of a gas, we compare the light
given by the gas burning from a 24-hole argand, at 5 feet per hour,
with a sperm candle burning at the rate of 120 grains.
§ E3 3.3
; ::::::::: Composition in 100 volumes.
3. 3...… 5
F. : 50 =
.# 3.0
bſ + H.C. bſ Nitrogen
#º 5 # 5 º Heavy | Equal to ...”
3 #5 £5 |Hydrogen, Marsh gas, Cºle Hydro- | Olefiant oº:: Il
.8 #º %3 H. Ha. co y Cºl.) bons gas, Carbonic
ă äää g; (CnH2)n. C2H4. acid.
= 3 3 & #3
Cannel gas . . . . . . ... 34 '4 25'82 51*20 7 '85 13°06 (22:08) 2:07
Coal gas . . . . . . . . . . 13-0 47.60 4l 53 7 '82 3'05 (6'97)

The gas is purified by condensation and by absorption.
(1.) By condensation (refrigerators) the solid and liquid impurities,
such as water, tar, etc., are removed.
(2) By absorption (lime or oxide of iron purifiers), the carbonic
acid, the presence of 1 per cent. of which is said to decrease the light
6 per cent, and the sulphur present as sulphuretted hydrogen, and
to a certain extent in other forms, are removed.
Flame.
Flame results from the combination of two gases under the
influence of heat. A gas to burn, therefore, is one essential
condition of flame, hence, a diamond cannot burn with flame,
because it cannot be volatilized. Further, it is essential that the
FLAME. - 233
temperature necessary to effect the union of the gases should be
maintained. Hence, a mass of cold metal introduced into a flame
will extinguish it.
The terms “combustible” and “supporter of combustion'' are, how-
ever, merely conventional, inasmuch as air may be made to burn in
coal gas. -
The temperature at which this combination of different gases (i.e.,
combustion) occurs, varies with different gases. Thus, phosphoretted
hydrogen ignites at ordinary temperatures, carbon disulphide vapor at
419°F. (215° C.), whilst marsh gas needs a temperature little short of
actual flame to effect its ignition.
Combustion may proceed both without fame, as instanced by a
smouldering taper, or by the action of a hot platinum wire on
mixed air and coal gas; and with flame, as in the ordinary cases of
combustion.
An ordinary flame burning in air, is an envelope dividing the coin-
bustible gas within from the supporter of combustion without. It
consists of several parts : —
(1.) A dark inner cone of unburnt gas. This is surrounded by—
(2.) A luminous cone of partially burnt gas. It is in this cone that
the carbon is separated and dense hydrocarbons formed. This occurs
as follows:—The air present is insufficient to burn both the hydrogen
and the carbon of the hydrocarbon ; consequently, the hydrogen
having a greater affinity for oxygen than the carbon, combines with
it, and the carbon is set free, which, becoming ignited in the burning
hydrogen, renders the flame luminous. This luminous cone is sur-
rounded by—
(3.) A non-luminous but intensely hot cone of completely-burnt gas.
(4) At the bottom part of the flame is a portion where the com-
bustion is complete, and where this division into the cones described,
is not apparent.
In a blow-pipe flame a free supply of air is effected within the
flame. Thus, the carbon of the hydro-carbon is burnt as well as the
hydrogen. A blow-pipe flame consists of two parts, each part having
a different chemical power. (a.) The point of the inner cone has a
reducing action, due to the presence of an eccess of carbon in the form
of carbonic oxide, which is ready to combine with more oxygen.
(3.) The point of the outer come has an oridizing action, due to the
presence of an excess of oxygen.
The heat of a flame depends on the energy of the chemical com-
bination. Thus the heat of a flame often bears no relationship
whatsoever to the light. The oxy-hydrogen jet is non-luminous
but enormously hot, the energy of the chemical action being
intense. If lime be introduced into the jet the light becomes
intense, but the heat is reduced, inasmuch as the lime not only does
not contribute to the chemical action, but conducts the heat away.
234 HANDBOOK OF MODERN CHEMISTRY.
The light of a flame depends on several circumstances. (a.) In most
cases, but not necessarily, as Frankland as shown, light depends on
solid, incandescent particles. Thus, when solid particles are introduced
into the colorless flame of hydrogen it is rendered luminous. We
may, however, have a luminous flame without solid particles. A
bright light is produced, for example, when metallic arsenic is burnt
in oxygen, although the metal and the product of its combustion are
both gaseous at the temperature of the flame. A mixture of nitrogen
dioxide and carbonic disulphide again, burns with a luminous flame.
(3.) Temperature. Thus Sulphur, phosphorus, and other bodies give
more light when burnt in oxygen than in air. The nitrogen in the latter
not only contributes nothing to the energy of the combustion, but
actually lowers the temperature, by removing the heat resulting from
the combination of the burning body with the oxygen. (y.) Density
of the gases. (1.) The density of the gas supporting combustion. An
alcohol flame burns with a very feeble light in air at 30° Bar. Pr.,
but with a good light in an atmosphere at 120° Bar. Pr. A candle
gives less light on the top of the mountain than in the valley,
although the tallow may be consumed at the same rate in both cases.
Thus increased light results from condensing, and decreased light from
rarefying the surrounding atmosphere. (2.) The density of the com-
bustible gas and the products of the combustion. It would appear that
luminosity is closely related to the vapor densities of the products, the
higher the specific gravity of the products, the more intense the
light. Thus, e.g., when hydrogen is burnt in air, it produces water,
which has a density of 9; whilst in chlorine, it forms hydrochloric
acid, which has a density of 1825. Hence, the light produced by
burning hydrogen in chlorine, is much greater than that produced
by burning hydrogen in air. Sulphur burnt in oxygen forms SO.
(density 32); phosphorus when burnt in oxygen forms P.O; (density
142); hence the greater light of the latter compared with the former.
The color of a flame depends on the kind of solid particles it con-
tains. Thus sodium renders a flame yellow, and lithium red. Further
there are cases where the temperature of the gas before combustion
affects the color of the flame, as happens with carbonic oxide, the
cold gas giving a blue, and the hot gas a yellowish-red flame.
We may here note that to obtain a maximum light from any flame:—
(1.) The supply of air must not be excessive, otherwise combustion
will be too complete, the luminosity of the flame being decreased for
two reasons, (a) that the carbon particles are consumed before they
are sufficiently heated to emit light, and (3) that the excess of atmo-
spheric nitrogen serves to cool the flame, thereby decreasing its
illuminating power. This is illustrated by blowing on a flame, or by
increasing the draught by lengthening the chimney.
(2.) The supply of air must not be too limited, otherwise the carbon
passes off unburnt. The flame thus becomes Smoky.
SILICIC HYDRIDE. 235
CoMPOUND of HYDROGEN AND SILICON.
Silicic Hydride (H,Si).
Synonym,_Hydride of Silicon.
Preparation.—(1.) By decomposing magnesic silicide with dilute
hydrochloric acid. (Wöhler.)
‘(2.) By passing a galvanic current, the positive pole consisting
of aluminium containing silicon, through a sodic chloride Solution.
Properties.—A colorless gas. When impure it fires spontaneously
in air, giving off white fumes of amorphous silica. The pure
gas does not ignite spontaneously. It is decomposed by heat.
It precipitates many metallic solutions but not those of lead or
platinum.
n 236 BIANDBOOK OF MODERN CHIEMISTRY.
SECTION II.--THE METALs.
CHAPTER X.
GENERAL REMARKS ON THE METALS.
Derivation and Definition of a Metal—Order of Discovery–Natural History—
Physical and Sensible Properties—Chemical Properties—The Oxides—Classifi-
cation of the Metals.
Derivation.—Méra)\\ov a metal. The word is found in every modern
language.
Definition.—Our definition of a metal is twofold. Physically, “a
metal is an opaque body, having a metallic lustre, and possessing for
the most part a good conducting power for heat and electricity.”
Chemically, “it is an element capable of forming a base by its com-
bination with oxygen, and a salt by its combination with a salt
radical.”
The division, however, of inorganic bodies into metals and
metalloids is, strictly speaking, one of convenience only.
Order of Discovery.-Seven metals were known to the ancients
(viz., Au, Ag, Cu, Pb, Fe, Hg, Sn); one was discovered in the fifteenth
century (viz., Sb); two in the sixteenth (viz., Bi and Zn); eleven in
the eighteenth (viz., As, Cr, Co, Mn, Mo, Ni, Pt, Te, Ti, W, U); and
the rest in the nineteenth. -
Natural History.—(a.) In the mineral kingdom, the metals are
found either (1) native, in a free state as gold, silver, etc., or as
alloys, as e. g., gold with silver, gold with palladium, etc.; or (2) in
combination with sulphur (galena, PbS), with oxygen (haematite,
Fe2O3), or with the haloids (common salt, NaCl); or (3) as oxy-salts,
as e.g., sulphates (heavy spar, BaSO4), carbonates (strontianite, SrCO3),
phosphates (apatite), etc. (ſ3.) In the vegetable kingdom, sodium and
potassium are found in all plants, and manganese, silver and lithium
in most. (y.) In the animal kingdom, iron is found in the blood,
manganese in the hair, calcium in the bones, etc.
As regards distribution, some are widely distributed over the whole
crust of the earth (e.g., Ca, Al, Mg, Na, Fe), whilst others are found
in small quantities only, and in few localities. Usually, they occur
in cracks (lodes), in particular rocks (as e.g., Au, Ag, etc.), whilst in
other cases, ores, such as ironstone, are found in the more recent
sedimentary formations.
I. Sensible and Physical Properties.-(1) Color. This varies as
follows:–(a). Red (Cu). (ſ3.) Bright yellow (Au). (y.) Tale yellow
METALS. 237
(Ba). (3.) Reddish grey (Co, Ni, Bi). (e.) Bluish (Pb, Zn, Cd). (...)
Grey (Fe, Mo, W, U, Mn, Sb), and (m.) White, which includes nearly
all the remainder (lunar metals).
(2.) Taste and smell. The taste of the metals is usually astringent
(metallic taste). This is probably dependent on some chemical or
electrical effect set up by the action of the saliva, and is often lost
when they exist in combination (as NaCl). They possess generally
but little odor. Iron, copper, and some other metals when rubbed give
out a peculiar smell, and arsenicum when heated emits a garlic
odor.
(3.) Lustre. In their massive and polished condition, but not when
finely divided, the metals generally possess a “metallic lustre,” de-
pending on the almost total reflexion of the rays of light from their
surface. Certain metalloids, moreover, also possess a certain degree
of lustre, as e. g., iodine, silicium, graphite, etc.
(4.) Opacity. The metals are almost perfectly opaque to light.
Fine gold leaf, however, is said to transmit a green light (Faraday,
Med. Gazette, Vol. 1, 1845); silver leaf, a purple light; mercury, a
blue light (Melseus and Arago, Chemical Gazette, February 1, 1846)
We must be careful not to confound the passage of light through
cracks, accompanied by the phenomena of diffraction, with the actual
transparency of the metal.
(5.) Teature. (a.) Some metals have a fibrous texture (Fe); (3.)
some are lamellated (Zn, Bi, Sb); (y.) and some are crystalline (Cu,
etc.)
(6.) Crystalline form. Most metals may be made to crystallise.
The crystals may be formed by such means as the following:—
(a.) By fusion and slow cooling (Bi, Pb).
(6.) By precipitation with another metal or non-metal (Ag by Hg
or P; Pb by Zn, etc.).
(y.) By sublimation (As).
(6.) By solution (Tin as in the moirée metallique; gold from an
ethereal solution).
(e.) By electrolysis.
The crystals generally belong to the cubic system, but they are
sometimes found in rhombohedra and hexagons, as e. g., zinc, arseni-
cum, antimony, nickel. (Chemical Gazette, 1848, p. 165.)
(7.) Hardness. This varies greatly. (a.) Hydrogen is believed to
be a gaseous metal, whilst (3) mercury is liquid, and gallium melts
by the heat of the hand. (y.) Some are so soft that they can be
indented with the nail (K, Na). (8.) Others can be cut with a knife
(Pb, Au, Ag); (e.) whilst the majority are extremely hard (Sn, W, Fe,
Ir, etc.)
The same metal may present great differences in hardness. Thus
iron may be rendered sufficiently soft to be cut with a steel saw, or so
hard that it will scratch glass.
238 HANIDBOOK OF MODERN CHEMISTRY.
(8.) Elasticity and Sonorousness. The sound-giving power of a body
is intimately associated with its elasticity, or “power of returning to
its original shape when disturbed.”
(a.) Some metals are very elastic (Fe, Mn, Al, Ag); (3), others bend,
but when let go do not return to their original shape (Pb, Sn, etc.),
whilst (y) others are brittle (As, Bi, etc.)
(9.) Malleability, i.e., “The capability of forming thin leaves when
hammered or rolled.” (a.) Some metals are very malleable. The
following is the order of the malleability of the malleable metals,
commencing with those in which the property is most marked, viz.,
Au, Ag, Cu, Pt, Pd, Fe, Al, Sn, Zn, Pb, Cd, Ni, Co. The alkaline
metals and frozen mercury are also malleable. (3.) The remaining
metals are not malleable.
(10.) Ductility, i.e., “The property of being drawn into fine wire.”
This property is closely but not necessarily related to malleability.
Iron is a less malleable metal than copper, but more ductile. Tin is
less ductile than zinc, but more malleable.
The order of the ductility of the ductile metals, beginning with those
most ductile, is as follows—Au, Ag, Pt, Fe, Cu, Pd, Cd, Co, Ni, Al,
Zn, Sn, Tl, Mg, Li.
Some non-metallic bodies, in a state of fusion, are also very ductile,
such as sulphur.
(11.) Tenacity, i.e., “The property of resisting weight.” This is
measured by the weight a given sized wire can support, the weights
being added as nearly as possible within the same time. Lead being
taken as 1, the following numbers represent the relative tenacity of
certain metals—Pb 1 ; Cd 1-2; Sn 1.3; Au 5.6; Zn 8-0 ; Ag 8:5;
Pt 13; Pd 15; Cu 17; Fe 26. This tenacity is influenced by many
circumstances, as, e.g.—(a.) By the purity of the metal. (3.) By the
temperature. Thus heat diminishes tenacity. Iron is more tenacious
when heated to 212°F. (100° C.) than when cold, but when heated
above this temperature, its tenacity is lessened. (y). By annealing.
Thus the tenacity of gold, by annealing, is reduced one-half; platinum,
one-third ; iron, one-fourth, etc.
(12.) “Brittleness, i.e., “The property of breaking into small pieces
when hammered.” This varies greatly. The disintegration of gold
or copper requires great force, whilst bismuth and antimony are, on
the contrary, very brittle. Brittleness is frequently influenced by
temperature. Thus, cold zinc is brittle, whilst hot zinc is malleable.
(13.) Specific gravity. This varies greatly from lithium, which has
one-half the specific gravity of water, to platinum which has twenty-one
times its density. (See Table of Elements.) It will be noticed that
the lightest metals, such as K, Na and Li, are the most oxidizable,
whilst the heaviest, such as Pt, Ir, etc., are the least oxidizable. It
has been remarked that the specific gravity is increased by hammering
and rolling.
METALS. 239
(14.) Thermotic properties. (a.) All metals expand by heat and contract
by cold. Lead, however, after it has been heated, does not, on cooling,
return to its original size. Each metal possesses its own rate of
expansion. The expansion of the metals generally is fairly uniform
for equal increments of heat up to 212°F. (100° C.), but beyond this
point expansion becomes irregular.
(3.) All metals conduct heat, but their conductivity varies. Thus,
if the conduction of silver be taken to equal 100, copper equals 74,
iron 12, lead 9, platinum 8, bismuth 2, etc. In estimating the con-
ductivity of a metal for heat, its specific heat must always be taken
into account.
(y.) Fusibility, i.e., the change from a solid to a liquid state by the
action of heat,” (fundo, I pour out).-The melting points of the
metals vary greatly. Thus, mercury fuses at —37.9°F. (–38-8°C.);
sodium and potassium between 143° and 212°F. (60° and 100°C.);
silver, copper, and gold at a bright red heat (1832° to 2012°F., or
1000° to 1100° C.); iron at a white heat (2732° to 4462°F., or 1500°
to 2500° C.); whilst others, such as platinum, etc., need the heat of
the oxy-hydrogen blow-pipe, or voltaic arc, to effect their fusion.
Welding implies the union of metals by pressure, when brought to
the pasty state, that is, a stage previous to complete fusion (e.g., Fe,
Pt, Tl, Li, K, Pd).
(6.) Volatility, i.e., “the capability of being converted into vapor,”
(volo, I fly).
(1.) Some metals are volatile at ordinary temperatures (Hg).
(2.) Others are volatile below redness (K, Na, As). In the case
of arsenicum, it volatizes before it melts; hence, in order to effect its
fusion, the heat must be applied to the metal under pressure.
(3.) Others are volatile in an ordinary fire (Mg, Zn, Cd).
(4.) Others are volatile by the heat of the blast furnace (Cu
Pb, Ag).
(5) Others are almost, but not absolutely non-volatile (as Au, Pt).
(e.) Specific heat (see page 37). If it be desired to raise the
temperature of 1 kilo. of platinum and 1 kilo. of water respectively
1 degree, we should find that it would require 31 times as much heat
to raise the water as it would to raise the platinum. This quantity
is called the specific heat of a metal. Therefore if the specific heat of
water = 1, the specific heat of platinum = sºr or 0.032.
If equal weights of the metals be taken, the specific heat will be
found to vary with the metal; but if atomic weights of the metals be
taken, the specific heat (or atomic heat as it is called in this case) will
be found in all cases to be equal.
Atomic heat therefore is specific heat estimated not on equal weights
as 1 kilo, but on atomic weights. It may also be estimated by multi-
plying the specific heat by the atomic weight.
It will further be observed that the atomic weight of a metal in any
y
240 IIANDBOOK OF MODERN CITEMISTRY.
doubtful case, may be checked by determining its specific heat. This
relationship is not, however, peculiar to the metals.
(15.) Electrical Properties. (a.) Conductivity. All metals conduct elec-
tricity, but their electric conductivity is unequal. Thus, the conduct-
ing power of silver and copper is five times greater than that of iron
and platinum, and twelve times greater than that of lead. Hydrogen
is not an electrical conductor, but it is to be noted that the metals
generally are not conductors in a state of vapor.
(3) The metals, when liberated from their compounds, appear at the ne-
gative pole of the battery.
(16.) Magnetic Properties. (a.) Certain metals are magnetic at
ordinary temperatures, their magnetic power being generally
increased by cold (Fe, Ni, Co). (3.) Other metals are attracted
equally by either pole of a magnet. If such metals be suspended in
the form of a bar over the poles of a horseshoe magnet, they arrange
themselves awially; that is, with their ends over each pole (Fe, Ni, Co,
Mn, Cr, Pd, Pt, Os). These metals are called magnetics. (y.) Other
metals are repelled by a magnet; when bars of such metals are
suspended over the poles of a horseshoe magnet they arrange
themselves equatorially; that is, contrary to the poles (Bi, Sb, As, Zn,
Pb, Sn, Hg, Au). These metals are called diamagnetics.
(17.) Power of absorbing gases (occlusion). Thus, platinum and iron
at a red heat freely absorb hydrogen (Deville and Troost). Platinum
is capable of absorbing 3-8 volumes of hydrogen at a red heat, whilst
palladium absorbs at a heat below 100° C. 643 times its volume.
This power of hydrogen (hydrogenium) of forming an alloy, and its
near relationship in this state to the metals (as, e.g., its power of
conducting heat and electricity, its magnetic properties, etc.) have led
chemists to regard hydrogen gas as the vapor of a highly volatile
metal.
II. Chemical Properties.—(1.) The metals being elements, resist
decomposition. We shall consider first of all their combinations with
Oxygen.
THE OXIDES.
All the metals may be oxidized, and often in several proportions.
The oxides are closely analogous to the chlorides; oxides being
regarded as substitution derivatives of one or more molecules of H2O,
and chlorides as derivatives of one or more molecules of HCl. There
are, however, certain oxides, as PbO2, without chlorine analogues.
The oxides generally are opaque, earthy-looking bodies, and destitute
of metallic lustre. -
A hydrocide is a compound where only a part of the hydrogen of
one or more molecules of water is replaced by a metal. Thus, K'
being a monad and Ca" a dyad, and Al" a hexad—
KHO=potassic hydroxide; Ca"(HO),=calcic hydroxide;
Alº"(HO)6=aluminic hydroxide.
THE OXIDES OF METALS. 241.
The soluble hydroxides have a strong alkaline reaction.
All metals except gold, platinum, iridium, rhodium, and ruthenium
are capable of combining with oxygen directly; that is, without the
intervention of a third element. Their rapidity of oxidation is
iargely influenced (a) By the presence of moisture, pure dry oxygen
having very little action on the metals at ordinary temperatures,
except on the alkaline metals; (3.) By the temperature; and (y.) By
the condition of the metals themselves; that is, whether they are in a
finely divided or in a massive state.
It is to be noted that the lightest metals are those most easily oſcidized
(as Na, K, etc.), and the heaviest metals those least easily owidized (as
Au, Pt). Thus the attraction of a metal for oxygen is inversely to its
specific gravity. We may classify the action of oxygen on the metals
as follows:—
(A.) Metals that combine with oacygen readily and part from it with
difficulty. Of these there are several classes.
(i.) Metals that combine with the oxygen of air and water at
ordinary temperatures, liberating hydrogen in the case of the water
(K, Na, Li, Ba, Sr, Ca).
(2.) Metals that combine with atmospheric oxygen slowly, and with
the oxygen of water only when heated (Mg, Zn, Al, Cd, Mn, Ni, Co, Fe).
(These metals decompose HCl and H2SO, at common temperatures,
liberating hydrogen).
(3.) Metals that combine with atmospheric oxygen very slowly, and
with the oxygen of water only when the metal is red-hot (Sb, As, Sn).
(These metals will not decompose HCl and H.SO, at common
temperatures, but will decompose KHO, liberating hydrogen.)
(4.) Metals that combine with atmospheric oxygen slowly at
ordinary temperatures and rapidly when red-hot, but will not
decompose water at any temperature (Cu, Pb, Bi). These oxides
cannot be decomposed by heat alone.
(B.) Metals that combine with oxygen with difficulty and part from it
readily (noble metals).
Thus, in the case of mercury both oxidation and deoxidation may
be easily effected by heat.
Preparation of Oxides.—I. Hydrated metallie orides. By precipi-
tating a metallic salt with an alkaline hydrate :-
ZnSO -- 2KHO R.S.O., + ZnH,0s.
Zincic sulphate + Potassic hydrate Potassic sulphate + Hydrated Zincic oxide.
[SO.Zno" + 20RīI SO, Koo + ZnHoo.
II. Anhydrous oxides. (1.) By burning a metal in air or oxygen, as in
the case of Zn, As, Pb, K, Na. (A protoxide may often be converted
into a peroride by heating it in a current of air or oxygen.
(2.) By the ignition of
(a.) Witrates, nitric anhydride being expelled (Hg, Bi, Cu, Ba, Sr.).
(3) Carbonates, CO., being expelled. (This occurs with all
carbonates excepting those of Cs, Rb, Na, K, Ba, Li),
R
=
242
HANDBOOK OF MODERN CEIEMISTRY.
(y.) Hydrated orides (Fe).
(6.) Sulphates (as those of alumina, ferric oxide).
(3.) All acid oxides may be prepared by deflagrating the metal or
its sulphide with nitre.
Warieties of Oxides.—Oxides may be divided into three classes:
I. Basic or alkaline oasides; i.e., oxides that act as bases (Ag30,
PbO).
II. Neutral, saline or indifferent orides ; i.e., oxides that have very
very slight disposition to enter into combination (MnO2).
III. Acid oacides or metallic anhydrides; i.e., oxides which when hy-
drated, form acids (As2O5).
Table of Ovides.
Names.
Formula.
Types.
Metals belonging
to the group.
I. Suboxides . .
II. Monoxides ..
III. Sesquioxides
IV. Three-fourths
Oxides . . . .
W. Dioxides . . . .
WI. Trioxides
VII. Anhydrides. .
'M',0
M”,0,
'M",0,
M30,
Or
M”O +M”,0a
(a.) MVO,
(3.) M',0,
.) Miv()
(y º:
M,0s
"Cu',0
A
O-
g,0
Ca"O
Al,”0,
Fe30,
Pt(),
Na,02
SnO,
CrO3
AS20s
Cu, Pb, Hg
The metals of the
alkalies with Tl',
Ag', and the met-
als of the alka-
line earths: with
Mg", Zn", Cd",
La", Di", Th".
Protoxides of Ce",
7 Co", Ni",
Fe", Cr”, Mn",
Sn", Cu", Pb",
Hg", Pd”
Al, Ce, Fe, Mn,
Cr, Sb, Bi, U.
Co, Ni.
As, Au,
Fe, Cr, U, Mn,Ni,
O;
Also double oxides
as Fe0,0r,0,
(chrome iron-
stone); MgO,
Al2O4 (spinelle);
ZnOAl,0s (Gah-
nite)
Pt, Pd
Na, Ag, Ba, Ca,
Sr, Mn, Pb
Sn, Ti
Cr, Mo, W, Ru,
Fe, Mn
As, W, Sb,
Characteristics
of group.
Basic. A dyad metal, becomes
equivalent to a single H atom.
Unstable bodies easily decom-
posed.
Basic. The alkaline oxides
combine with water to form
hydrates, one molecule of
each forming two molecules
of hydrate (Na,0+H,0=
2NaIIO).
The alkaline earth-oxides also
form hydrates, one molecule
each of the oxide and water
forming one molecule of hy-
drate (CaO +H,0=CaB,02).
Feebly Basic. Salts redden
litmus.
Neutral. Evolve Cl with HCl.
Feebly acid.
Neutral. By the action of acids
they form MO-H-M,0s.
Feebly Basic. Form hydrates
(Pt(),2H,0.) -
Either neutral,or else form very
unstable salts which evolve O
with H.S.O. With HCl
they either furnish hydroxyl
or evolve chlorine,
Acid as hydrates.
Acid (metallic anhydrides.)
Acid.
THE OXIDES OF METALS, 243
Properties of the Oxides.—(a.) Physical, etc. The oxides are solid
bodies, of various colors, having generally a more or less metallic
taste, but no smell. They are harder than the metals from which
they are formed, but of less specific gravity.
Action of heat on metallic oſcides.—(A.) Fusibility. An oxide of a metal
is generally less fusible than the metal. To this general rule there
are three exceptions, viz., Fe0, Craſ), MoQ3.
(i.) Some oxides are volatile at ordinary temperatures (As2O3, Sb2O3,
OsO4).
(ii.) Some oxides fuse at a red heat (K2O, Na2O, PbO, Bi,0s).
(iii.) Some oxides require a white heat (CuO, MoQ3, Cr,0s,
Fe3O4).
(iv.) Some oxides need the heat of the oxy-hydrogen jet (BaO, Sr0,
Al2O3).
(v.) Some oxides are absolutely infusible (zirconia, yttria).
(B.) Reduction. At a red heat certain oxides are completely, whilst
others are partially, decomposed.
(i.) Reduction is complete in the case of the oxides of Au, Ag, Pt,
Pd, Hg, etc.
(ii.) Reduction is partial in the case of such peroxides as PbO2, Co,0s,
Ni,0s, BaO2, which by heat become protoxides, as Pb"O, Co"O, Ni"O,
Ba"O. Again, the anhydrides As40s, and CrO3 become when heated
AS20s and Cr30s, and MnO2 becomes Mn2O4.
(C.) Heated in a current of hydrogen, all the oxides may be completely
reduced, excepting Al2O3, Cr30s, MnO, and the oxides of the alkalies
and of the alkaline earths. The oxides of mercury, silver, platinum
and gold, are reduced at 212°F. (100° C), and the rest at a red heat.
Example—(CuO + H2=Cu+ H2O).
[Note here reciprocal action. Free hydrogen reduces the oxide of
iron, forming steam ; steam passed over red hot iron yields oxide of
iron and free hydrogen.]
(D.) Heated with carbon, all the oxides may be reduced, except the
Oxides of lithium and the oxides of the earth-metals. In the case of
the readily oxidizable metals (as K, Zn, Fe), CO is evolved, the CO2
first produced being afterwards decomposed; but with the less readily
oxidizable metals (such as Cu, Pb, etc.) the CO2 is evolved without
suffering further decomposition.
Action of electricity on metallic oacides. The protoxides are insulators,
whilst some of the peroxides are conductors.
Action of Water on the Oxides.—The oxides of the alkaline metals,
together with the oxides of barium, strontium, calcium, and thallium,
and the hydrated acid oxides, are freely soluble in water; the oxides
of lead, silver, and mercury, are slightly soluble, and the remainder
are insoluble.
Most oxides unite chemically with water to form hydroxides, or
hydrated oxides. All hydroxides neutralise acids. In some cases the
244 HANDBOOK OF MODERN CHEMISTRY.
metal will not part with its water molecule at any temperature, as in
the case of the alkaline hydrates, whilst in the case of other hydrates
heat will easily effect the separation.
(3.) Chemical.—The chemical properties of the oxides are very
varied, depending to a great extent on the different degrees of oxida-
tion of which the metal is capable.
Thus of the oxides of manganese, MnO and Mn2O3 are basic oxides;
Mn2O, is an indifferent oxide (that is neither basic nor acid), whilst
MnO, and Mn2O, are acid oxides. As a rule the higher the oxide the
less basic it becomes.
Action of Chlorine on the orides.—All metallic oxides are decomposed
when heated in an atmosphere of chlorine except magnesia and the
oxides of the earths. The metal is reduced in the case of the oxides
of the noble metals, whilst in other cases a metallic chloride is formed.
Chlorine decomposes certain oxides, as AgaO, at ordinary temperatures.
With the hydrated oxides suspended in water, chlorine forms in
the case of the alkalies and alkaline earths bleaching compounds (see
page 280), whilst with the hydrated oxides of iron, manganese, chro-
mium, cobalt, and nickel, it forms either a mixture of a chloride and a
hydrated sesquioxide (300H2O2+ Cl2=CoCl2 + Co., Hé06); or if the
liquid be strongly alkaline, a metallic sesquioxide only (20orf2O2+
2KHO + Cl2=Co., HSO5+2KCl); or if the metal be capable of forming
an acid, a salt results by the action of the acid on an excess of the
alkali (Fe2H606-1-10KHO + 3Cl2=2|K.FeO44-6ECC1-1-8B30).
Action of sulphur on the oacides.—At high temperatures sulphur decom-
poses most metallic oxides, with the exception of MgO, Al2O3, Cr,03,
SnO2, TiO2, and the oxides of the earths proper. In most cases a
sulphide is formed, and SO2 escapes; whilst in the case of the
oxides of the alkalies and alkaline earths, a mixture of a sulphide and
a sulphate of the metal is formed.
Action of nascent hydrogen on the orides.—Most oxides are decom-
posed by nascent hydrogen.
Action of acids on the metallic oxides.—(1.) Hydrochloric acid.—In
most cases, water and a corresponding metallic chloride are formed.
Thus—
Cuprous oride forms cuprous chloride (Cu,0+2HCl=H20+Cu2Cl2).
Sesquioxides form sesquichlorides (Fe2O3 + 6HCl=3|H2O+Fe2Cl6).
Binorides form tetrachlorides (SnO2+4FICl=2H20+ SnCl4).
If chlorides corresponding to the oxides do not exist, other changes
result; thus, in the case of the following oxides, the following re-
actions occur : — -
Antimonic oride; Sb2O3 + 6 HCl=3 H20+ 2SbCla.
Dimanganic trioride; Mn2O3 + 6HCl=3|H.0+2MnCl2 + Cla.
Manganic peroride; MnO2+4HCl=2H20+ MnOl., + Cl2.
Chronic anhydride; 20r.04+ 12HCl=6H20+CraCl6+3Cl2.
(2.) Sulphuric acid—Sulphuric acid combines with basic orides to
METALS. 245
form salts, the oil of vitriol displacing all other acids with which the
oxide may be united ; whilst on either indifferent or on acid oacides the
sulphuric acid causes an escape of oxygen, and combines with the
base formed. Thus—2MnO2+2Eſ...SO4–2MnSO4+2H20+ O2.
In all cases when sulphuric acid acts on orides, water is formed, whilst
when it acts on metals, hydrogen is liberated.
(3.) Hydro-sulphuric acid (H2S). — Most metallic oxides (except
magnesia, alumina, and chromic oxide) are converted by H2S into
sulphides or sulph-hydrates of the metal and water—
PbO--H.S=PbS4-H.O.
We may now return to the metals themselves, and consider their
other chemical relations.
(2.) Action of the haloid elements.-Chlorine combines directly with
all the metals, often at common temperatures (as e.g., with Sb), but
under all circumstances by the application of heat (see page 75). Bro-
mine, iodine, and fluorine also combine with most metals directly.
(3.) Action of carbon.—Iron, manganese, palladium, iridium, and a
few other metals, form compounds with carbon, called carbides. The
carbides are generally more fusible than the metals themselves.
(4.) Action of phosphorus.-Phosphorus combines with the metals
to form phosphides.
(5.) Action of nitrogen.—The affinity of nitrogen for the metals is
slight, the compounds formed, called nitrides, being usually explosive
and difficult of examination. They are generally prepared by the
action of ammonia on various oxides (Au, Ag, Pt, Cu, Hg, Fe), but
in the case of vanadium, titanium, and molybdenum, direct union of
the metal and nitrogen may be effected.
(6.) Action of hydrogen.—Hydrogen forms hydrides with five metals
(As, Sb, Cu, Fe, K). The hydrides of arsenicum and antimony are
gaseous, and are completely decomposed by a red heat. A solid
hydride of arsenicum is believed to exist.
(7.) Silicon, boron, selenium, and tellurium also combine with certain
of the metals to form silicides, borides, selenides and tellurides.
(8.) Action of water on the metals :-
(a.) Certain metals decompose water at common temperatures (K, Na,
Li, Ba, Sr, Ca).
(3.) Others, when the water is boiling (Mg, Al, Cd, Mn).
(y.) Others, when the metal is red hot (Sb, As, Sn, Zn, Fe, Cr,
Co, Ni).
(8.) Others, when the metal is white hot (Al, Pb, Bi, Cu), whilst
(e.) Others do not decompose water at all (the noble metals).
The action of the metals on water is modified (1) by the presence of
air, whereby the action of a metal on water is rendered more ener-
getic; and (2) by the contact of two metals, whereby a galvanic current
is set up, and the energy of solution intensified.
246 HANDBOOK OF MODERN CHEMISTRY.
(9.) Action of the acids on metals.-(A.) Sulphuric acid :—
(a.) Sulphuric anhydride cannot be made to combine directly with
the metals. .
(6.) The concentrated acid acts on very few metals without heat,
whilst, -
(y.) The dilute acid acts on most metals at ordinary temperatures,
a metallic sulphate being formed with the liberation of hydrogen (Zn,
Fe, Co, Ni, Mn).
(6.) In certain cases heat is required to bring about combination
with the dilute acid, when a metallic sulphate is commonly formed
and sulphurous acid liberated (Ag, Cu, Hg, As, Sb, Bi, Sn, Pb)
(Ag3 +2(H2SO4)=Ag2SO4+2H20+SO2).
(e.) The acid (strong or dilute) has no action on gold, platinum,
rhodium, or iridium. Thus, sulphuric acid is used to part silver from
gold, and gold from copper.
(4.) When the vapor of sulphuric acid is passed over red hot
platinum, it is decomposed into oxygen and sulphurous acid (see p. 57).
(B.) Witric acid. Nitric acid dissolves most metals, and more
readily when dilute than when concentrated. (a.) Upon gold and
platinum nitric acid has no action; whilst (b.) tin and antimony are not
dissolved but oxidised by nitric acid, the insoluble anhydrides SnO2
and Sb2O3 being formed.
We may here note that dilute sulphuric acid by its action on metals
usually liberates hydrogen, but that nitric acid does not. No doubt,
however, hydrogen is in the first instance set free, but owing to the
intense action of the nitric acid the hydrogen formed is rapidly oxidised.
Many products result from the action of nitric acid on the metals,
of which we may note the following:—
(a.) Nitrous oride (N2O). By the action of the dilute acid on an
energetic metal, such as zinc :—
4Zn + 10HNO3 = 4(Zn2NO) + 5H2O + N2O.
Zinc + Nitric acid = Zincic nitrate + Water + Nitrous oxide.
4Zn + 10NO, Ho- 4 | §§Zao'+ 5OH2 + ON2.
(6.) Witric oxide (N.O.). By the action of an acid of specific
gravity 1.25 on such metals as Cu and Hg :—
3Cu + 81 INO, a 3(Cu2NOs) + 4H20 + N202.
Copper + Nitric acid = Cupric nitrate + Water + Nitric oxide.
3Cu + 8NOg|Ho = 8||Nº. Cuo" + 4OH2 + {N}.
2 NO2 2 NO.
(y.) Nitrous anhydride (N2O3). By the action of the acid on silver
or palladium :—
2Age -- 6HNO3 + 4AgNO3 + 3H20+ N,0s.
Silver + Nitric acid = Argentic nitrate + Water + Nitrous anhydride.
ſ NO.
& O
2Age + 6NO.Ho- 4NOAAgo + 3OH2+ | No
METALS. ! 247
(3.) Nitric perovide (N20,), By the action of an acid of specific
gravity 1:42 on tin, copper, etc. :—
5Sn+ 20BINOs - Sn;010, 5H2O + 5II.20 + 10N2O4.
Tin -- Nitric acid = Metastannic acid + Water + Nitric Peroxide.
5Sn+ 20INO2Ho-Sn;05.Holo + 5OH2 + 10N2O4.
(e.) Nitrogen. By the action of the acid on copper at a high
temperature :-
5Cu + 12HNO2 = 5(Cu2NOs) + 6H2O + N2.
(4.) Ammonia (NH3). Any metal capable of decomposing water
will generate ammonia in dilute nitric acid. (a) In the first stage nas-
cent hydrogen is set free; (3) this reacts on the nitric acid, forming
water with the oxygen, and ammonia with the nitrogen; (y) and lastly,
the excess of ammonia combines with the excess of acid. Thus:-
(a.) 2HNO3 + Zn Zn2NO3 + H2.
Nitric acid + Zinc Zincic nitrate + Hydrogen.
2NO2Ho + Zn N20,2no" + H2.
(3.) 2BNO, + 9H. 2NH, + 6H2O.
Nitric acid + Hydrogen
Ammonia –H Water.
2NO2Ho + 9PI2
2NH, -i- 6OH2.
(y.) 2EINO, + 2NHs 2(NH,0, NO2).
Nitric acid + Ammonia
Ammonic nitrate.
2NO.Ho + 2NH3 2NO2(NH,0).
(C.) Hydrochloric acid. The affinity of a metal for chlorine is
somewhat greater than its affinity for oxygen ; hence the action of
hydrochloric acid on a metal is always a little in excess of the action
of water on a metal. All metals that decompose water at a red heat,
decompose hydrochloric acid, hydrogen being liberated and a chloride
of the metal formed (2HC1-i-Zn=ZnCl2 + H2). It is to be noted
that—
(a.) Silver does not decompose water at any temperature, but is
slowly decomposed and dissolved by strong hydrochloric acid.
(3.) Gold and platinum are not acted on by hydrochloric acid unless
free chlorine be present.
(D.) Nitro-muriatic acid (aqua regia). This is a mixture of one
part of HNO3 and three parts of HCl, Gold, platinum and the
noble metals generally are dissolved by it, free chlorine, together
with red fumes (viz., the oxy-chlorides of nitrogen NOCl and NOCl.)
being evolved.
(E.) Hydrosulphuric acid (sulphuretted hydrogen).
(a.) On certain metals sulphuretted hydrogen acts at ordinary
temperatures (Hg, Ag); whilst
(3.) On other metals the action does not occur without heat, when
the displacement of the hydrogen from the H.S may be, either
(1.) Complete, as e.g., H.S + Sn = SnS + H2, or
(2.) Partial, as e.g., 2PI.S + 2K = 2KHS + H2.
=
=
248 . HANDBOOK OF MODERN CHEMISTRY.
(10.) Action of alkalies. Certain metals snch as iron and copper
when red hot decompose ammonia gas. When potassium is gently
heated in dry ammonia, KHAN is formed, which is regarded by some
as a substitution derivative of H3N, and by others as a compound of
potassium and amidogen (H3N).
Platinum as well as other metals are oxidised when heated
with potassic hydrate.
Classification of the Metals.-The classification of the metals
according to their atomicity has manifest advantages. The table
(page 42) illustrates their arrangement accordingly.
We prefer, however, (regarding the primary object of classification
as convenience,) to adopt simply a division into the various groups
occurring in the ordinary process of systematic analysis, commencing
with Group VI. (the alkaline metals) and working backwards.
249
p CHAPTER XI.
ALLOYS AND SALTS.
Alloys—Changes in property effected by Alloying—Acids—Bases—Salts. Haloid
Salts—Chlorides, Bromides, Iodides, Fluorides, Sulphides, Selenides, Phosphides,
Carbides, Borides, Silicides. Ory - Salts—Sulphates, Selenates, Chromates,
Manganates, Tungstates, Molybdates, Tellurates, Hyposulphates, Thiosulphates,
Sulphites, Hyposulphates, Nitrates, Nitrites, Hyponitrites, Chlorates, Bromates,
Todates, Perchlorates, Periodates, Chlorites, Hypochlorites, Phosphates, Hypo-
phosphites, Phosphites, Arsenates, Antimonates, Arsenites, Carbonates, Silicates,
Borates. Double Salts.
We proceed to consider:-
I. The compounds of the metals with metals (alloys).
II. The compounds of the metals with the metalloids (salts).
ALLOYS (ad to, and ligo I bind).
Definition.—An alloy is a compound formed by the union of metals
amongst themselves. If the alloy contains mercury it is then called
an amalgam.
Are the alloys mere mechanical mixtures, or are they chemical compounds 3
To answer this question we must ask, Is there any evidence of definite
change resulting from the admixture of metals, such as happens in the
admixture of metalloids P. Matthiessen (who has specially studied
the subject of alloys) considers that alloys may be divided into two
classes:—
(1.) Physical Alloys, or mere mechanical mixtures of metals, in
which, at the time of mixture, no heat is evolved, and where each
metal imparts to the alloy its properties in the proportion in which
it exists in the alloy. As illustrations of this class we may mention
a mixture of lead and tin, or of zinc and cadmium.
(2.) Chemical Alloys, i.e., where, at the time of mixture, heat is
evolved, and where the metals forming the alloy do not impart their
properties to the alloy in the proportion in which they exist in it.
This class includes alloys of all the metals, excepting mixtures of lead,
tin, zinc, and cadmium amongst themselves.
Definite compounds no doubt exist; necessarily, however, as intensity
of combination largely depends on dissimilarity of property, the ties
of union are weak, and the separation of the components easy. Thus
(1) heat will drive off zinc from its alloy with copper, or arsenicum
from its alloy with platinum; whilst (2) slight mechanical causes,
such as the mere Squeezing through leather, will remove the excess
of mercury from a mixture of mercury and silver.
250 HANDBOOK OF MODERN CEIEMISTRY.
Change of property is the essential result of a chemical act. We
shall consider now the changes that result in the formation of alloys.
I.—CHANGES IN THE SENSIBLE AND PHYSICAL PROPERTIES OF ALLOYs.
(a.) Color. Thus the addition of 18 per cent. of nickel to brass
renders it white (Packfong, or German silver). Similarly, an alloy of
arsenicum with copper, or of platinum or palladium with gold, renders
the copper and the gold white. The alloy of gold and silver has a
pale greenish tint.
(6.) Hardness. The hardness of an alloy is usually greater than the
mean hardness of the constituent metals. Thus alittle copper (8.33 per
cent.) is added to the gold used for coinage, in order to increase the
hardness of the gold. The alloy of tin, lead, and antimony forms the
hard type-metal. The alloy of copper and zinc forms a hard compound
that may be cast or turned. The alloy of copper and tin forms a
very hard bronze. Manganese or tungsten increase the hardness of
steel to so great an extent, that the alloy may be used for boring
through steel.
(y.) Elasticity and Sonorousness. An alloy of copper and tin
(=Cu6Sn), or of copper with zinc or lead constitutes the Sonorous
bell-metal.
(3.) Malleability. The malleability of a metal is usually decreased by
alloying. Thus, if 0.5 gr. of lead be added to 1 oz. of gold, it
destroys its malleability. If melted gold be kept for some time, even
in the vicinity of melted tin, it becomes brittle. The alloy of two
malleable metals may form a brittle alloy (e.g., gold and lead); but
no case is known where the alloy of two brittle metals forms other
than a brittle alloy. A mixture of copper, zinc, and platinum forms
a very malleable alloy; but if a trace of iron be added, in the pro-
portion of 0.5 gr, to 4 oz. of the alloy, it renders it brittle.
(e.) Tenacity. This is both increased and diminished by alloying.
(1.) Increased. If a gold wire be taken that will bear a strain of
25 lbs., it will be found that a similar sized one of copper will bear a
strain of 25-30 lbs. If now a wire of the same gauge, made of an
alloy of gold with 8.4 per cent. of copper be tested, it will be found
to bear a strain of from 70-75 lbs.
(2.) Diminished. If a copper wire be taken which bears a strain of
from 25 to 30 lbs., the same sized tin wire will be found to bear a
strain of less than 7 lbs., whilst a wire formed by the alloy of equal
parts of tin and copper will not bear a strain above 7 lbs.
(...) Specific Gravity. The gravity of an alloy may be either above or
below the mean of the gravities of its constituents. Standard gold
consists of 11 parts of gold and 1 of copper, the specific gravity of the
alloy being 17-157, the mean specific gravity being 18:47.
(n.) Thermotic properties. The fusing-point of an alloy is invariably
SALTS. 251
below the mean fusing points of its constituents, just as the fusibility
of double chlorides, carbonates, or silicates, is generally lower than
the separate salts of which these double salts are composed. Thus an
alloy of four parts of bismuth (which fuses at 507°F., or 264°C.),
2 of lead (which fuses at 607° F., or 309.5°C.), and one of tin (which
fuses at 442°F., or 227.8°C.), a mixture nearly corresponding to the
formula BioPbSn melts below 212°F. (100° C). Platinum, which is
very difficult of fusion, melts easily when alloyed with arsenicum.
In the extraction of silver from lead by Pattinson's process (see Index),
it is found that the part which cools last contains nearly all the silver,
owing to the greater fusibility of the alloy of lead and silver.
(0.) The conductivity of metals for heat and electricity is usually de-
creased by alloying.
II. CHANGES IN THE CHEMICAL PROPERTIES.
These, it must be acknowledged, are not well marked.
(1.) A certain change in the capability of a metal for oa;idation may be
noted as the result of alloying. An alloy, e.g. of two oxidizable metals
(such as an alloy of lead and tin) is generally more readily oxidized
than either of its constituents.
(2.) A change in the action of acids may be remarked. For example
—German silver is completely soluble in dilute sulphuric acid,
although the acid will not attack copper, which is one of its chief con-
stituents. An alloy of 1 part of platinum and 12 parts of silver is
soluble in nitric acid, in which free platinum is insoluble. Further,
the presence of iridium and rhodium, as commonly occurs in commercial
platinum, renders the platinum less easily attacked by chemical re-
agents.
SALTS,
ACIDS, BASES, SALTs.
Chemical nomenclature, prior to 1786, was both unsystematic and
imperfect. Acetic acid to the older chemists was a mineral acid,
because it was sour. A Salt was regarded as a solid, crystallizable
substance, soluble in water.
In 1786 Lavoisier defined an acid as “an oacidized body, sour, capable
of reddening vegetable blues, and of combining with and neutralising alkalies.”
All the acids known to Lavoisier contained oxygen; he regarded this
element, therefore, as the acidifying principle of an acid, and essential
to its existence (acid-begetter). A salt Lavoisier defines as “the
wnion of an acid,” that is an anhydride, as we call it, but which
Lavoisier and his school regarded as an acid, “with an oride of a metal”
(a base). Thus KO,SOs, formed the salt sulphate of potash. This
constituted “the dualistic theory of salts.” -
In 1795 Sir H. Davy pointed out that the very type of salts (viz.
252. HANDBOOK OF MODERN CHEMISTRY.
common salt) contained neither acid nor base, and that there were
bodies in existence corresponding to Lavoisier's definition of an acid,
except that they contained no oxygen. Hence Lavoisier's definition
of acids and salts had to be modified. Acids were consequently
divided into two classes, and salts into two classes; viz.:-
(1.) Oryacids; bodies containing oxygen, which, combined with an
oxide of a metal (a base), formed oxy-salts.
(2.) Hydracids; bodies in which hydrogen was an essential ingre-
dient, the combination of the radical or characteristic element of which
with metals, formed haloid salts.
In 1812, that is, very shortly after the discovery of chlorine, Davy
recognized the similarity in the action of oxyacids and of hydracids
on metals. He further pointed out that all acids contained hydrogen,
and that an anhydride was not an acid. He suggested that all acids
were salts, and that all salts were compounds of a radical (simple or
compound) with a metal. He thus laid the foundation of “The
Pinary Theory of Salts.” Lavoisier's “Dualistic Theory” expressed
nitrate of potash as KO, NO3, or a compound of the acid (as he re-
garded it) NOs and the base KO ; whilst Davy’s “Binary Theory”
expressed it as KNO6, or a compound of the metal potassium (K)
with the acid radical NO6. Moreover, Davy remarked a close simi-
larity of constitution between Oxy-salts and haloid salts, as, for ex-
ample, between KCl and KNO6.
In 1819, Berzelius introduced his Electro-Chemical Theory, accord-
ing to which he regarded salts as compounds of an electro-negative
(that is, a body attracted by the positive pole of a battery), and an
electro-positive (that, is, a body attracted by the negative pole). All
the metalloids (excepting hydrogen) were electro-negative; all the
metals (including hydrogen) were electro-positive. This much re-
mains a fact, viz., that the elements differing most in their chemical
relationships usually exhibit the greatest activity of combination;
but, that the chemical functions are determined exclusively by the
electrical relationships, has been disproved by the discoveries of 1834
and following years. For the laws of substitution (introduced and
elaborated by Dumas, Gay Lussac, Laurent, Gerhardt, etc.) prove
the possibility of an electro-negative body like chlorine taking the
place of an electro-positive body like hydrogen in a compound. The
“ theory of types” was then called in, to aid the “theory of substi-
tution,” thus paving the way for the fuller acceptance of Davy's
“Binary theory.”
We shall here discuss the definitions of (I.) an acid, (II.) a base,
(III.) a salt.
I. Acids (akm, a point).
An Acid is “a compound containing one or more atoms of hydrogen,
capable of displacement by a metal presented to it in the form of a hydrate.”
TYPES OF DIFFERENT ACIDS. 253
Acids are of different basicities, according to the number of atoms of
displaceable hydrogen they contain. -**
A monobasic acid contains one atom of displaceable hydrogen, that is,
of hydrogen that may be displaced by a metal, e.g. :—
HNO3 (nitric acid) forms KNO3, NaNO3, Ca"2(NO3).
EICl (hydrochloric acid) forms KCl, NaCl, Ca"Cla.
A polybasic acid contains two or more atoms of displaceable hydro-
gen. It is called dibasic when it contains two atoms of displaceable
hydrogen (e.g., H2SO); tribasic when it contains three atoms (e.g.,
H3PO); and so on.
Types of different Acids,
(1.) (a.) A monobasic acid has been regarded as formed on the type
of a single molecule of water (# o) where one hydrogen atom of the
water molecule has been displaced by a compound monatomic radical.
(3.) The anhydride of such monobasic acid is regarded as formed by
the displacement of both hydrogens of the water molecule by two
molecules of the compound radical.
(y.) The Salt of a monobasic acid is regarded as formed by the
displacement of the second hydrogen atom of the acid, by a metal.
This will be seen as follows:—
(a) \% | O = HNO, (acid).
NO iº
& * } 0 = N20s (anhydride).
(ſ3.) NO, } 205 (anhydride)
FC
(2.) (a.) A dibasic acid has been regarded as formed on the type of
a double molecule of water (#. | O
double water molecule have been displaced by a compound diatomic
radical.
(3.) The anhydride of such dibasic acid is formed by the displace-
ment of the four hydrogen atoms, by two atoms of the compound
diatomic radical. -
(y.) The Salt of a dibasic acid is formed by the displacement of one
or both hydrogen atoms of the acid by a metal. -
If one of the hydrogens only be displaced by a metal, an acid salt is
formed; if both hydrogens be displaced by the same metal then a
normal salt is formed; whilst if the hydrogens be displaced by different
metals then a double salt is formed. Thus—
(a ) iº Oci-H2SO, (acid).
(3.) § Os=2SOs (anhydride).
(y.) Nº O = KNOs (salt).
J. where two hydrogen atoms of the
254 HANDBOOK OF MODERN CHEMISTRY.
(y.) #} O3=KHSO, (acid salt).
sº O3=K2SO4 (normal salt).
(3.) Similarly, a tribasic acid is regarded as formed on a treble
water type #: | O3; (a) the acid resulting from the Ha being replaced
3
by a triatomic compound radical; (3) the anhydride by the 2H, being
replaced by two atoms of the triatomic radical; and (y) the salts by the
displacement of one or more of the hydrogens of the acid by a metal.
Thus—
PO
(a) Hs
(3) #3 | O3=P,0s (anhydride).
| Os=HaBO, (acid).
(y.) §. | Os=Na,FO, (salt).
II. Bases.
A Base is “a compound body capable of being converted into a salt by
the action of an acid, and of thereby more or less neutralizing the reactions of
the acid.” Bases may be divided into three classes.
(1.) Compounds of metals with oaygen (such as baryta, lime, magnesia).
A metal usually forms but one oxide capable of producing salts with
acids; but to this general rule there are many exceptions. Thus—
The protocide of iron (Fe0) forms salts (e.g., Fe0, SO3) distinguished
as protosalts, or more commonly as ferrous salts.
The peroxide of iron (Fe2O3) forms salts (e.g., Fe2O3, 3SOs) distin-
guished as persalts, or more commonly as ferric salts.
(2.) Compounds of metals with the compound radical hydroxyl (HO)
(hydroxides, e.g., sodic hydrate NaHO (soda); potassic hydrate KHO
(potash), etc.) A hydroxide consists of one or more water molecules,
where one or more of the hydrogens are replaced by a metal. Thus—
; | o–KHo; # } O2=Ca"H2O2.
The soluble hydroxides are called alkalies, and have the power of
blueing red litmus.
(3.) Certain compounds with nitrogen, phosphorus, arsenic, and antimony,
as, for example, ammonia (NHS).
III. Salts.
A Salt is “a compound formed by the mutual action of an acid on
a base.” The name given to the salt depends on the base and
the acid present. Thus sodic nitrate implies a salt formed by a combi-
nation of sodium and nitric acid; sodic nitrite, a salt formed by a
combination of sodium and nitrous acid.
SALTS. 255
VARIETIES OF SALTs.
(1.) Haloid Salts. Compounds of a metal with a halogen, or salt radical.
A haloid salt, therefore, contains neither oxygen nor sulphur (e.g.,
NaCl, KI).
(2.) Oay-Salts. Compounds formed from an oaygen acid, by the displace-
ment of all or a part of its hydrogen by a metal or by a compound radical.
Of these we recognize several classes.
(a.) Normal Salts. A salt where all the displaceable hydrogen of the
acid is earchanged for an equivalent amount of a metal or of a positive com-
pound radical. Thus, for example,
R.S.O., from HaSO, ; NaNos from HNO3; Ca";2(PO,) from 2H3PO,.
A normal salt was formerly termed a neutral salt, that is, a salt
which neither reddens blue-litmus nor blues red-litmus. Neutrality,
however, depends more on chemical energy than on actual proportion.
Thus ZnSO, reddens blue litmus, and Na2COs blues red litmus, whilst
other normal salts, such as KNO3, are strictly neutral. Yet in mone
of these is there any free acid nor free base present. Litmus being
itself a salt consisting of a feeble vegetable acid of a red color, com-
bined with a metallic base, the addition of a salt containing a strong
acid, may set free the red litmus acid, owing to the greater intensity
of the strong acid of the salt for the litmus base, than that possessed
by the litmus acid itself. Hence a normal salt may redden blue
litmus.
(6.) Acid Salts. A salt in which the displaceable hydrogen of the acid
is only partially exchanged for a metal or positive compound radical. Acid
salts are invariably salts of polybasic acids. All acids, the hydrogen
of which plays the part of a true metal atom, and is not simply the
hydrogen of water of crystallisation, are, in a sense, true acid salts.
Thus—
RHSO, is derived from H.SO, ; KHCOs from H2COs; HNa. PO,
from HaPO,.
(y.) Basic Salts. A salt where the number of bonds of the metal or
compound radical exceeds the number of atoms of displaceable hydrogen in
the acid. This implies that the proportion of base present predominates
over the acid. Thus—
HgSO4,2Hg.0 =Turpeth Mineral.
CuCOs, Cul-I.O. =Malachite.
2PbCOs, PbH,02–White lead.
Here it will be seen that the base is in excess of the acid.
(3) Sulpho-Salts.-Compounds analogous to oxysalts, but containing
Sulphur in the place of oaygen. Thus—
Sodic sulph-arseniate; 3Na2S,AS.Ss, or 2Na,AsS, ;
Sodic sulpho-stannate; 2Na2S,SnS.
(4.) Double Salts.-Compounds where the displaceable hydrogens of the
256 & HANDBOOK OF MODERN CHEMISTRY.
acid are exchanged by different metals or compound radicals. Thus
Rochelle salt is a compound formed from tartaric acid (H.C, H,06), in
which the two atoms of hydrogen are displaced by an atom of sodium
and potassium respectively (KNaC, H,06).
Double salts may be formed, and more often are formed, from
oxides of different classes. Thus common alum consists of potassic
and aluminic sulphate, K.SO, Al23SO = R2Al44SO4. Double salts
may also be formed by a combination of haloid salts. Thus 2 KCl,
PtCl4 forms potassic platinic chloride. These combinations are re-
garded as molecular rather than atomic.
The terms oxychloride, owyiodide, etc., imply compounds formed by the
union of one or more molecules of a metallic oxide with one mole-
cule of a chloride or iodide of the same metal. Thus PbCl2,7I’b0=oxy-
chloride of lead (Turner's yellow).
HALOID SALTS (&Ac the sea).
Definition.—A haloid salt is a compound either of a metal or of a
compound radical, capable of acting as a metal (such as NH), with
a salt radical which may be either simple, like chlorine, or compound,
like cyanogen. -
Members.-Chlorides, iodides, bromides, fluorides, sulphides, sele-
nides, phosphides, carbides, borides, silicides, cyanides.
I.-Chlorides.
Definition.-Compounds of metals with chlorine (the radical of HCl).
Natural History.—The chlorides are found in all three kingdoms
of nature, chiefly in combination with the alkalies. Sodic and potassic
chlorides occur in sea water and in rock salt. Mercurous chloride
(Hg2Cl2) and silver chloride (AgCl) occur as natural minerals.
Preparation.—( 1.) By the direct action of chlorine, either (a) on
a metal (Mg+ Cl2=MgCl2); or (3) on a basic owide, either in the cold
(as AgCl), or when heated to redness, whereby the oxygen of the
oxide is expelled; or (y) on a heated mixture of carbon and a metallic
oride, whereby carbonic oxide is evolved (M,0+C+Cl2=MCl2+CO);
or (3) on a Sulphide, whereby a chloride of sulphur and a metallic
chloride are formed. -
(2.) By dissolving a metal in aqua regia (this being in reality the
action of nascent chlorine), evaporating the solution to dryness, and
redissolving the residue in water (e.g., Au, Pt, etc.). -
(3.) By the action of hydrochloric acid gas, either (a) on a metal
(Na2+2HCl=2|NaCl-H Ho); or (3) on an owide (CuO +2FICl=CuCl2+
H2O); or (y) on a sulphide of a metal.
(4.) By dissolving either a metal (see page 247), an oxide, a hy-
drate, or a carbonate of a metal in liquid hydrochloric acid, and
VARIETIES OF CHLORIDEs. 257
evaporating. The hydrated chlorides may be prepared by this pro-
cess. Many hydrated chlorides, however, evolve their chlorine as
HCl, when their solutions are evaporated—
(MgCl2 + H2O=MgO +2HCl).
(5.) The insoluble chlorides may be prepared by adding hydro-
chloric acid (or a soluble chloride) to a salt of the metal (e.g., AgCl,
PbCl2, Hg2012).
(6.) A chloride of a metal may sometimes be formed by treating the
metal itself with the chloride of another metal, whereby the first
metal will appropriate the chlorine of the second metal. Thus, if
Sodium be heated with magnesic chloride, sodic chloride and free
magnesium are produced; or, if potassium be heated with uranous
chloride, potassic chloride and free uranium are formed. (Similarly,
SnClt, SbOls, or BiCls may be prepared by heating Sn, Sb, or Bi
with HgCl2.)
varieties of Chlorides—(1) suchlorida (M.C.) {:}; as eq,
Mercurous chloride (Hg2Cl2), Cuprous chioride (Cu2Cl2).
(2.) Monochlorides (M'Cl as KCl); Dichlorides (M"Cl, as Ca"Cl.);
Trichlorides (M"Cl, as Sb"Cls); Tetrachlorides (Mivol, as PtivC1,);
Pentachlorides (MVCls as Sb'Cls); Herachlorides (MVCls as MoviCl3).
(3). Sesquichlorides ("M"...Cls) º as Ferric chloride (Fe2Cl6).
3
One metal is often found to combine with chlorine in more than
one proportion. Thus—
(a.) FeCle, Ferrous chloride; Fe2Cl6, Ferric chloride.
(3) PtCl2, Platinous chloride; PtCl, Platinic chloride.
Properties.-(a.) Sensible and Physical. The colors of the chlorides
are various; the alkaline chlorides are white. Their taste is mostly
saline or bitter. Generally they have no odor. They usually crys-
tallize in cubes, but sometimes in square prisms (calomel), sometimes
in rhombohedra (CaCl2), and sometimes in oblique prisms (BaCl.).
Some chlorides are soft, as argentic chloride (horn silver), and those
chlorides known as metallic butters (SbCls, SnCl2); whilst some are
liquid, and are known as metallic oils (SbCl, AsCls). When exposed
to the air they are mostly deliquescent.
Action of Heat.—(a.) They are all fusible and volatile. (1.) Some
volatilize at about 212° F (100° C.), as, e.g., Al Cls, Fe,Ols. AsCls,
etc.; (2) some at a red heat, as NiCle; (3.) but most of them at a
higher temperature.
(3) Some are partly decomposed by heat. Thus 2CuCl2 becomes,
at a red heat, Cu2Cl2 + Cla.
(Y.) Some are completely decomposed by heat; as, e.g., PtCl,
PdCl3, AuCls.
S
258 HANDBOOK OF MODERN CHEMISTRY,
(6.) Many (the chlorides of the noble metals excepted) when ignited
in air or owygen are decomposed, with the formation of an oxide and
the escape of chlorine.
(e.) Many (the chlorides of the alkaline metals and those of barium
and mercury excepted) when heated in the presence of water, form
oxides and hydrochloric acid. [N.B. Bismuth forms an oxychloride.]
(4.) All (excepting the chlorides of the alkalies and alkaline
earths) when ignited in a free current of hydrogen are decomposed, hy-
drochloric acid being formed.
Solubility in Water.—The chlorides are generally deliquescent, and
very soluble in water; PbCl, is, however, only very slightly soluble,
whilst AgCl, Hg2Cl2, AuCl, and PtCl2 are insoluble.
Solubility in Alcohol and Ether.—Most chlorides are very soluble in
alcohol, but NaCl is only slightly soluble, and some others, as KCl,
BaCl2, AgCl, and Hg2Cl2 are insoluble. Excepting those of the noble
metals, the chlorides are insoluble in ether.
Action of Light.—Some chlorides, as, e.g., AgCl, are decomposed by
exposure to light.
Action of Electricity.—The chlorides are mostly decomposed by
electricity.
(6.) Chemical.—The chlorides have generally an acid, but never an
alkaline reaction. The chlorides of the alkaline metals are neutral.
Water dissolves most chlorides without decomposition, but there
are certain exceptions, such as, e.g., SbCls, BiCl3, SnCl2, which form
hydrochloric acid, and an oxychloride when treated with water
(BiCl3+ H2O=2|HCl·HBiClO).
Acids, especially when heated, decompose the chlorides (argentic
and mercurous chlorides excepted), setting free hydrochloric acid.
All the soluble chlorides, when heated with sulphuric acid and man-
ganic peroxide, evolve chlorine, which is also commonly given off
when they are heated with nitric acid. The chlorides of the metals
combine with each other (2KCl, PtCl), also with the chlorides of the
non-metals (KCl, IC13), and also with metallic oxides, forming oxy-
chlorides (3HgC), HgCl2).
Tests, For the soluble chlorides.
(a.) Argentic nitrate: a white precipitate of AgCl, insoluble in nitric
acid, soluble in ammonia and in potassic cyanide. The precipitate
blackens on exposure to light.
(3.) Mercurous nitrate: a white precipitate of mercurous chloride
(calomel) [Hg2(NO2), +2NaCl=2|NaNO3 +Hg.C..] soluble in chlorine
water, and blackened by ammonia.
(y.) Plumbic acetate gives, in strong solutions, a white crystalline
precipitate of plumbic chloride (PbCl.), soluble in excess of water.
(2.) For the insoluble chlorides (AgCl, Hg,Cl2, PbCl2). -
[Note.—PbCl, is readily soluble in boiling water.]
Boil the insoluble chloride in a pure solution of potassic hydrate,
IODIDES. 259
filter off the undissolved oxide, acidulate the solution with nitric acid,
and test with argentic nitrate for chlorine.
Estimation of Chlorides.—100 grains of AgCl=2474 of chlorine.
Uses.—Common salt in diet, etc. The mercury and other chlorides
are used in medicine.
II. Iodides.
Definition.—Compounds of metals with iodine (the radical of HI).
Natural History.—The iodides are found in all three kingdoms of
nature, but chiefly in sea and in mineral waters, and in the plants and
animals living therein. Argentic iodide is a natural mineral.
Preparation.-1. (a) By the direct union of iodine and the metal
(e.g., HgI2; Asſs); or (3) by passing iodine vapor over metallic oxides,
either alone or mixed with carbon.
2. By the action of hydriodic acid on metals (as Hg), or on the
oxides, the hydrates, and on certain salts (as AgCl) of the metals.
3. By the action of iodine on a solution of the alkalies and alka-
line earths, whereby an iodide and an iodate are formed, the iodate
on ignition becoming an iodide (Process of P.B. for making KI).
4. The insoluble iodides may be prepared by adding a metallic salt
to a solution of potassic iodide (HgI2, AgI, PbT2).
Properties.-The iodides are closely allied to the chlorides,
(a.) Sensible and physical. The alkaline iodides are white, but the
remaining iodides, as HgI2, PbTe, etc., are most often colored. They
commonly crystallize in cubes. They are mostly soluble both in alcohol
and in water; but HgI2, AgI, PbTe, Biſs, PdL2, are insoluble in
Water.
Action of heat. The iodides are less fusible and less volatile than
the corresponding chlorides.
(1.) Most iodides are fusible, and many are volatile at high tem-
peratures.
(2.) When ignited in air or oxygen they are usually decomposed,
iodine being set free, and an oxide of the metal formed (Exceptions—
ICI, NaI, PbTe, Bils). In the case of Auſs, AgI, Pt.I., PdL, the
metal is reduced and iodine is set free.
(3). When heated in the presence of water, they are mostly decom-
posed into hydriodic acid and an oxide of the metal.
Light acts on many of the iodides. Thus AgI is blackened; Hg.I.,
is decomposed into Hg and HgI2.
(3) Chemical. The iodides are decomposed (1) by chlorine and bromine,
iodine being set free, (2) also by hydrochloric acid, hydriodic acid, and
a chloride of the metal being formed, (3) also by sulphuric, nitric, and
nitrous acids, and (4) also when heated with sulphuric acid and man-
ganic peroxide, when iodine is evolved. The iodides of those metals
which form acids with oxygen, viz., SnIt, Sbla, Teſt, Asſs, are decom-
posed by water, and an oxide of the metal precipitated.
260 . HANDBOOK OF MODERN CHEMISTRY.
The iodides readily combine amongst themselves; also with oxides,
forming oxy-iodides, and with chlorides (SnI,SnCl,). Moreover,
the metallic iodides absorb ammonia in definite proportions.
Tests for Iodides—(1) Starch water, with a trace either of chlo-
rine water or of nitric or sulphuric acids (added to liberate the
iodine) forms, with a soluble iodide, the blue iodide of starch.
(2.) Mercuric chloride (HgCl), a scarlet ppt. of mercuric iodide
(HgI2), soluble in excess both of the iodide and of the test solution.
(3.) Plumbic acetate, a yellow ppt. of plumbie iodide (PbT.), soluble
in hot water, and precipitated in yellow crystalline scales on cooling.
(4.) Argentic nitrate, a buff ppt. of argentic iodide (AgI), insoluble
in nitric acid, sparingly soluble in ammonia, soluble in potassic
cyanide.
(5.) A mixture of cupric sulphate and ferrous sulphate, a white ppt. of
cuprous iodide (Cu,I.).
(6.) Salts of Palladium, a brown ppt. of Palladious iodide (PbT.), in-
soluble in water. (The PdC), is freely soluble.)
Estimation,-If chlorides and bromides be absent, the iodine may
be estimated as AgI (100 grs. =54-04 I); but if chlorides or bromides
be present, it must be precipitated as PdL (100 grs. = 70.457 I).
Uses.—Chiefly in medicine. KI (a solution of which is used as a
solvent for iodine), CdI2 or Feſ., (prepared by direct union), Pble
(prepared by the action of KI on Pb2NO3), and S.I., are officinal.
III.-Bromides.
Definition.—Compounds of metals with bromine (the radical of
HBr).
Natural History. — Bromides are found in sea-water and in
saline springs. Argentic bromide occurs as a natural mineral.
Preparation.—Their preparation corresponds to that of the iodides.
Warieties. These correspond to the chlorides.
Properties.—(a.) Physical.-They are all solid. They may all
be fused and volatilized, excepting AuDrs and Pt.Prº, which are de-
composed by heat. *
(6.) Chemical.—When heated in chlorine, the bromides are con-
verted into chlorides. Heated with hydrochloric acid, hydrobromic acid
is evolved. They are all decomposed by sulphuric and by nitric acids,
hydrobromic acid being set free, which is itself decomposed if the
sulphuric or the nitric acid be in great excess, when free bromine is
evolved, together with SO2 or N2O4. By the joint action of sulphuric
acid and manganic peroxide, the bromides evolve free bromine. The
bromides combine amongst themselves, as well as with oxides, to
form oxy-bromides, and with sulphides. They also freely absorb
ammonia.
Tests for Bromides.—(1) Add to a solution of a bromide a little
FLUORIDES. . 261
chlorine water or a few bubbles of chlorine (avoiding excess). The liquid
becomes red, from bromine being set free. Divide this into two parts
(a and (3).
(a.) Shake up one part with ether or with carbonic disulphide, by which
means the bromine will be dissolved out of the solution.
(ſ3.) Add starch water, when the yellow bromide of starch will be
formed.
(2.) Argentic nitrate; a whitish-yellow ppt. of argentic bromide
(AgBr), insoluble in hot nitric acid, sparingly soluble in ammonia.
(3.) Mercurous nitrate ((Hg2)"2NOs); a yellowish-white ppt. of
mercurous bromide (Hg2 Bra), soluble in chlorine water, bromine being
set free.
(4.) Plumbic acetate; a white ppt. of plumbie bromide (PbPrº), less
soluble in water than PbCle, soluble in dilute nitric acid. .
(5.) Palladic nitrate (in solutions not containing chlorides); a black
ppt. of palladic bromide.
Estimation of Bromides.—In the absence of chlorides, the bromine
may be estimated as AgBr (100–42.55 Br).
Uses.—Chiefly in medicine. NH4Br (prepared by the action of
HBr on NH3), Felbre (prepared by direct union), KBr (prepared as
RI) (page 259), are officinal.
IV.-Fluorides.
Definition.—Compounds of metals with fluorine (the radical of
HF).
Natural History.—The fluorides are abundant in the mineral
kingdom, and are also found in animals and vegetables.
Preparation,-(1.) By the action of hydrofluoric acid on a metal
or on its oxide.
(2.) The insoluble fluorides may be prepared by mixing a solution
of a salt of the metal with potassic or with sodic fluoride.
Properties.—(a.) Physical. They are mostly solid, and crystallise in
cubes. Silicic fluoride (SiF4) is a gas.
Action of Heat.—All the fluorides fuse by heat (fluo, to flow).
Many, such as SbF3, ASFs, Crg F6, Hg Fe, SnRa, Zn,Fe, are volatile.
They are not decomposed, either when ignited alone or with carbon.
Action of Water.—A few fluorides are freely soluble (as AgP, SnRA),
their solutions corroding glass; some are sparingly soluble (as KF,
NaP, Fe2F6), but the majority are insoluble.
(6.) Chemical.—The fluorides of ammonium, sodium, and potassium
have an alkaline reaction. When ignited in a current of steam they
form oxides of the metals and hydrofluoric acid; when ignited in a
current of chlorine many of them are decomposed, and a chloride of
the metal produced.
They are not readily acted on by nitric acid. With sulphuric acid
262 HANDBOOK OF MODERN CHEMISTRY.
they evolve hydrofluoric acid, leaving a metallic sulphate. They
exhibit a marked tendency to combine amongst themselves, and also
with another molecule of the acid (HF,KF).
Tests.—(1) The fluorides gives precipitates with salts of lead,
barium, and magnesium, but give no precipitate with nitrate of silver.
(2.) A salt of calcium gives an almost invisible jelly-like precipitate
of CaF2, which is rendered more apparent by the addition of am-
monia. The precipitate is not very soluble in acids, but when treated
with sulphuric acid, fluorine is evolved, which acts on glass.
Estimation of Fluorides.—Mix the fluorides with powdered glass
and sulphuric acid, and distil into an ammonia solution. The SiR,
which comes over is decomposed by the water. Evaporate the con-
tents of the receiver to dryness, by which means the silica will be
rendered insoluble. Dissolve out the ammonic fluoride with water,
and weigh the silica. (Wilson.)
Uses.—Chiefly for glass etching.
W.-Sulphides (HYDROSULPHATEs).
Definition.—Compounds of metals with sulphur (the radical of H2S).
Natural History.—Found largely in the mineral kingdom.
Preparation.—(1.) By the direct union of sulphur with a metal
(such as CuS, FeS, PbS, SnS), or with a metallic oxide. In this
latter case, however, a variable proportion of sulphate is formed
simultaneously.
(2.) By heating a metallic oxide in a current of H2S or CS, vapor.
In this way titanic sulphide may be prepared from titanic anhydride
(TiO2+CS2=TiS2+ CO2).
(3.) By the ignition (reduction) of sulphates, either (a) with carbon
or with organic substances generally (as, e.g., in the preparation of
sulphides of the alkalies and alkaline earths) when CO is evolved
(K.S0,4-4C=K.S.--4CO); or—
(3.) In a current of hydrogen, as, e.g., in the preparation of the
protosulphides of the alkalies, and the subsulphides of other metals,
when some of the sulphur volatilizes.
(4.) By the precipitation of metallic solutions, either (a) by sul-
phuretted hydrogen, the solution of the salt of the metal being acid in
the case of the formation of Sb2S3, SnS, As2S3, Au,S3, Pts, ; or
either acid or neutral in the case of PbS, HgS, Aggs, BigS3, CuS,
CdS ;—
(3.) By an alkaline sulphide, e.g., ZnS, MnS, etc., or—
(y.) By a hyposulphite, added to an acid solution. In this case hypo-
sulphurous acid is set free, and is immediately decomposed into
sulphur and sulphurous anhydride (S.O. =S+SO2), which sulphur Com-
bines with the metal present to form a sulphide. In this way antimony
vermilion (Sb.S.) is prepared from an acid solution of the chloride of
- SULPHIDES. . 263
antimony by the action upon it of the hyposulphite of lime derived
from alkali waste.
Properties.—(a.) Physical. All the sulphides are solid, and many
are crystalline (cubic). They are of various colors; thus, ZnS is
white; MnS is flesh red; CdS, As2S3, SnS., are yellow ; SnS is choco-
late; whilst the rest are more or less black. Many have a metallic
lustre. The sulphides of the alkali metals, and those of barium and
strontium are freely soluble in water; calcic and magnesic sulphides
are slightly soluble, whilst the rest are insoluble. They are generally
fusible and volatile. The further action of heat upon them will be
studied under the chemical properties.
(3.) Chemical.—There is a close relationship between the oxides
and the sulphides. As oxygen often combines with a metal in more
than one proportion, forming protoxides and peroxides, so sulphur
forms protosulphides, as ferrous sulphide (FeS), and persulphides as
ferric sulphide (Fe2S3). This law, however, is not absolute. There
is no sulphide, e.g., corresponding to MnO2, and no oxides corres-
ponding to K2S3 and K2S5.
Action of air.—On exposure to air, even at common temperatures,
some sulphides become sulphates (CuS+O4=CuSO4), an action
utilized in the separation of copper from tin ores. Some, as, e.g.,
those metallic sulphides which form alkaline oxides, when exposed
to moist air, yield, in the first instance, a mixture of an oxide with a
bisulphide, and afterwards of an oxide with a hyposulphite, this latter
being formed by the further oxidation of the bisulphide. Thus—
(a.) 4Na2S + O2 = 2Na2O + 2Na2S2.
Sodic sulphide-H Oxygen = Sodic oxide + Sodic bisulphide.
(3.) 2Na2S2 + 3O2 = 2Na2S2O3.
Sodic bisulphide + Oxygen = Sodic hyposulphite.
Some sulphides, when exposed to the air, part with their sulphur
and become oxides. In this way the spent oxide of gas-works is
revivified. Thus—
4FeS + 3O2 = 2Fe2O3 + 2S2.
Ferrous sulphide-H Oxygen = Ferric oxide + Sulphur.
Some sulphides combine with oxides to form oxy-sulphides
(Sb2O82Sb2S3), and some with carbonic disulphide to form sulpho-
carbonates (K2S, CS2).
4ction of heat.—(a.) The protosulphides, if air be excluded, are
not decomposed by heat.
(3.) Heated in the presence of air, some sulphides are partially
decomposed, as e.g., FeS2 becomes FeS. Some are changed into sul-
Phates, as e.g., in the formation of zincic sulphate from blende
(ZnS-H2O2=ZnSO). In some the sulphur is expelled as sulphurous
anhydride, and an oaſide of the metal formed, as e.g., in extracting
Copper from the ore (Cu3S--203–20uO +SO.). In some the metal is
264 HANDBOOK OF MODERN CHEMISTRY.
entirely reduced, as e.g., Au.Ss, Pts, ; whilst in some a mixture of the
reduced metal and a sulphate is formed (Ag).
(y.) Some sulphides sublime when heated, as, e.g., As2S, (orpi-
ment), and Hgs (cinnabar).
(6.) Some sulphides are reduced when heated in a stream of hydrogen,
as e. g., Ag,S, CuS, BioSs, SnS2, Sb2S3.
(e.) Some sulphides are reduced when heated with iron, as e.g.,
PbS, SnS.
(..) All sulphides are decomposed when heated in a stream of chlo-
rine, chloride of sulphur and a chloride of the metal being formed.
Action of acids.-Cold dilute sulphuric acid and also hydrochloric acid
dissolve most of the sulphides, sulphuretted hydrogen being evolved.
With HCl a chloride of the metal is formed (Sb2,S,--6HCl=2SbCl,
+ 3H2S). The sulphides of cobalt, of nickel, and of platinum are
not acted upon by hydrochloric acid unless the sulphides be boiled in
the acid. All the sulphides (excepting mercuric sulphide) are decom-
posed by nitric acid, sulphuric acid and a nitrate of the metal being
formed. They are all freely attacked by nitro-hydrochloric acid.
Action of Sulphuretted hydrogen. Sulph-hydrates.—When sulphuretted
hydrogen is passed through a solution of the sulphide of an alkali or
of an alkaline earth, a soluble sulph-hydrate, hydrosulphide or hydric-
sulphide, as it is called, is formed (K.S.--H.S=2|KHS). This com-
pound holds an intermediate position between sulphuretted hydro-
gen and the ordinary sulphide, and closely corresponds in constitu-
tion to a hydrate. The ammonic hydric-sulphide (NH4FIS) belongs
to this class. The sulph-hydrates smell of sulphuretted hydrogen,
which is set free when they are acted upon by a metallic salt, a
reaction which serves to distinguish them from simple sulphides —
Sulphides (like oxides) are both basic and acid. Thus, an acid
sulphide (as As2S5) can react on a basic sulphide (as Na2S) to form
a new and double compound, as, e.g., (3Na2S, As2S3.) Most of these
double sulphides are soluble in water. The importance of this fact in
analysis is manifest, inasmuch as we are often enabled in a mixed
precipitate of metallic sulphides to dissolve out one sulphide by the
addition of a sulphide of an alkali metal (as NH4HS), and so effect
its separation from a second sulphide.
Action of alkalies and alkaline carbonates.—The sulphides are decom-
posed by fusion with alkaline carbonates or with hydrated alkalies.
Tests for the Sulphides :—
(1.) Heated with the blowpipe they emit an odor of SO2.
(2.) Moistened with HCl they evolve H.S, which blackens lead
paper.
(3.) Sodic nitro-prusside gives a purple color with a neutral or an
alkaline solution of a sulphide.
PHOSPHIDES. - 265
Estimation of Sulphides.
(1.) By first oxidizing the sulphur to sulphuric acid by aqua regia
or by chlorine, and afterwards precipitating the sulphuric acid with
BaCl (100 BaSO,-13-73 of S).
(2.) To determine the quantity of free H.S or of a soluble sulphide
present in solution, mix the solution with a little starch water and
acidulate with acetic acid; add to this a standard solution of iodine
in potassic iodide, until the blue iodide of starch is formed.
The H2S converts the iodide into HI, whilst the sulphur is set free
(2H2S--2I2–4HI+.S.).
FoEMATION OF SULPHIDES BY H2S.
Class I.-Metals not precipitated by H.S, their sulphides being soluble in water.”
Examples (K, Na, Li, Ba, Sr, Ca, Mg).
Class II.-Metals precipitated by H.S in an ACID solution, but not in an ALKALINE
solution, their sulphides forming double and soluble salts, with the
alkalies.
Hence: they are soluble in, and not precipitated by an excess of ammonic
sulphide.
Bxamples (Sb, Sn, As, Au, Pt).
Class III.-Metals precipitated by H2S in an ALKALINE solution, but not in an AcID
solution, the acid dissolving the Sulphide. They do not form double
compounds with the alkalies.
Hence : they are insoluble in, and precipitated by, ammonic sulphide.
Examples (Ni, Co., Zn, Mn, Fe).
Class IV.-Metals precipitated by alkaline sulphides as oxides and not as sulphides.
Examples (Cr, Al).
Class W.-Metals precipitated by H2S, either in an acid or in an alkaline solution.
Hence : they are precipitated equally by H2S and by ammonic sulphide.
Examples (Pb, Hg, Ag, Bi, Cu, Cd).
WI. and VII.-Selenides and Tellurides.
Definition.—Compounds of metals with selenium (the radical of
Selen-hydric acid or selenetted hydrogen, HaSe) and with tellurium
(the radical of hydro-telluric acid or telluretted hydrogen, H.Te).
These salts are closely allied to sulphides.
The presence of selenium may be known by the peculiar smell emitted
when the selenide is heated in the reducing flame of the blowpipe.
VIII-Phosphides.
Definition.—Compounds of metals with phosphorus.
Natural History.—The phosphides are never met with native.
Preparation.—In one or other of the following ways.
(1.) By the direct union of phosphorus and a metal (Au,Pt).
(2.) By igniting a metal with phosphoric anhydride (or with a
phosphate) and carbon.
(3.) By passing the vapor of phosphorus over a heated oxide (CalP).
* Baudrimont (J. Pharmac. Chem. Series IV, xxii. 15-19) points out that a 40°
Baumé solution of sodic, and probably of potassic hydrate at 15° C., is precipitated by
H.S, the precipitate having the composition Na,S, 9H,0. It is very soluble in water.
266 HANDBOOK OF MODERN CHEMISTRY. .
(4.) By passing phosphoretted hydrogen through a solution of a
metallic salt. •
Properties.—The phosphides are brittle solids, with a metallic
lustre. They are decomposed by heat, especially in the presence of
air, with the formation of either a phosphate or phosphoric anhydride
and the free metal. The phosphides of the alkalies and of the alkaline
earths decompose water, generating self-inflammable phosphoretted
hydrogen.
IX. —Carbides.
Definition.—Compounds of metals with carbon.
The carbides of iron are the only carbides of importance. Manga-
nese, palladium, etc., also form carbides. The carbides are usually
more fusible than the metals.
X, and XI.-Silicides and Borides.
Definition.—Compounds of metals with silicon and boron.
They are of very little importance.
The Cyanides will be considered under cyanogen.
OXYSALTS.
Definition.—Salts formed from an oxygen acid by the displacement
of all, or of a part of its hydrogen by a metal, or by a compound radical.
I-Sulphates.
Definition.—Salts formed from sulphuric acid H2SO4 (SO3Hog).
Natural History.—The sulphates are found in the animal, in
the vegetable, and in the mineral kingdoms.
Varieties and Constitution.—(a.) Normal Sulphates (MgSO, or
SO.Mo.). A sulphate where all the displaceable hydrogen of the
H.SO, is exchanged for a metal, etc., as K2SO, ; Ba'SO, ; Pb"SO4,
etc.
(3) Acid Sulphates (MHSO, or SO.MoHo). A sulphate where the
displaceable hydrogen of the H.SO, is only partially exchanged for
a metal, etc., as HNaSO, (hydric sodic sulphate, also called bisul-
phate). -
(y.) Basic Sulphates. A sulphate where the base present is in
excess of the acid, as e.g., Hg";SO6 (turpeth mineral).
(3) Double Sulphates are formed by the combination of two sul-
phates, as e.g., in the alums (K-SO4, Al28SO4+24.4%).
Many sulphates are anhydrous (K, Ba, Sr, Pb, Ag); some contain
5 molecules of water (Cu); most contain 7 molecules (Mg, Zn, Fe,
Co); and some 10 molecules (Na). The alums contain from 12 to 27
molecules.
Preparation,-(1.) By the artificial or spontaneous oxidation of
sulphaTEs. - 267
sulphides. Thus FeS and CuS, by roasting or by exposure to weather,
become FeSO, and CuSO4.
(2.) By the action of sulphuric acid on a metal or on an oxide,
carbonate, or other salt of a metal.
(N.B.—Sulphuric acid displaces all acids that boil at a lower
temperature than itself).
(a.) The action of a dilute acid on metals is accompanied with
the evolution of hydrogen.
(3.) The action of a concentrated acid and heat on the metals is
accompanied with the evolution of sulphurous anhydride (e.g. Cu, Ag,
Sb, Sn, Hg).
(y.) Action on orides (e.g. ZnO--H2SO,-ZnSO,--H20: 2MnO2+
2H2SO4–2MnSO,--2H20+O2).
(3) Action on sulphides (e.g. FeS + H2SO4=FeSO4+ H2S).
(e.) Action on hydrates (e.g. MnH2O,--H...SO,-MnSO,--2H2O).
(4.) Action on carbonates (e.g. Na2CO3+ H2SO4–NagsO4+ H20+
CO2.)
(m.) Action on chlorides (e.g. 2NaCl- H2SO,-NassO4+2HCl).
(3.) By the action of sulphurous anhydride on metallic peroxides—
SO2+ PbO2=PbSO,.
(4.) The insoluble sulphates are formed by adding a soluble
sulphate to a soluble salt of the metal. Thus— -
BaCl2 + H2SO4=BaSO,--2HCl.
(N.B.—The sulphates often occur as residues in the preparation of
volatile acids. Thus K2SO4 is obtained in the nitric acid, and
NagSO4 in the hydrochloric acid manufacture). -
Properties.—(a.) Physical,—The sulphates are all crystallizable
solids. The crystals are of different shapes; viz., cubic, as in the
alums; singly oblique, as in the sulphates of sodium, iron, and cobalt,
and also in the non-aluminous double sulphates; doubly oblique, as in
the sulphates of copper and manganese. They are generally white,
but some few are colored. Their taste is usually a saline-bitter and
astringent. They have no odor.
Action of heat.—(a). The normal sulphates of the alkalies and of
the alkaline earths, and plumbic sulphate, are not decomposed by
heat.
(3.) The sulphates of Mg, Mn, Zn, Cd, Ni, Co, and Cu are decom-
posed by an intense heat, SO2 and O being evolved (CuSO4 =
CuO +SO2+O). (Thus, ZnSO4 has been suggested as a source of
oxygen.)
(y.) The remaining sulphates are decomposed easily when heated,
sulphuric anhydride being evolved in the case of the sulphates of the
noble metals, and sulphurous and sulphuric anhydrides in the case
of the remainder (2FeSO4–Fe2O3 +SO.--SOs).
The sulphates are mostly soluble in water, whilst many are soluble
in alcohol.
268 HANDBOOK OF MODERN CHEMISTRY.
(B.) Chemical.—All the sulphates redden litmus, except the normal
sulphates of the alkalies and alkaline earths. º
Heated with carbon or with hydrogen, they may all be decomposed.
Different reactions occur as follows:–
(a.) In some cases, as with the sulphates of the alkalies and
alkaline earths, a sulphide remains, CO, H2O, or H2S being evolved”
(K2SO4+ Cº-K2S--4CO; K2SO4+4H2=K3S-1-4H2O).
(3.) Sometimes an oxide is formed (Mg, Zn).
(y.) Sometimes an oxy-sulphide is formed (Sb, Mn).
(6.) Sometimes the metal is reduced (Cu, Hg, Bi, Ag, and the noble
metals).
[Note that in those cases where a sulphide is formed from a
sulphate by heating with carbon (a), (e.g., BaSO,--4C=BaS-1-4CO),
the presence of the sulphate may be known by moistening the result-
ing sulphide with HCl, and testing for H2S with lead paper.]
Action of acids.-Nitric acid and hydrochloric acid act on the neutral
alkaline sulphates, forming acid sulphates and chlorides respectively.
The faced acids, such as boric acid and phosphoric acid, when fused
with the sulphates, decompose them, liberating sulphuric anhydride
(see page 7).
Action of water.—The sulphates generally are soluble in water,
but—
(a.) The basic sulphates, with BaSO4, PbSO, and SnzSO, are
insoluble.
(3.) SrSO, CaSO4, Ag:SO, are nearly insoluble.
(y.) And HgSO, is decomposed by the action of water into “turpeth
mineral” (2Hg0, HgSO), a similar result occurring in the case of the
sulphates of bismuth and antimony.
All the insoluble sulphates are decomposed when boiled in a
solution of sodic carbonate, a soluble sulphate and an insoluble car-
bonate being formed.
Organic matter also decomposes the sulphates.
Tests and Estimation of Sulphates.—(A.) Soluble sulphates:-
(1.) A soluble barium salt; a white ppt. of BaSO4, insoluble in nitric
acid. 100 grs. BaSO4=42grsſig SO4.
(2.) A soluble lead or lime salt; a white ppt. of PbSO, or CaSO,
(B.) Insoluble sulphates:– -
(1.) Fuse the sulphate with a mixture of sodic and potassic car-
bonates, digest the residue with water, and test the filtrate for a
soluble sulphate with BaCl2.
Or, (2.) Boil the sulphate in a solution of sodic carbonate, and
test the filtrate for a soluble Sulphate. --
* NotE.—In waters containing calcic sulphate and organic matter, a calcic sulphide
is formed, even at ordinary temperatures, by the action of the organic matter on the
sulphate. The sulphide is decomposed by the carbonic acid, H.S being set free, which
imparts to the water an unpleasant taste.
CFIROMATES. 269
Or, (3.) Fuse the insoluble sulphate, mixed with charcoal and sodic
carbonate, on charcoal with the blow-pipe. Touch the residue with a
drop of acid, when H2S will be evolved from the sulphide formed.
Uses,—Plaster of Paris (CaSO4) is used in the arts. The sulphates
are largely used in medicine, especially Epsom salts (MgSO4,7H2O),
Glauber's salts (NagsO4,10H2O), Ferrous sulphate or green vitriol
(FeSO,7H2O), Zincic sulphate or white vitriol (ZnSO4,7EI2O).
ALLIES OF THE SULPHATEs.
Selenates (from selenic acid, H.SeO, or SeO. Hoo); Chromates (from
chromic acid H2CrO3, or CrO2Hog); Manganates (from manganic acid,
H.MnO, or MnO, Hoo); Tungstates (from tungstic acid, H.WO, or
WO. Ho.); Molybdates (from molybdic acid, H2MoC), (?), or
MoQ.Ho.(?)); Tellurates (from telluric acid, H.Te04, or Te02Hog).
II.-Selenates,
Definition.—Salts formed from selenic acid, H2SeO4 (SeO3Hog).
The selenates are closely allied to the sulphates. They are decom-
posed when boiled with hydrochloric acid, chlorine being evolved and
selenic acid liberated. This is first converted into selenious acid,
which is immediately reduced by the sulphurous acid, and selenium
deposited.
Tests.--(1) Salts of barium, strontium, and lead; white ppts. of
Base04, SrSeO4, PbSeO, respectively, insoluble in dilute nitric acid.
(2.) Baric selenate may be known from baric sulphate by the re-
action mentioned above with hydrochloric acid, and also by its
emitting the characteristic selenium odor when heated on charcoal
with the blow-pipe.
III. – Chromates.
Definition.—Salts formed from chromic acid (H2CrO, or CrO. Ho.).
Both normal (M'. CrO4), acid and basic chromates are known. They
are all more or less of a yellow or red color. With potash, chromic
acid forms four salts; viz. –(1) K2O, CrO3 (chromate), (2) K2O,2CrO3
(bichromate), (3) K2O,3CrO3 (trichromate), (4) K2O,4CrO3 (tetra-
chromate).
They are mostly very soluble in dilute nitric acid, and more or
less soluble in water, excepting lead chromate, PbCrO, (chrome
yellow), argentic chromate, Ag:CrO4, and the basic chromates, which
are insoluble. The chromates are usually decomposed by heat. They
are not acted upon by sulphuretted hydrogen, but the green chromic
hydrate (Cr26HO) is precipitated when they are treated with ammonic
sulphide, or with the caustic alkalies or their carbonates, in which
latter, excepting in the case of ammonic carbonate, they are soluble
in an excess.
270 - HANDBOOK OF MODERN CHEMISTRY.
Tests, (1.) Salts of silver give a crimson ppt. (Ag:CrO.); salts of
barium and lead, yellow ppts. (BaCrO4, PbCrO4); and mercurous salts, a
brick-red ppt. (Hg2CrO4). These precipitates are soluble in nitric
acid, and insoluble in acetic acid.
(2.) Mix the dry chromate with two or three drops of sulphuric
acid in a test-tube, and apply heat, when chloro-chromic anhydride
(CrO2Cl2) is set free, and may be known by the red fumes that con-
dense in the glass.
(3.) The insoluble chromates must be ignited on platinum foil with
a mixture of nitre and an alkaline carbonate, by which means a
soluble alkaline chromate is obtained (KNaCr(),). The residue is to
be dissolved in water, neutralized with acetic acid, and tested as
above. -
(4.) Chromates (and all chromium salts) impart an emerald green
color to the borax bead.
IV.-Manganates.
Definition.—Salts formed from manganic acid (H2MnO, or
MnO2Hoz).
Preparation.-By the action of heat, in air or oxygen, on a
mixture of manganic peroxide with caustic potash, or baryta, or other
substance, according to the salt required.
Properties.—The manganates are colored and unstable salts. They
are soluble in water containing a free alkali. In common water,
however, and more particularly if it contains a trace of acid (even of
free carbonic acid), the salt is decomposed into manganic peroxide
and a permanganate (3R,MnO,--2H2O=K.Mn2Oa-i-MnO2+4KHO).
A manganate solution is decomposed by boiling, the solid salt being
also decomposed by heat with the evolution of oxygen. The Iman-
ganates are decomposed by all acids;–with sulphurous, phosphorous,
and hypophosphorous acids they are reduced to manganous salts,
whilst with sulphuric acid, permanganates are formed. All organic
matter, (e.g., a filter paper) deoxidizes them, setting free the brown
manganic oxide (Mn2O3). The presence of alkalies renders the man-
ganates more stable.
Uses.—The manganates are employed as disinfectants, owing to
the readiness with which they yield oxygen to organic matter.
“Condy’s green disinfecting fluid,” is a solution of sodic manganate
(Na,MnO,) dissolved in potash. It turns red (a permanganate being
formed) on the addition of an acid.
W.—Tungstates.
Definition.—Salts formed from tungstic acid (H.WO, or WO. Hog).
Tungstic acid forms both normal and acid salts. Many of the tung-
states are of very complex constitution. They all redden litmus, and
THIOSULPHITES. 271
are all decomposed by hydrochloric acid, a hydrate of tungstic acid
being precipitated (H.WO4, H2O).
Uses.—Sodic tungstate (Na, WO,2aq) is used by the calico-printers
as a mordant, and also for the purpose of rendering muslins unin-
flammable. Tungstate of baryta has been used as a paint, in the place
of white lead.
WI.-Molybdates.
Definition. — Salts formed from molybdic acid (H2MoC), or
MoQ.Hog Ž) [N.B.-MoQs has been obtained, but no definite hydrate
is known.]
Normal and acid molybdates have been prepared. The alkaline
molybdates are soluble.
Ammonic molybdate is used in the laboratory for the purpose of
precipitating phosphoric acid. The solution must be first acidulated
with nitric acid, and afterwards boiled.
VII.-Tellurates.
Definition.—Salts formed from telluric acid (H.Te0, or Te0. Hoe).
The tellurates are unstable salts. They give a black precipitate with
H2S. When heated they evolve oxygen, a tellurite remaining.
OTHER Oxy-SULPHO SALTs.
VIII.-Hyposulphites or Hydrosulphites.
Definition.-Salts formed from hypo- or hydro-sulphurous acid
(H2SO, or SHo.). The acid H2S2O3, or SS"OHoc (thiosulphuric
acid), is often improperly called hyposulphurous acid.
The hyposulphites are prepared by the action of zinc on solutions of
the acid-Sulphites, the zinc merely removing an atom of oxygen from
the sulphite (NaHSOs--Zn=ZnO-H-NaHSO2). The sodic hyposul-
phite or hydrosulphite (NaHSO2) is soluble in water, rapidly absorbs
oxygen from the air, becoming NaPISOs, possesses marked bleaching
powers, reduces salts of silver, of mercury and of other metals, and
when warmed with an oxalic acid solution, becomes of a deep orange
tint, H2SO, being liberated. This orange color of the solution rapidly
disappears, free sulphur being deposited.
IX-Thiosulphates or Sulpho-Sulphates (sometimes called Hypo-
sulphites).
Definition.— Salts formed from dithionous, thiosulphuric, or
sulphosulphuric acid (often called hyposulphurous acid) (H2S,0s=
SS"OHog). r
The thiosulphate or hyposulphite of soda, (Na2S2O3), as it is called,
and other thiosulphates may be prepared either (1) by digesting
272 HANDBOOK OF MODERN CHEMISTRY.
together sulphur and a sulphite (Na,SO,--S=Na.S.O.), or (2) by
passing SO2 through a solution of a metallic sulphide.
Sodic hyposulphite (Na2S2O3) is prepared commercially, by expos-
ing either the refuse of alkali works (soda or tank waste), or the
refuse lime of gasworks which contains calcic sulphide, to the air,
whereby a calcic hyposulphite is obtained (20aS+2O2=CaS2O3 +
CaO). When a solution of this salt is precipitated with sodic car-
bonate, the soluble sodic hyposulphite is formed, and calcic carbonate
is precipitated (CaS2O3 + Na2CO3=CaCO3 + Nags.O.).
The thiosulphates are sometimes called sulpho-sulphates, from being
regarded as Sulphates where a sulphur atom has displaced an oxygen
atom (e.g., NagsO4–NagsSO3). The thiosulphates are all decomposed
by heat and by acids, sulphurous acid being evolved (S.O. =S+SO2).
For this reason a metallic sulphide is often precipitated when a hypo-
sulphide is added to an acid solution of a metal. Thus “antimony
vermilion ” (Sb2S3) is prepared commercially by acting on an acid
solution of chloride of antimony, prepared by dissolving crude anti-
mony ore (Sb2S3) in hydrochloric acid, with calcic hyposulphite pre-
pared from alkali waste.
Uses.—Sodic Hyposulphite, or thiosulphate, is used for extracting
argentic chloride from an ore. It is largely used in photography, the
alkaline thiosulphates being solvents of the insoluble argentic salts,
thereby forming the sweet-tasted argentic thiosulphate, which, with
any excess of sodic hyposulphite forms NaAgS,03.
2AgCl + Nag'S2O3 = 2NaCl + Ag.S.03.
Argentic –H Sodic - Sodic + Argentic
chloride thiosulphate chloride thiosulphate.
[Note: The white AgCl, i.e., the salt when unacted upon by light, is
entirely soluble in Na2S2O3. When the AgCl has been exposed to
light it blackens, forming argentic subchloride, Ag:Cl, and free chlo-
rine. When this argentic subchloride (Ag3Cl) is acted on with a
solution of a hyposulphite, it is decomposed into AgCl–H Ag, the
chloride being soluble in the hyposulphite, the reduced metal remain-
ing undissolved.
Sodic thiosulphate is also used as an “antichlor” for removing the
last traces of chlorine from bleached goods, a process known as “killing
the bleach.” It is also used in medicine (hyposulphite of soda, B.P.).
Tests.--(1.) Soluble thiosulphates dissolve the insoluble argentic
salts.
(2.) Lead salts; white ppt. of plumbic thiosulphate (PbS,0s).
(3.) Mercurous nitrate; black ppt. of mercurous sulphide (Hg2S).
(4.) The thiosulphates decolorise an alcoholic solution of iodine.
(5.) A thiosulphate is decomposed by HCl, the thiosulphuric acid
(H2S2O3) set froe being instantly decomposed (2H2S2O3=2H2SO4+S.).
EIYPOSULPHATES. 273
Sulphites (CLoseLY ALLIED To CARBONATEs).
Definition.—Salts formed from sulphurous acid (H2SO4 or SOHO2).
The acid forms both normal and acid salts (e.g., Na2SO3, KHSO3).
Preparation.—By acting with sulphurous acid on the oxides or on
the carbonates of the metals, either in solution or in suspension in
Water.
Properties.—The sulphites are solid inodorous salts. The alkaline
sulphites are very soluble in common water, the sulphites of barium,
strontium and calcium being also soluble in water containing free
SO2; the remaining sulphites are insoluble.
When heated they are decomposed with the liberation of SO2.
When treated with sulphuric acid or with hydrochloric acid, SO2 is
evolved ; nitric acid changes the sulphites into sulphates.
The sulphites have a great affinity, especially when moist, for
oxygen, attracting it from the air. They act, therefore, as powerful
reducing agents, changing ferrous to ferric salts, arsenic to arsenious
acid; reducing chromic acid, and precipitating gold, tellurium, etc.,
from solutions containing an excess of hydrochloric acid.
Tests.-(1.) A sulphite, when treated with hydrochloric acid,
evolves SO3. Sulphurous acid is known by its action on paper
moistened with starch and iodic acid.
(2.) Add to a sulphite dissolved in a little water, a fragment of
zinc and hydrochloric acid; H.S (known by its blackening lead paper)
will be evolved.
(3.) Argentic nitrate ; a white ppt. of argentic sulphite, soluble in
excess of the sulphite. When boiled, the metal is partially reduced,
and sulphuric acid formed. w
(4.) Baric nitrate; a white ppt. of baric sulphite, soluble in HCl. If
a few drops of chlorine water be added to this solution, baric sulphate
is formed, which is insoluble in acids.
Uses.—The sulphates are employed to check fermentation, and to
prevent the growth of fungi. They are also used as “antichlors” to
expel chlorine (Na2SOs--H20+Cl2=Na2SO,4-2HCl.)
Hyposulphates (DITHIONATES).
Definition.—Salts formed from hyposulphuric or dithionic acid
(), Ho
H2S2O6 Ol' | §).
Preparation.—The dithionate of manganese is prepared by passing
SOs through ice-cold water containing peroxide of manganese (MnO,
+2SO2=MnS2O6).
Properties.—All the hyposulphates are soluble in water. They are
all decomposed by heat, a sulphate being formed and SO, evolved.
They are all decomposed when heated with sulphuric acid (SO, being
given off), but they are unaffected by the cold acid, thereby dis
tinguishing them from either sulphites or hyposulphites. -
T
274 HANDBOOK OF MODERN CHEMISTRY.
The trithionates (salts of H2S4O6); tetrathionates (salts of H2S,06), *
and pentathionates (salts of H2S506) are unimportant.
N.B. Action of Sulphuric Acid on Oaſysulpho Salts.
(a.) On Sulphates. No odor is evolved, either with cold or hot, or
with strong or dilute acid.
(6.) On sulphites. The odor of SO2 is evolved with dilute acid in the
cold.
(y.) On hyposulphates. No odor is evolved with dilute acid in the
cold, but SO2 is evolved when the mixture is heated.
(6.) On thiosulphates. The odor of SO, is evolved with a dilute acid,
the action being accompanied with the deposition of sulphur.
Nitrates,
Definition,-Compounds formed from nitric acid (HNO3 or NO. Ho).
Synonyms.-Azotates ; Saltpetres.
Natural History.—Nitrates are produced whenever the ammonia
of organic matter is oxidized in the presence of an alkali. They are
found in the shallow well-waters of towns as sewage products, formed
by the oxidation of the nitrogen during the passage of animal matters
through the soil. They are found, too, in the juices of plants, and in
the urine of patients who have taken ammonia.
Potassic nitrate (KNO3), or prismatic nitre, is found on the soil in
India, the crude nitre extracted by solution and Crystallization being
imported into this country under the name of “grough.” Sodic nitrate
(NaNO3) or cubical nitre, is found beneath the soil in Chili and Peru.
Although sodic nitrate is unsuited for gunpowder manufacture,
owing to its hygroscopicity and low oxidizing power, it is easily
converted into potassic nitrate by the action of potassic chloride,
a salt imported into this country from the salt mines of Stassfurth, as
well as obtained from the refuse of the sugar beet manufacture
(NaNO,--KCl–KNO,--NaCl).
Nitre heaps or plantations consist of masses of animal refuse mixed
with old mortar, etc., and moistened from time to time with urine or
stable runnings. These heaps are freely exposed to the air, but
sheltered from the rain. In time nitrates of the several bases present
are formed, and collect both on the surface of the heap and in the
superficial layer of earth (nitrified earth).
Theories of Nitrification.—Two theories have been advanced to
account for these changes.
I. Schönbein believed that the formation of the nitrates was due to
the union of atmospheric oxygen and nitrogen, the combination being
favored by the presence of porous solids and of matters undergoing
oxidation.
II. Most chemists, however, hold that the nitrogen of the ammonia
evolved as the organic matter putrefies, becomes oxidized, the oxida-
NITRATES. 275
tion being promoted by the presence of lime and of porous materials.”
Putrefjing nitrogenized matters, moisture, and free access of air are,
therefore, the essential conditions of nitrification, whilst the presence of
a basic substance, such as lime, to fix the acid formed, and of porous
materials to assist oxidation, are the conditions that specially favor
the action.
Impurities of saltpetres.—(a.) Insoluble earthy and vegetable
matters; (6.) potassic and sodic chlorides and sulphates; (y.) calcic
sulphate; (6.) moisture. Potassic chloride is, moreover, a special
impurity of the potassic nitrate, manufactured from sodic nitrate.
Purification of nitre (Refining). —A Saturated solution of the im-
pure salt in boiling water is first prepared. This, whilst boiling, is
filtered, to remove the insoluble impurities. The boiling filtrate is then
placed in troughs and kept constantly agitated, so that the crystals of
potassic nitrate that form may be small (saltpetre flour). As the water
cools the nitrate crystallizes out, it being four or five times more
soluble in hot than in cold water ; whilst the sodic and potassic
chlorides do not crystallize out, inasmuch as they are almost as soluble
in cold as they are in hot water. In this way the separation of the
chloridos from the nitre is effected. The nitre is then washed with a
little water, the mother liquor and the washings being afterwards
evaporated to dryness, and the residues added to the “grough" or
impure nitre.
Any coloring matter present is got rid of by animal charcoal. A
pure nitre is known—
(1.) By its solution in water being clear and neutral to test-paper.
(2.) By the absence of insoluble matter.
(3.) By argentic nitrate giving no precipitate (proving the absence
of chlorides).
(4.) By baric nitrate giving no precipitate (proving the absence of
sulphuric acid).
(5.) By ammonic oxalate giving no precipitate (proving the absence
of lime). :
Preparation (artificial).-By the action of nitric acid on metals,
or on their oxides or carbonates.
Properties.-The nitrates are all crystallizable solids, of various
colors and shapes; some are rhombohedric (NaNO3), some doubly
oblique (BiêNO3), but most generally right prismatic. They have a
saline taste, but no odor. Many are anhydrous, but they more
generally contain six molecules of water.
Action of heat.—They are all decomposed by heat, and generally
fuse before decomposing.
(a.) In some cases the metal is entirely reduced by heat, as e.g., the
nitrates of the noble metals.
* Mr. Warrington has lately suggested that nitrification is a process similar to the
acetic fermentation, and may be induced in an ammonia solution preserved in the dark
by the action of a mycoderm.
276 EſANDBOOK OF MODERN CHEMISTRY.
(3) In some cases nitric peroxide (N.O.) and oxygen are evolved,
an oxide remaining (Pb2NO, ; Cu2NOs).
(y.) Ammonic nitrate (HAN,NOs) breaks up into nitrous oxide
(N2O) and water.
(6.) The alkaline nitrates are first changed into nitrites, oxygen
being evolved, the nitrite being afterwards decomposed with the
evolution of nitrogen and oxygen, the oxide only remaining.
In the presence of an oxidizable body (such as carbon) the action
of heat on the nitrates is very energetic. Thus they deflagrate
when placed on red-hot charcoal. (It should be noted that the chlo-
rates and allied salts act similarly.)
Nascent hydrogen decomposes them, forming ammonia.
Sulphuretted hydrogen decomposes the nitrates of those metals that
have a strong affinity for sulphuric acid, such as Ba, Pb, etc.
Action of water.—The nitrates are nearly all soluble in water,
except the basic nitrates, such as the green basic cupric nitrate
(Cu2NO3,3Cul-I,02). Mercurous nitrate (Hg.,2NO3,2H2O) and bis-
muthous nitrate (BiêNO3,5EH2O) are decomposed by water, a basic
salt being formed.
Many of the nitrates are deliquescent, such as NaNO3, Ca2NO3,
NH4NO3, etc.
Action of acids.-The nitrates are all decomposed by acids. With
sulphuric acid nitric acid is set free, and with hydrochloric acid chlorine.
The fiaſed acids (such as phosphoric, boracic, etc.) decompose them by
heat.
Action of alcohol.—They are generally insoluble in alcohol, except-
ing a few, such as calcic nitrate, cupric nitrate, strontic nitrate,
etc.
Tests.-(1.) Hydrochloric acid, mixed with a nitrate, dissolves
gold-leaf. (N.B.-A similar result occurs when HCl is added to
solutions of chlorates, bromates, and iodates.)
(2.) If a nitrate be heated with a few drops of water, and a little
sulphuric acid and a few copper turnings added, N.O. will be evolved,
which is known by its forming red fumes (N.O.) in the presence of
air or oxygen. (When the nitrate is present in very small quantity,
the presence of N2O4 may be known by its action on paper moistened
with starch and potassic iodide.)
(3.) If a crystal of ferrous sulphate (FeSO,) be dissolved in a
nitrate solution, and sulphuric acid be poured down the sides of the
test-tube so that it may form a layer at the bottom, a brown line will
be produced at the junction of the two layers, due to the solution in
one portion of the ferrous salt, of the nitric oxide set free by the
deoxidizing power of another portion.
(4.) The conversion of the nitrogen of a nitrate into ammonia, by
the action-of nascent hydrogen set free either by zinc and sulphuric
acid, or by a caustic soda solution and aluminium, and the estimation
NITRITES. 277
of the ammonia by Nesslerising, constitute a very delicate quanti-
tative test for the presence and estimation of nitrates.
Uses.—For gunpowder, manures, and for the manufacture of nitric
acid. The nitrates are in constant requisition in the laboratory as
oxidizing agents.
In medicine, the ammonic, ferric, plumbic, argentic, and potassic
nitrates, and a subnitrate of bismuth (really an oxy-nitrate, BiONO3)
are officinal.
OTHER NITRO-OxYGEN SALTs.
Nitrites.
Definition.—Compounds formed from nitrous acid (HNO3 or
NOHo).
Preparation.—( 1.) By the action of nitrous acid on metallic
oxides or hydrates (KHO + HNO2=RNO. 4-H2O).
(2.) By the action of heat on certain nitrates, whereby oxygen is
evolved (KNO3=KNO2+O).
(3.) By the oxidation of ammonia or nitrogenized organic matter
(as in polluted well-water).
(4.) Nitrites of the alkalies, etc., may be prepared from nitrates,
by stirring their boiling solutions with a rod of zinc or cadmium
(Schönbein).
(5.) Ammonic nitrite is said to be produced during the spon-
taneous oxidation of phosphorus in the atmosphere, due to the action
of ozone on moist air.
Properties.—The Initrites are soluble in water and in alcohol, in
which latter solvent, for the most part, the nitrates are insoluble.
The nitrites of silver, sodium and lead are anhydrous. Several double
nitrites have been prepared, as e.g., a compound of nitrite of po-
tassium with a nitrite of either barium, zinc, or nickel.
Acid solutions of the nitrites act both as (a) oridizing agents, as
shown by their decolorizing indigo, and also (3), as reducing agents, as
shown by their decolorizing potassic permanganate, reducing potassic
chromate to a green chromium salt, and auric chloride or a mercurous
salt to their respective metals.
Tests.--(1.) Argentic Nitrate. A white ppt. of argentic nitrite
(AgNO3).
(2.) A nitrite solution, acidulated with a few drops of sulphuric
acid, sets free iodine from KI, which turns blue with starch. (This
test gives no action with nitrates.)
[Note: If organic matter be present in the solution, the nitric acid
set free from a nitrate by sulphuric acid, may be reduced, and will then
show the reactions of a nitrite. Hence, in such a case, acetic acid
should be added, the liquid distilled, and the distillate tested.]
Uses.—Nitrite of ethyl (C2H5NO2) is the chief constituent of spi-
ritus aetheris nitrosi (sweet spirit of nitre).
278 HANDBOOK OF MODERN CHEMISTRY.
The Hyponitrites (salts of N2O as NaNO) are of no importance.
Sodic hyponitrite (NaNO) is said to be formed by the action of sodium
amalgam on a nitrate. On the addition of an acid N2O is evolved.
SALTs ALLIED TO THE NITRATEs.
Chlorates (formed from chloric acid, HClO3, or | 3.) ; Bromates
(formed from bromic acid, HBrO3, or | 3.) ; Iodates )formed from
* * : * g. I
iodic acid, HIOs or | 3. ) e
We shall consider these together.
Natural History.—None of them are found native.
Preparation.—By the action of chlorine, bromine, or iodine on a
metallic hydrate. Thus—
6KHO + 3Cl2 = 5KCl + KClO3 + 3H2O.
Potassic hydrate + Chlorine = Potassic chloride + Potassic chlorate + Water.
* | OCl
(gokH + 30, − 5KC + 5.K., +3OH.)
Properties.—They are all very nearly related to nitrates. In one
respect the iodates are peculiar, viz., that a basic molecule may com-
|bine with more than one molecule of the acid. Thus we have—
(1.) Normal potassic iodate (KIO's); (2) Potassic diiodate (2KIOs, I2O3);
(3) Potassic triiodate (KIO, I,03).
Action of Heat.—The chlorates, bromates, and iodates are all de-
composed by heat, one of two results occurring—either (a.) Oxygen
only is driven off—a chloride, bromide, or iodide remaining—i.e., if the
affinity of the metal for the haloid is greater than it is for oxygen.
Thus 2KIO,-2KI+ 3O2; or, conversely—
(3.) Oxygen and the haloid element are both given off, an owide
remaining, i.e., if the affinity of the metal for oxygen is greater than
it is for the haloid. Thus 2(Ba2103)=2|BaO +50. --2I.
Mixed with a combustible element they all deflagrate when heated,
and explode when struck. Paper soaked in their solutions and dried
burns like touch-paper.
Action of acids.--They are all decomposed by acids. Sulphuric acid
decomposes them, setting free from the chlorates the yellow chloric
peroxide (Cl2O), whilst from the bromates and iodates, oxygen and
bromine, or oxygen and iodine, are set free respectively. Hydrochloric acid
liberates euchlorine from the chlorates, and chlorine with bromine, or
chlorine with iodine, from the bromates and iodates respectively.
Nitric acid forms with the chlorates a nitrate and a perchlorate, with
the liberation of oxygen and chlorine.
Action of water.—The chlorates are nearly all soluble in water, and
are deliquescent (mercurous chlorate excepted). The bromates are
mostly soluble in water, the mercurous, silver and lead bromates being
PERCHLORATE3 AND PERIODATES. 279
the least soluble. The iodates, excepting the alkaline iodates, are
but sparingly soluble in water.
Action of alcohol.—Many of the salts are soluble in alcohol.
All the salts of this group act as oxidizing agents. The chlorates
for this purpose are in constant use in the laboratory, chloric acid
being set free by the action of hydrochloric acid upon them. In
this way protosalts may be changed to persalts.
Tests.-They all deflagrate when placed on red hot charcoal. e
Chlorates.—(1.) No precipitate with argentic nitrate; a chlorate is
thus known from a chloride. If the salt be one (like KClO3) forming
a chloride by heat, the solution of the residue after ignition (KCl) will
give a precipitate of AgCl with argentic nitrate.
(2.) Add a few drops of indigo to a solution of a chlorate. On
adding a solution of sulphurous acid, the indigo will be bleached.
A chlorate may in this way be known from a nitrate, for with the
latter the blue color remains unaltered. -
(3.) On heating a chlorate with HCl the yellowish green gas called
euchlorine is evolved.
(4.) On adding sulphuric acid to a chlorate, chloric perovide is
evolved. -
Bromates.—Bromine is set free when a bromide is heated with sul-
phuric acid.
Iodates.—If a sulphurous acid solution be added to a solution of an
iodate, an iodide is formed (KIOs--3H2SOs=KI+3H2SO4). The
iodide may then be detected in the usual way, with AgNO3 or by
starch.
OTHER OXY-SALTs OF CHLORINE, BROMINE, AND IoDINE.
Perchlorates and Periodates.
OCl
Definition.—Salts formed from perchloric acid (aco. OT | O )
OHo
TOI
and from periodic acid (no. Or | )
OHo
Potassic perchlorate is formed either by heating potassic chlorate,
discontinuing the heat when one-third of the oxygen has been
evolved (2KClOs = KCl + KClO, + O.); or by acting on potassic
chlorate with boiling nitric acid (3KC10s.--2HNO2=2|KN Os--H20+
RC10,--Cl3+202).
Sodic periodate is formed by the action of chlorine on a mixed
solution of sodic hydrate and iodate (NaIO.--2NaHO-H Cle=NaIO,
+ H20+2NaCl). -
The perchlorates are all soluble in water, and many are soluble in
alcohol. They are all decomposed by heat, with the formation of a
chloride and the evolution of oxygen.
280 HANDBOOK OF MODERN CHEMISTRY.
The periodates are sparingly soluble in water, but soluble in dilute
nitric acid. They are all decomposed by heat. Periodic acid has a
tendency to form basic salts, just as iodic acid has a tendency to form
acid salts.
To distinguish a chlorate from a perchlorate, add a few drops of
sulphuric acid to some crystals of the salt. A yellow gas is evolved
in the case of chlorates, but none in the case of perchlorates.
Chlorites.
Definition.--—Salts formed from chlorous acid (HC10, or OCIPIo).
Preparation.—By the action of chlorous acid upon a base.
Properties.—The chlorites are solid deliquescent salts, decomposed
by heat and by the feeblest acids (as CO2). They possess considerable
bleaching power, and deoxidize an acidulated solution of potassic
permanganate.
Hypochlorites.
Definition,-Salts formed from hypochlorous acid (HClO or OCl H
or ClFIo).
Preparation.—By the action of hypochlorous acid on metallic
oxides or hydrates.
RHO + FICIO - KCIO + H2O.
Potassic hydrate + Hypochlorous acid = Potassic hypochlorite + Water.
(OKH + ClFHO - ClFCO + OH2).
Properties.—The hypochlorites are bleaching salts, and are de-
composed by the feeblest acids. Heat decomposes them, forming a
chloride and a chlorate (3KC10–2KC1+ KClO3).
The interest of the hypochlorites is centred in what is called
“chloride of lime,” or bleaching powder. This is prepared by acting
on slaked lime (calcic hydrate) with chlorine. The temperature must
be maintained below 100°F., or otherwise calcic chloride and chlorate
would be formed. The potassic and sodic chlorides are prepared in
a similar manner. It was formerly thought that a chloride and a
hypochlorite were formed during this process. Thus—
20al-I2O2 + 2Cl2 CaCl2 + Ca"Cl2O2 + 2 H2O.
Calcic hydrate + Chlorine Calcic chloride + Calcic hypochlorite + Water.
(2GaRIo, + 2Cl2 CaCl2 + Cao"Cl2 +2OH2).
but of this there is considerable doubt, inasmuch as bleaching-
powder contains no calcic chloride, and is not deliquescent (when
properly made). Hence the composition of bleaching-powder is
usually stated as consisting of a calcic chloride hypochlorite, CaCl(OCl).
Thus—
CaRI2O3 + Cl2 = CaCl(OCl) + H2O.
Calcic hydrate + Chlorine = Bleaching powder + Water.
(CaFIoz + Cl2 = Ca(OCl)Cl + OHz).
=
ORTHOPEIOSPHATES. - - 281
When “chloride of lime” is exposed to the air it gives off chlorine,
by the action of atmospheric carbonic anhydride upon it. Hence its
use as a disinfectant. The evolution of chlorine is considerable when a
strong acid is added to the compound (Ca(OCl)Cl·H H2SO4–CaSO4+
H2O+Cl2). It is also used as a bleaching agent (depending on the
oxidizing action of chlorine), the goods being first digested in a solu-
tion of bleaching-powder, and afterwards transferred to a weak acid
solution, whereby the chlorine is set free and the bleaching effected.
To distinguish a chlorite from a hypochlorite, add to the solution of the
salt a solution of arsenious anhydride and nitric acid; the bleaching
power of the chlorites remains unaffected, whilst that of the hypo-
chlorites is destroyed. -
Phosphates (see page 134).
Classification:—
Orthophosphates, compounds formed from orthophosphoric acid, H3PO,.
Pyrophosphates, } } 2 3 pyrophosphoric acid, H.P.01.
Metaphosphates, 2 y 2 3 metaphosphoric acid, HPOs.
I.-Orthophosphates, or Common Phosphates.
Definition.—Salts of tribasic phosphoric acid, H3PO4, or POHos.
Preparation of Hydric Disodic Phosphate (common sodic phos-
phate).-By the action of sodic carbonate on acid calcic phosphate.
Varieties of Orthophosphates.—One or all of the hydrogens of
the acid may be replaced by a metal. Thus—
NaH2PO4–Sodic-dihydrogen phosphate
(superphosphate). | Acid salts.
Na. HPO,-Disodic-hydrogen phosphate
Na3PO, =Trisodic phosphate ... • * * Normal salt.
Or the three hydrogens may be replaced by different metals. Thus—
HNaNH, PO,4-4aq=Hydric sodic ammonic phosphate(microcosmicsalt).
Properties.—The orthophosphates are solid salts, having a saline
taste but no odor. They fuse by heat, but are not decomposed if the
base of the salt be a fixed one. Acids decompose and dissolve them.
The phosphates of the alkalies are soluble in water, but the rest are
insoluble. The insoluble phosphates, excepting calcic phosphate, are
decomposed on boiling with sodic carbonate.
Tests.-(1.) Argentic nitrate; a yellow ppt. in a neutral solution
(Ag3PO4).
(2.) Magnesic sulphate and ammonia; a white ppt. (NH,MgFO,--
6H2O), which by heat becomes Mg., P.O. (100 parts=63-96 of P.O.).
(3.) Ammonic molybdate; a yellow ppt. when boiled in a solution
containing HNO3.
282 HANDBOOK OF MODERN CHEMISTRY.
II.-Pyrophosphates.
Definition.—Salts of pyrophosphoric acid (H.P.O., or P.O.EIoa).
Preparation of Sodic pyrophosphate.—By igniting common sodic
phosphate. (Thus, 2Na.HPO,-H,0+Na, P.O.)
Most of the pyrophosphates are solid, excepting the salts of
potassium and ammonium. They are easily converted into meta- and
Ortho-phosphates, by the addition or abstraction of water, or of a
metallic base. -
Tests. – Argentic nitrate; a white ppt. in alkaline solutions
(AgaF207).
III.-Metaphosphates.
Definition.—Salts of metaphosphoric acid (HPOs, or PO. Ho).
Preparation of Sodic metaphosphate.—By the ignition of micro-
cosmic salt (HNaNH2PO4–NaBO,--NH4+ H2O).
Test.—Argentic nitrate; a white gelatinous ppt. (AgPO3).
Two other phosphates have been studied by Fleitmann and
Henneberg. They are formed by fusing together, (1) one part of
pyrophosphate and two of metaphosphate, the salt formed having
the composition 2Naspoa, P.O; ; and (2) one part of pyrophosphate
and eight of metaphosphate, the salt formed having the composition
4Na,FO,3P,0s. They are unstable salts, but form definite argentic
and magnesic compounds (see page 139).
All phosphates are converted into tribasic phosphates by fusion
with an alkaline hydrate or carbonate.
OTHER Oxy-PHOSPHORUs SALTs.
Hypophosphites.
Definition.—Salts formed from hypophosphorous acid (HPH2O2,
or POH.Ho).
Preparation.—By acting on a metallic hydrate with phosphorus
(Pa-H 6H,0+30a H2O,-3(Ca"2PH.O.)+2PHs.
Properties.—The salts are monobasic, as, e.g., NaIPH2O, and
Pb"2PH2O2. They are all deliquescent crystalline stable solids. By
evaporating down their solutions they are converted into phosphites.
The hypophosphites reduce gold and silver salts. They are all soluble
in water; whilst the alkaline hypophosphites are also soluble in
alcohol. They are all decomposed by heat.
“Soda, hypophosphis'' is a pharmacopoeial preparation.
Phosphites.
Definition.—Salts formed from phosphorous acid (H2PHO3, or
P0HHo.).
ARSENIATES. 283
These salts may be normal (M.PHOs), or acid (MHPHOs).
Properties.— Solid bodies, sparingly soluble in water, except
the phosphates of the alkalies, which are freely soluble. On the
application of heat, the normal phosphites evolve hydrogen and
phosphoretted hydrogen, whilst the acid phosphites evolve hydrogen
only, and leave a metaphosphate.
Tests.--(1.) Mercuric chloride; a white ppt. of calomel in a solu-
tion acidulated with acetic acid.
(2.) Sulphurous acid is reduced by the phosphites to H2S, the pre-
cipitation of sulphur resulting from the action of the H2S on the
excess of sulphurous acid (3H, PHO3 + H2SO3=3|HapC), + H2S).
ALLIES OF THE PHOSPHATES.
Arsenates (salts of arsenic acid, H3AsO3, or AsOHos); Antimo-
mates (salts of antimonic acid, or antimonic anhydride Sb2O5).
Arsenates.
Definition.—Salts formed from arsenic acid (H3AsO, or AsOHos).
The arsenates are isomorphous with the phosphates. Thus—
Nasaso, 12H2O is prepared by adding an excess of sodic hydrate
to arsenic acid, and evaporating.
Nao HAsO4,12H2O is prepared by adding sodic carbonate to a hot
solution of arsenic acid until effervescence ceases, and evaporating.
NaH2AsO.H2O is prepared by adding to the previous salt an
equivalent quantity of arsenic acid to that which it already contains.
KH2AsO4 is prepared by fusing together nitre and arsenious acid,
dissolving the residue in water, and crystallizing.
(HIN)MgAsO,6H2O, a body isomorphous with the phosphate salt,
is prepared by adding magnesic sulphate to a solution of an alkaline
arsenate to which ammonia has been added.
Properties.—In form and reactions the arsenates are very similar to
the tribasic phosphates. Arsenates are also known corresponding to
the meta- and pyro-phosphates (Na, As2O7). The arsenates may be
prepared in an anhydrous state, but when redissolved they recover
their basic water. Heat alone, provided a fixed base be present,
does not decompose them. They are decomposed by nascent hydro-
gen, arseniuretted hydrogen being evolved. Acids decompose them.
Water dissolves the alkaline arsenates only, but they are all soluble
in dilute nitric acid.
Tests.--(1.) Lime, lead, and barium salts; white ppts.
(2.) Argentic nitrate; a brownish-red ppt. of triargentic arsenate
(Ag3AsO4). (This test distinguishes the arsenates from the arsenites.)
(3.) Sulphuretted hydrogen; a yellow ppt. of As, Sg, soluble in
8.I.O.IIlOIllà.
(4.) Add a few drops of cupric sulphate, and carefully drop in dilute
284 4 HANDBOOK OF MODERN CHEMISTRY.
ammonia until a green precipitate is produced (CuIIAsO.). The
*Senate solution must be neutral. The cupric arsenate is soluble in
acids and in alkalies.
Uses.—The arsenate of soda and the arsenate of iron (Fe,2AsO.)
are used in medicine.
The Wanadates, or salts of a base and vanadic anhydride (W.O.),
have been studied by Roscoe. They are usually red or yellow bodies.
Boiled with sulphuric acid, alcohol, and sugar, or heated with
sulphuretted hydrogen or sulphurous acid, they form a deep blue
solution.
The Antimonates closely resemble the arsenates. The alkaline
salts are obtained by the action of antimonic anhydride on a hydrate.
They are decomposed by an acid, Sb,054 H.0 being precipitated.
There are said to be two modifications of antimonic acid, viz., antimonic
acid, forming the normal salts K2Sb2O6, and metantimonic acid, which
forms the normal salt K.Sb2O7.
The soluble acid metantimonate of potassium (K.H.Sb.0,6H2O) pre-
cipitates soda-salts as an insoluble acid sodic metantimonate
(Na2H2Sb2O7,6EI2O). The acid potassic salt rapidly changes to a
normal salt, but this latter does not effect the precipitation of sodic
compounds.
OTHER OXY-ARSENICUM SALTs.
The Arsenites of the alkalies may be formed by dissolving
arsenious anhydride (As2O3) in solutions either of the alkalies or of the
alkaline carbonates. M'3AsO3 is believed to represent the formula
for these salts. The alkaline arsenites are soluble in water; the
arsenites of the earths are insoluble in water, but are soluble in
acids.
The tripotassic arsenite (Fowler's solution, or liquor arsenicalis)
(KAAsO3), is used in medicine. The alkaline arsenites are used as
sheep-dipping mixtures, and also by naturalists as an arsenical soap
to preserve the skins of animals. Sodic arsenite is used to prevent
the incrustation in boilers.
Cupric arsenite, or “Scheele's green,” (CuIHAsO3), and a mixed cupric
arsenite and acetate, or “Schweinfurt green” (3CuAs2O4,Cu2C3H2O2), are
used as pigments.
The arsenites have a great tendency to become arsenates, owing to
the greater stability of the latter.
Carbonates.
Definition.—Saltsformed from carbonic acid (H2CO3 or CO. Hoe (?)).
Natural History.—They are found in all three kingdoms of
nature; (a.) in the mineral kingdom (as e.g., CaCO3, etc.); (3.) in the
SILICATES. 285
vegetable, as e.g., pearlash (potassic carbonate) in the ashes of land-
plants, and sodic carbonate in the ashes of marine plants; (y.) in
the animal kingdom, carbonates are found in bones, shells, blood,
urine, deposits, etc.
Preparation.—(1) Sodic carbonate is prepared from sodic chloride,
by first converting it into a sulphate, and afterwards heating it
with chalk and coal (see page 302).
(2.) From the ashes of plants by lixiviating.
(3.) By the action of an alkaline carbonate on a metallic salt
(Pb.NO3 + Na2CO3=2|NaNO3 + PbCO3).
[N.B.-The carbonates are never formed by the action of carbonic
anhydride on a dry metallic oxide.]
Properties.—The carbonates generally crystallize in right prisms;
some in oblique prisms (Na), and some in rhomboids (Ca, Fe, Zn).
Action of heat.—Ammonic carbonate volatilizes when heated. The
carbonates of the alkaline metals and barium are unaffected by heat.
All other carbonates are decomposed, CO2 being evolved, and a
metallic oxide left.
Action of acids.--All carbonates are decomposed by acids, with the
evolution of CO2.
Action of water.—The alkaline carbonates are soluble in water. Many
carbonates that are insoluble in common water, are soluble in water
containing CO2 in solution, but are deposited as the CO2 escapes.
Many of them are anhydrous.
Tests.—An acid sets free CO2, which whitens baryta or lime-water
(forming BaCO3 and CaCO3), the precipitates being soluble in an
acid.
Uses.—The sodic salt is largely used in every day life, and also in
medicine. The ammonic, bismuthic (really an oxycarbonate), ferrous
(which mixed with sugar forms the saccharated carbonate), lithic,
magnesic, potassic, and zincic carbonates are also used medicinally.
Silicates.
Definition.—Compounds of silicic acid [viz., H3SiO, or SiHo,
(tetrabasic acid); and also of H2SiO3 or SiOHoc (dibasic acid), this
latter acid being said to be produced by the evaporation “in vacuo'?
of a solution of the tetrabasic acid}.
Natural History.—They are found in nature abundantly, as clay,
felspar, mica, etc.
Varieties.—The salts having the formula M'4SiO4, have been
named ortho-silicates, and the salts with the formula M'2SiOs meta-
silicates. There exists also an intermediate class, formed by the com-
bination of a molecule of each. The double silicates are numberless.
Preparation of Alkaline Silicates.—By fusing silicic anhydride
or the insoluble silicates, with the alkaline hydrates or carbonates.
286 HANDBOOK OF MODERN CHEMISTRY.,
Properties.—Action of heat. The silicates are mostly fusible, their ;
fusibility being increased by admixture.
Action of water.—They are all insoluble in water, excepting the
alkaline silicates which contain an excess of base.
Action of acids.-The anhydrous, normal and acid silicates of the
earths, are not decomposed by any acid except hydrofluoric. The
hydrated silicates are decomposed by all acids. If CO., be passed
through a solution of sodic silicate, silicic acid is precipitated as a
gelatinous deposit.
The silicates are alkaline to turmeric.
The Borates (salts of boracic or boric acid B.Hoa or HBO, H.O),
are formed by the action of the acid on metallic hydrates, oxides or
carbonates. They resemble the silicates in the variety of the propor-
tions in which they enter into combination with the alkaline bases.
All the borates are more or less soluble in water, the alkaline
borates being very soluble and the others less so. They are all
soluble in dilute nitric acid. The borates impart a green light to
flame.
Double Salts.
Definition.—Salts in which the displaceable hydrogens of the acid
have been exchanged by different metals, or compound radicals.
Varieties.-(I.) Salts formed by a combination of two metals with the
same acid radical.
(a.) The bicarbonates (HNaCO3), binoxalates, etc., are thus double
salts, the hydrogen playing the part of a metal.
(3.) One hydrogen of a dibasic acid may be displaced by one
metal, and the second hydrogen by a different metal, as in Rochelle
salt, where sodium and potassium are combined with tartaric acid
(KNaC, H,06), or as in the sodic potassic disulphate (NaKg2SO4),
where 2SO4 is combined with K3 and Na.
Thus we have double sulphates, double carbonates, double sili-
cates, etc.
(II.) Combinations of owides of different classes with their several equiva-
lents of the acid radical. .
Thus in common alum we have a sulphate of potash combined with
a sulphate of alumina or K2O, SO3 with Al2O3,3SOs, forming the com-
pound K2Al44SO,--24aq.
(III) Combinations of salts with saline or constitutional water.
Thus one molecule of water in magnesic sulphate (MgSO4, H20+
6H2O) cannot be expelled by a heat of 212°F., as the other six mole-
cules of water may be. This seventh H2O, represents a salt (and is
hence called saline water), and may be replaced in the salt by a
molecule of certain anhydrous salts not isomorphous with it, such as
potassic sulphate, forming (MgSO, K2SO46H2O).
DotſBLE SALTS. a 287
IV. The combinations of two acid radicals to one basic radical. These
are comparatively unimportant, and can scarcely be regarded as true
double salts.
W. The combinations of haloid salts with haloid salts, as e.g., the potassic
platinic chloride (2KCIPtCl2).
Preparation.—Double salts are prepared (1) either by mixing
together solutions of two salts in equivalent proportions, or (2) by the
fusion of the two salts.
The following are some of the double salts :—
1. Double Haloid Salts.--Where an alkaline haloid salt is com-
bined with a haloid salt of a metal, having a feebler affinity for oacygen than
the alkaline salt, as (KCIPtCl4) (NaCl, AuCls2H2O).
2. Double Sulphur Salts.-(a.) Double sulphides, as e. g., alkaline
sulphides with higher sulphides (3Na2S, As2S3,15EH2O); (3Na2S,Sb2S3,
18H2O). (3.) Hydrosulphides, as e.g., (KHS); (MgH2S2). (In these
salts H acts as a metal).
3. Double Oxysalts.-(a.) Double sulphates, such as the acid
sulphates or bisulphates (NaHSO4); the alums; and such other double
sulphates as N.Ca2SO4 (glauberite), MgSO4, K-SO,6EI2O ; and also soda
with magnesia, potash with manganese or with zinc, etc. .
(3) Double carbonates, such as MgCa2COs (dolomite), BaCa2COs
(baryto-calcite), etc.
(y.) Double silicates, such as alumina with potash (felspar), with
soda (albite), with lime (anorthite), with glucinum (emerald), etc.
Porcelain is a double silicate of lime and alumina, glass of potash or
soda with lime, magnesia, alumina, lead, etc.
(6.) Double tartrates, such as Rochelle salt. Similarly there are
double citrates, etc.
288
HANDBOOK OF MODERN CHEMISTRY.
THE ALKALINE METALS.
CHAPTER XII.
e & Electric
Symbol Atomic Atomic | Specific Fusing Point. Specific º
Weight. Volume. Heat. oc. Top |Gravity.jssºr.
Potassium . . . . K 39 - 1 45.20 || 0-16956 || 62 “5 144 - 5 || 0-865 20-85
Sodium . . . . . Na. 23.0 23:66 0.29340 97.6 207.7 || 0-972 37.43
Lithium . . . . . L 7.0 11.80 || 0-94080 | 180° 0 || 356-0 || 0:593 19-0
Caesium . . . . . Cs 133-0 (?) (?) (?) (?) (?)
Rubidium . . . . Rb 85-4 56.18 tº gº 38°5 | 101.3 1 52
gº NH
Ammonium. . { (or Ah) ! 18:0 (?) (?) (?) (?)


GENERAL REMARKS.
Characters, The alkaline metals decompose water at Ordinary
temperatures, forming soluble oxides and carbonates, having an
alkaline reaction.
History.-The existence of a metal in the alkalies was prophesied
by Lavoisier (1793). Sir H. Davy obtained potassium and sodium
in 1807, by decomposing the alkalies with the galvanic battery.
Lithia was first prepared by Arfvedson in 1817, the existence of the
metal lithum being afterwards demonstrated by Davy. It was first
prepared in quantity by Matthiessen (1855). (Phar. Journ, XV., p.
231.) Rubidium and caesium were discovered by Bunsen and Kirch-
hoff in 1860, by their peculiar spectra.
General Properties.-(a.) Physical. The alkaline metals are soft,
easily fusible, and volatile.
(6.) Chemical. They tarnish rapidly in the air. They decompose
water and liberate hydrogen at ordinary temperatures. They are
univalent. They furnish several oxides, but only one basic oxide
(M',0), this oxide being deliquescent, very caustic, and very alkaline
to test paper. The hydrates (MIHO) cannot be decomposed by heat.
They rapidly absorb CO2, forming both normal and acid carbonates.
The alkaline metals form but one chloride. Nearly all their salts are
soluble and alkaline.
POTASSIUM. 289
POTASSIUM (K2).
Atomic weight, 39:1. Atomicity Monad () (KCl, KI). Specific gravity,
0-865. Fuses at 144.5° F. (62.5°C.). Boils at a low red heat.
History.—Discovered by Davy (1807).
Natural History.—F ound (a.) in the animal kingdom ; (3.) in
the vegetable kingdom, as a sulphate, chloride, and also combined
with vegetable acids; (y.) in the mineral kingdom, in sea and spring
water, and in such bodies as alum, felspar, mica, etc.
Preparation.—(1.) By decomposing potassic carbonate with char-
coal (Curandau and Brunner), as follows:–
(a.) The crude tartar from wine casks (i.e. hydric potassic tartrate,
KHC, H4O6) is first incinerated, whereby a residue of potassic car-
bonate and carbon is formed—
2KHC, H,06 = K2CO3 + 5H2O + 4CO + 3C.
Hydric potassic = Potassic + Water + Carbonic + Carbon.
tartrate carbonate oxide
(3.) This residue is now intensely heated, when the metal distils
over and is received into naphtha-
-*
Potassic carbonate + Carbon = Carbonic oxide + Potassium.
3CO + Ks.
.*
(Chalk is commonly added to the mixture to prevent fusion.) --
(2.) By the electrolysis of potassic hydrate (Davy, 1807), (2KHO=
K2 + H2 + O.).
+
(3.) By the action of white hot iron on potassic hydrate (Gay
Lussac, 1808), (4RHO + 3 Fe=Fe30,--2K2 +2H3).
Properties.—(a.) Physical. Potassium is a soft silvery-white metal.
It has a less specific gravity than water, and therefore floats upon it.
It is brittle at 32°F. (0°C.), but becomes malleable at a little above
this temperature. At a red heat it forms a green gas. Its spectrum
consists of two red lines at A and B, and a violet line at the blue end.
(3.) Chemical. It oxidizes instantly in air, and burns with a violet
flame when heated. It removes oxygen from CO2 when heated in its
presence, liberating carbon (2R2+3CO2=2|KCOs-i-C). It decomposes
water at ordinary temperatures, liberating hydrogen (K. --2H2O=
2KHO + H2). It burns in chlorine. It decomposes HSS, forming
K.S (SH2 + Ke=K.S + H2).
290
HANDBOOK OF MODERN CHEMISTRY.
Compounds of Potassium.
i4
10
12
13
14
15
16
17
18
19
20
21
22
23
24
26
27
28
29
30
31
32
#-
º
Formula Formula TE 3
Salts. (General). (Constitutional). # #
#P
Potassic oxide (potash,
o, potassa) . . . . . . K,0 OK, 94.2
# A Potassic dioxide ... .. K2O2 O.K., 110-2
|-4 OK
O º - O
,, peroxide .. K,0. O 142-2
OK
,, hydrate (caustic
potash) • * * * REIO OKH 56-1
Potassic chloride .. RC1 KCl 74-6
,, iodide . . . . FOI FOI 166-1
, bromide . . . . KBr JKBr 119 - 1
,, fluoride . . . . RF RF 58-1
,, hydric fluoride RHF, KF, HF 78.1
,, fluosilicate 2KF,SiF, 2KF,SiF, 220-7
tº , cyanide .. KCy KCN 65. 1
3 ,, ferrocyanide
‘E (yellow prussiate) R.CycKe K. Fe(CN), 368.4
§, Potassic ferricyanide (red
O prussiate) . . . . . . KaCysFe K., Fe(CN), 329-3
Dipotassic sulphide (pro- -
º tosulphide). . . . . . K.S SK, 1 10-2
3 | Dipotassic disulphide . R.S., K.S., 142'2
# } } trisulphide
E. (sesquisulphide) K.S., K.S., 174.2
5 | Dipotassic tetrasulphide R.S., R.S., 206-2
5 y pentasulphide
(persulphide) . . . . K.S.; R.Ss 238.2
Potassic sulph - hydrate
(hydric sulphide) RHS RHS 72-1
2 (Dipotassic sulphate (nor-
– 3 mal salt) . . . . . . K.S0, SO, Ko, 174-2
3.5 ) Hydric potassic sulphate
Q4 (acid salt) . . . . . . HKSO, S0, Hoko 136-1
* Dipotassic carbonate(nor-
2 3 mal salt) . . . . . . K.CO, COKo, 138.2
; : ) Hydric potassic carbonate
O (acid salt) . . . . . . HKCO, COHOKo 100-1
Potassic nitrate (nitre or
saltpetre) . . . KNO, NO, KO 101 - 1
Potassic nitrite KNO, NOKo 85. I
§ , chlorate . . KC10, {3}. 1226
º OC1
É ,, perchlorate KC10, | O 138.6
C OKo
,, tartrate . . K.C, H,0s - 226-2
Hydric potassic tartrate
§ (cream of tartar) KHC, H,0s 188' I
# j Sodic potassic tartrate
# (Rochelle salt) . . . . KNaC, H,0s 210: 1
H CO(SbO.)
Potassic antimonious tar- CHHO
trate (tartar emetic) . . . K(SbO2)C, H,0s CHHO 341 - 1
C()Ko
Potassic silicate (water
glass) . . . . . . . . SiK.0, SiRo,
##-3
c-
Specific 3 #3
Gravity. 5 º'... 3
& c. 3 #,
Ed
100.0
86°48
66-24
2-1 83.95
1 - 994 63' 13
3.056 28-35
2.670 39-54
2.454 81*06
42.68
72°30
51*14
42 °90
85-48
2.66 K.0 54-07
2.475
2-267 K,068-17
2-052
2-070 46'59
2: 326 38°42
33-98
POTASSIUM. 291
CoMPOUNDs of PotASSIUM AND OxYGEN AND HYDROXYL.
Potassic oxide & a tº tº e º e - tº E.O.
Potassic dioxide * tº º tº e tº tº e tº K2O2.
Potassic peroxide ... e c tº • * * K2O,
Potassic hydrate ... * c & © º º ECHO.
(1.) Potassic Oxide; Potassa; Anhydrous potash (K20).
Preparation.—(1.) By heating together potassium and potassic hy-
drate (2KHO-F Kº-2K2O+Hz).
(2.) By fusing a mixture of potassium and potassic peroxide in an
atmosphere of nitrogen (K2O,--3K2=4K2O).
Properties.—A white, deliquescent solid, possessing powerful basic
properties. It combines with water with the evolution of great
heat and the formation of potassic hydrate (K2O+ H2O=2KHO). It
fuses at a red heat, and volatilizes at high temperatures.
(2.) Potassic Dioxide (K.O.), and (3.) Potassic Peroxide (K20.)
do not form corresponding salts with acids.
(4.) Potassic Hydrate; Potash; Caustic potash (KEIO, or OKH,
or KHo).
Preparation.—(1.) By the action of calcic hydrate (CaFI.O.) on a
dilute solution of potassic carbonate (pearlash) (K2CO3 + Cali-Og=
2KHO-H CaCO3). The solution of potassic hydrate (KHO) must be
decanted from the insoluble calcic carbonate (CaCO3), and evaporated
down in a silver basin.
(2.) By burning potassium in pure dry oxygen, and treating the
oxides formed with water.
(3.) By igniting a mixture of nitre (1 part) and copper foil (3 parts)
in a copper vessel, and dissolving the residue in water,
Properties.—Potassic hydrate is a very deliquescent solid, soluble in
water with the evolution of heat, and, unlike most potassium com-
pounds, soluble in alcohol. It has a strong caustic taste, and a
nauseous smell. At a high temperature it is wholly volatile. The
water of the hydrate cannot be expelled by heat. It must be regarded,
therefore, as a potassic hydroxide (KHo) rather than as a hydrate of
potash (K2O, H2O).
Caustic potash has an intensely alkaline reaction. It acts rapidly
on all organic matters. It rapidly absorbs carbonic acid, hence one of
its chief laboratory uses. It unites with silica when heated, forming
potassic silicate. It decomposes the fixed oils, converting them into
soaps; hence its use as a lye in soap making.
Tests for purity.—Pure potassic hydrate (1) is perfectly soluble in
water and in alcohol; (2) gives no precipitate with baryta water
(proving the absence of carbonates and sulphates); (3) gives no pre-
cipitate with ammonic oxalate (proving the absence of lime); (4) gives
no precipitate with argentic nitrate in a solution neutralized with
292 HANDBOOK OF MODERN CHEMISTRY,
HNO3 (proving the absence of chlorine); (5) gives no precipitate
with ammonic sulphide (proving the absence of iron, etc.).
Purification.—The potash is dissolved in alcohol, and the clear
solution evaporated to dryness. In this way the removal of potassic
peroxide, carbonate, sulphate, and chloride, and also the silicates of
lime, alumina, iron, and lead, all of which are insoluble in alcohol,
may be effected. The solution in water must be preserved in glass
free from lead, otherwise the lead oxide will be dissolved.
The liquor potassae of the B.P. contains 6 per cent. of KHO (Sp. Gr.
1.058). The specific gravities of solutions of various strength are
given in Table W. of the Appendix.
(5.) Potassic Chloride (KCl). Sources.—This salt is obtained
from sea-water residue (Balard); also from the ashes of sea-weed
(called “kelp ’’); also from the refuse of beet-sugar manufacture;
also as a product of the potassic chlorate manufacture. It is also
found as a natural product in the salt mines of Stassfurth, near
Magdeburg (Carnallite; KCl, MgCl2, 6H2O).
Properties.—The salt crystallizes in cubes. It is soluble in water
(1 in 3). It fuses at a red heat, and is volatile above this tempera-
ture. It absorbs the vapor of SOs, forming KClSO3, which salt is
decomposed by water. It is largely used in the nitre manufacture
(see page 274). Its laboratory use depends on the insolubility of
the double salt formed by it with platinic chloride in alcohol
(KCl, PtCl,).
(6.) Potassic Iodide (KI).
Preparation.—(1.) (a.) Iodine is added to a solution of caustic
potash (KTIO), a potassic iodide (KI) and a potassic iodate (KIO)
being formed; thus—
6|KHO + 3T3 = 5KI + KIO, + 3 H2O.
Potassic hydrate + Iodine = Potassic iodide + Potassic iodate + Water.
(3.) This mixture is then heated, whereby the KIO, is reduced to
RI, with the evolution of oxygen.
(2.) By dissolving potassic carbonate (K2CO3) in hydriodic acid.
Potassic + Hydriodic = Potassic + Carbonic + Water.
carbonate acid iodide anhydride
(3) (a.) By digesting iron and iodine in water, a ferrous iodide
(FeI.) and a ferric iodide (Fe, Ig) are formed ;
(3.) To the boiling solution of these salts, potassic carbonate is
added, carefully avoiding an excess.
FeI, + Fe...I -- 4K2C0A = 8KI + Fe30, -- 4CO2.
Ferrous + Ferric + Potassic = Potassic + Magnetic + Carbonic
iodide iodide carbonate iodide oxide of iron anhydride.
The Fe,0, is now filtered off, and the solution of KI evaporated
down.
(4.) By adding potassic sulphate to baric or calcic iodide.
COMPOUNDS OF POTASSIUM. 293
Properties.—Potassic iodide is a white crystalline (cubic) solid,
somewhat deliquescent, very soluble in water and in alcohol (1 part
in 6). Its solution dissolves iodine. It is decomposed by nitric acid,
chlorine, etc.
Test of purity.—There should be no change on adding hydrochloric
acid to its solution. If the solution turns brown, potassic iodate
(KIOA) is present ; if it effervesces, the presence of a carbonate is
indicated.
(7.) Potassic Bromide (KBr). Its preparation is similar and its
properties closely correspond to the iodide.
(8.) Potassic Fluoride (KF) is prepared by neutralizing HF
With KHO.
(10.) Potassic Fluosilicate (2KF,SiF.). This is the most in-
soluble of the potash salts. It is formed as a gelatinous precipitate,
when hydro-fluosilicic acid (2HF,SiFi) is added to a solution of a
potassium salt. When dry it has the appearance of an earthy-looking
powder.
(11.) Potassic Cyanide (KCy).
Preparation.—By fusing a mixture of potassic carbonate and
potassic ferrocyanide.
2K, FeCys -- 2K2CO3 = 10KCy + 3KCy0 + Fe. -- 2CO2.
Potassic + Potassic Potassic + Potassic + Iron + Carbonic
ferrocyanide carbonate cyanide cyanate anhydride.
Properties.—A white, deliquescent, peculiar-smelling, alkaline salt,
freely soluble both in water and in alcohol. It easily decomposes,
liberating hydrocyanic acid (HCy). It melts at a low temperature,
when it acts as a powerful reducing agent, owing to the ease with
which it forms a cyanate (KCyO). Hence it is used as a flux.
(Thus: PbO + KCy=KCy0+Pb).
Its solution dissolves the insoluble silver salts; hence its use in
photography and in electro-plating.
(12.) Potassic Ferrocyanide, Yellow prussiate (KFeCy3+3aq).
Preparation.—By heating a mixture of potassic carbonate (K.COs),
iron, and nitrogenized organic matter. The fused mass is lixiviated
(dissolved in water), and the clear solution crystallized.
Properties.—The salt has a yellow color, is permanent in air, and
is decomposed by heat. It is insoluble in alcohol, but is soluble in
water (1 in 4 at 60°F., and 1 in 2 at 212°F.).
It is used as a test re-agent, as a case hardener, and in the manu-
facture of Prussian blue.
(13.) Potassic Ferricyanide, Red prussiate (KFe"Cyg).
Preparation.—By passing chlorine (avoiding excess) through a cold
dilute solution of potassic ferrocyanide until it turns red.
Properties.—It is decomposed by an excess of chlorine, and by
oxidizing agents, such as H.S.
294 HANDBOOK OF MODERN CHEMISTRY.
CoMPOUNDS of PotASSIUM AND SULPHUR.
Tipotassic sulphide • * p tº tº º • * * K.S.
T)ipotassic disulphide ... & © tº gº tº º R2S2.
Dipotassic trisulphide ... © º e º e - K2S3.
Dipotassic pentasulphide ... to º º tº º tº K2S5.
Potassic sulphydrate º e - © º º e e Q ECEIS.
(14.) Dipotassic Sulphide (KS).
Preparation.—By the action of KHO on KHS.
ECEIO + KHS - SK2 + H2O.
Potassic hydrate + Potassic sulphydrate = Dipotassic sulphide + Water.
(15.) Dipotassic Disulphide (K.S.), an orange-colored fusible
solid.
(16.) Dipotassic Trisulphide (KAS).
Preparation.—By passing CS2 vapor over ignited potassic carbonate.
Potassic + Carbonic – Dipotassic + Carbonic + Carbonic
carbonate disulphide trisulphide oxide anhydride.
The “hepar sulphuris,” or “liver of sulphur,” is a compound of
3K2S3 and K2SO4, and is prepared by fusing together sulphur and
potassic carbonate.
4K2CO3 + 5S2 = K2SO4+3]K2S3 + 4CO2
\—
——’
Potassic carbonate + Sulphur = Liver of sulphur + Carbonic anhydride.
(18.) Dipotassic Pentasulphide, Potassic Persulphide (K.S.).
Preparation.—Either by the fusion of a solid sulphide, or by boiling
a solution of a sulphide with an excess of sulphur.
Properties.—A deliquescent solid, forming when dissolved a deep
yellow solution.
All the sulphides have an alkaline reaction, and a sulphuretted
hydrogen odor. They all liberate sulphuretted hydrogen when treated
with acids. On adding an acid, note, however, this distinction; that
(a.) With K.S and KHS, sulphuretted hydrogen is evolved, and no
sulphur is precipitated; but that
(3.) With the other sulphides, not only is sulphuretted hydrogen
evolved, but finely-divided white sulphur is precipitated.
The higher sulphides, on exposure to air, become white from the
formation of potassic thiosulphate (K2S2O3), the excess of sulphur
being liberated.
(19.) Potassic Sulph-hydrate, or Potassic Hydric Sulphide (KHS).
Preparation.—By Saturating potassic hydrate (KHo) with sulphu-
retted hydrogen.
ECEIO + H.S - E HS + H2O.
Potassic hydrate + Sulphuretted hydrogen = Potassic sulph-hydrate + Water.
The solution turns yellow on exposure to air, and freely absorbs
oxygen (4KHS +O2=2K.S. +2H2O).
POTASSIUM. 295
THE OxySALTs of PotASSIUM.
(20.) Dipotassic Sulphate (normal salt; K.S.O.). Properties.—The
crystals are six-sided prisms, soluble in water (1 in 12). The solution
is neutral. The crystals decrepitate when heated.
(21.) Hydric Potassic Sulphate; Potassic Bisulphate (acid salt;
HKSO,). This salt is a residuary product of the nitric acid manufac-
ture. The crystals are rhomboidal tables.
(22.) Dipotassic Carbonate (normal salt, K2CO3). Preparation.—
(1.) Wood-ashes, which contain potassic carbonate, sulphate and
chloride, are first of all lixiviated (i.e., mixed with water). The clear
solution is then evaporated until it begins to crystallize. The clear
liquor, containing the more soluble potassic carbonate, is then poured
off and boiled downin an iron-pot (hence the term pot-ash), and the resi-
due calcined. This residue is known as “American ash” or “pearl-ash.”
(NotE.—The potassium is not present in the plant as potassic
carbonate, but in combination with various organic acids. These
salts are decomposed by heat, the hydrogen and excess of carbon
passing off as H2O and CO2. Further, the younger the plant, the
larger the yield of pot-ash.)
(2.) By deflagrating a mixture of cream of tartar and nitre.
Properties.—Potassic carbonate is a white deliquescent salt, crys-
tallizing in oblique rhombic octahedra. It is soluble in water (1 in
1 aq.), the solution having an alkaline reaction. It melts at a red
heat, and is slightly volatile at a higher temperature. When sand
(SiO2) is added to the melted salt, CO2 escapes, and a potassic silicate
is formed. *
(23.) Hydric Potassic Carbonate; Bicarbonate of Potash (HKCOs).
Preparation.—By passing CO2 through a solution of potassic car-
bonate (K2CO3).
Properties.-A neutral body crystallizing in right rhombic prisms,
which are permanent in air. It is less soluble in water than K2CO3
(1 in 4). It fuses when heated, forming the normal salt. If a solu-
tion of the salt be boiled or exposed to the air, it loses one-fourth
of its CO2, and forms what is called the sesquicarbonate.
(24.) Potassic Nitrate, Nitre or Saltpetre (KNOs), is obtained
naturally, as an efflorescence, on the soil in India, and is prepared
artificially in the nitre-plantations of Sweden (see page 274).
Properties.—A white crystalline solid. It is dimorphous, crystal-
lizing both in rhombohedra and in six-sided prisms. It is insoluble
in alcohol, but soluble in water (1 in 3-5). When heated to 674°F.
(358° C.) it melts, the fused mass forming when cast into shape
“sal prunelle balls.” When potassic nitrate is heated to redness, oxygen
is evolved, and a potassic nitrite (KNO2) formed; but when heated
above this temperature, the nitrite itself is decomposed into O, N,
and K.O. When thrown on hot coal, the nitrate deflagrates. Paper
296 HANDBOOK OF MODERN CHEMISTRY.
saturated with a solution of the salt and dried, constitutes touch-paper.
It is used in the gunpowder manufacture.
Gunpowder.
Composition.—A mixture of nitre, charcoal and sulphur in the
following proportions:–


Pºiº Prussian. Chinese. French.
Nitre * * tº e tº º 75 75-0 75-7 75-0
Charcoal .. & e * & 15 13.5 14'4 12.5
Sulphur .. * * tº e 10 11-5 9:0 12.5
100 - 0 100'0 100-0 100'0
Nitre.—Sodic nitrate is never used in the manufacture of gunpowder
on account of its being far more hygroscopic than potassic nitrate, and
possessing much less powerful oxidizing properties. It is of im-
portance that the nitre used should be free from sodic and potassic
chlorides, as their presence in gunpowder render it liable to become
damp.
Charcoal.—Light wood charcoal, such as that from the alder and
willow, is the best adapted for the manufacture of gunpowder, owing
to its very ready combustibility.
Sulphur.—The sulphur commonly used is distilled, and not sublimed
sulphur. On mixing a quantity of the sulphur with water the solution
should be barely acid to litmus, proving the absence of oxidized pro-
ducts. It should, when burnt, leave no ash. The distilled sulphur
is the electro negative or soluble variety, but the sublimed sulphur
contains a considerable quantity of the positive or insoluble variety.
Hence the superiority of the distilled over the sublimed.
Properties.—Gunpowder is an angular grey solid, absorbing from
0.5 to 1.0 per cent. of moisture when exposed to the air. It explodes
with difficulty by actual flame. It should, after firing, leave no
residue, and moreover, it should not set light to a piece of paper on
which it may be fired.
Decomposition.—When gunpowder is fired, nitrogen is set free,
the carbon combining with the oxygen of the KNO3 forming CO2
and CO. Some of the CO., thus formed immediately combines with
the potash to form K.CO3. The sulphur becomes oxidized to SOs,
and this also combining with potash forms KøSO4. Hence the solids
formed by the explosion of gunpowder are potassic sulphate and
potassic carbonate, and the gases, nitrogen, carbonic oxide, and car-
bonic anhydride.
4KNO3 + C, 4- S =K.S.O., -i-K.CO3 + N2 + 2CO3 + CO.
Potassic -- Carbon-HSulphur= Potassic + Potassic -i-Nitrogen-H Carbonic + Carbonic
nitrate sulphate carbonate anhydride oxide.
SODIUM. - 297
Other bodies, however, such as K.S., H2S, and CH4 are also formed.
Theory of gunpowder explosions.—The nitrogen and the carbonic
anhydride set free by firing the powder, occupy at 0°C. and 80 B.P.
280 times the volume of the original powder; but this volume of gas
is again expanded by heat to as much, probably, as five times its
normal bulk.
(15.) Potassic Nitrite (KNO2). This is prepared by heating
potassic nitrate (see above). It is a white, crystalline, deliquescent salt.
(16.) Potassic Chlorate (KClO3). Preparation.—(1.) By passing
chlorine through a hot solution of potassic hydrate.
6KHO + 3Cl2 = 5|ECC1 + 5.KClO3 + 3EI2O.
Potassic hydrate + Chlorine = Potassic chloride + Potassic chlorate + Water.
The chlorate crystallizes out from the concentrated liquor, whilst
the potassic chloride remains in solution owing to its much greater
solubility.
(2.) By passing chlorine through milk of lime, whereby a calcic
chlorate (Ca2ClO3) and a calcic chloride (CaCl2) are formed. Potassic
chloride is then added to the solution. Thus:–
(Ca2ClOs) + 2KCl = CaCl2 + 2KClO3.
Calcic chlorate + Potassic chloride = Calcic chloride + Potassic chlorate.
The chlorate is now crystallized out, the CaCls being a very much
more soluble salt than the chlorate.
Properties.—Potassic chlorate is a white crystalline solid (six sided
prisms). It is not very soluble in water (1 in 16). It melts at
806°F. (430°C.), giving off oxygen, the residue consisting of potassic
perchlorate (KClO4) and chloride, which at a greater heat is entirely
decomposed into potassic chloride and oxygen.
(17.) Potassic Perchlorate (KClO4). (See above.)
(18.) Potassic Tartrate (K.C.H.O6) is prepared by boiling to-
gether cream of tartar and potassic carbonate.
(19.) Hydric Potassic Tartrate; Potassic Bitarfrate ; Cream of
Tartar.—This is one of the most insoluble of potash salts. It is found
deposited in casks used for the storage of wines.
(30.) Sodic Potassic Tartrate, Rochelle salt (KNaC, H,06), is pre-
pared by boiling together cream of tartar and sodic carbonate.
(31.) Potassic Antimonious Tartrate, Tartar emetic (K(SbO.),
C.H.O6), is prepared by boiling together cream of tartar and antimonic
oxide (Sb2O3).
Tests for Salts of Potassium.—See ANALYTICAL TABLEs.
SODIUM (Nas).
Na'-28. Monad (NaCl; ONaH.) Specific gravity 0.972. Fuses at
207-79 F.
History.—Discovered by Davy (1807).
Natural History.—It is found in animals, in vegetables (as in
298
HANIDBOOK OF MODERN CEIEMISTRY.
“barilla’’), and in minerals.
bonate, nitrate, Sulphate and borate.
Preparation.—Its preparation is similar to that of potassium, viz.,
(1), by igniting a mixture of sodic carbonate and carbon ; (2) by
electrolysis; and (3) by the ignition of a mixture of sodic hydrate and
metallic iron.
It occurs naturally as a chloride, car-
Properties.—(a.) Physical. A soft silvery white metal, burning
with a yellow flame.
spectrum consists of a yellow line at D.
(6.) Chemical. Sodium oxidizes rapidly and burns when heated. Its
properties are similar to, but less energetic than, potassium.
Uses.—It is employed for the extraction of metallic aluminium and
magnesium.
extract gold and silver from their ores.
Compounds of Sodium.
It volatilizes more readily than potassium. Its
(See Aluminium and Magnesium.) It is also used to
<- 32 Contains
3 & # | Specific Na,0, or
Formula Formula 3 : 5.3 || Gravity equal to Na,0
Names. - - - - © e- 2
(General.) (Constitutional). 3.};}|... of per cent. of
z}= 3 Crystals. Anhydrous
Salt.
1 | Sodic oxide (soda) . . Na,0 ONa, 62 100-00
2 ,, dioxide . . . . Na2O, O,Na, 78 79°48
3 ,, hydrate (caustic -
soda) . . . . . . NaIHO ON al-H 40 2-13 77.5
4 | Sodic chloride .. NaCl NaCl 58-50 2-24 Na-39-31
5 ,, iodide NaI NaI 150 3:45 Na-15-33
6 , bromide . . . . NaBr NaBr 103 3:08 Na+22°33
7 ,, sulphate (Glau-
ber's salt) . . . . Na,SO,10H,0 SO,Nao, 10OH, 142 1 °469 43-67
8 | Hydric sodic sulphate
(bisulphate).. NaHSO, SO,HoNao 120 2.742
9 | Sodic sulphite. . Na,S0,10H,0 SONao, 10OH, 126 1:736
10 | Hydric sodic sulphite NaHS0,4H,0 | SOHoNao,4OH, 104
11 | Sodic hyposulphite . . Na,SO, SNao, 1 10
12 , thiosulphate . . Na,S,03,51H,0 SS"ONao,50H, 158 1-672
13 ,, carbonate Na,CO3,10H,0 CONao, 10OH, 106 l'423 58-49
14 | Hydric sodic carbonate -
(bicarbonate) NaHCO, COHoNao 84 2, 192 36-90
15 Sodic nitrate (cubic
nitre) . . . . . . NaNO, N0,Nao 85 2°26
16 || Trisodic phosphate -
(sulphosphate) Na,P0,12H,0 PONaos, 12OH, 164 1-618
17 | Hydric disodic phos-
phate (rhombic) ... Na, HP0,,12H,0 |P0HoNao, 120 H, 142 1°525 43'66
18 || Sodic dihydric phos-
phate y © tº a e NaH,PO,H,0 P0Ho,Nao,0H, 120
19 | Sodic pyrophosphate
(tetrasodic phos-
phate). . . . . . . Na,P,0,10H,0 P.O.NaO,100H, 266 1-836
20 | Sodic metaphosphate NaPO, 0,Nao 102 30-39
21 ,, diborate (borax). Na,0,2B,0s,10H,0|| B,0s Nao,100H, 202 1-73 30-69
SODIUM. 299
CoMPOUNDs of SoDIUM witH OxYGEN AND HYDRoxy L.
Sodic oxide - tº dº ſº • * * ... Na2O.
Sodic dioxide & ºr ſº * * * ... Na2O2.
Sodic hydrate tº º g e de g ... NaOH.
(1.) Sodic Oxide; Soda (Na2O). Preparation.—By burning the
metal in oxygen or in dry air. (The product contains more or less
Na2O2.) Properties.—A yellowish white body, very deliquescent, form-
ing NaHO when dissolved in water.
(2.) Sodic Dioxide (Na2O2). Preparation.—By heating sodium to
392°F. (200°C.) in a current of dry air. Properties.—It is a white
solid when cold, and yellow when hot. On heating its solution in
water, oxygen is expelled.
(3.) Sodic Hydrate; Caustic Soda (NaHO). For its preparation
see Potassic hydrate, to which it is in all respects similar (page 291).
Preparation.—(Commercial.) Caustic soda is largely prepared from
the red liquor of the alkali works (see page 303). The solution of the
black ash is concentrated to 1-5 specific gravity, the sodic carbonate,
sulphate and chloride crystallizing out in the course of the evapora-
tion. The liquor left constitutes “red liquor ’’ which retains the sodic
hydrate, owing to its greater solubility. Certain other compounds
are present in small quantity, such as the sulphides of iron and
sodium, to which the peculiar red color of the liquor is due. The hot
liquor is now treated either with sodic nitrate and a current of air, or
with sodic nitrate only, in order to oxidize the sulphides present, ferric
oxide being deposited. The solution is then evaporated until the
sodic hydrate is obtained as a fused mass.
Kryolite (3NaH', Al Fa) is also employed in the preparation of sodic
hydrate by decomposing it with calcic hydrate.
Properties.—Sodic hydrate is a white fusible deliquescent substance.
By exposure to air it first becomes liquid from absorbing water, and
afterwards dries up from absorbing carbonic anhydride.
It acts rapidly on Organic structures. It is largely used both in
the manufacture of hard soap (i.e., caustic soda and fat or oil), and of
marine soap (i. e., caustic soda and cocoa-nut oil).
For the specific gravity of solutions of different strength, see
Table VI., in Appendix.
CoMPOUNDS OF SODIUM AND THE HALOIDs.
(4.) Sodic Chloride; Common salt; Muriate of soda (NaCl). Sources.
—(1.) From beds of “rock salt,” such as are found at Northwich, Car-
dona, Wielitzka, etc. Rock salt often occurs of a red tint, from the pre-
sence of iron. The perfectly white crystallized specimens occasionally
found are known as “sal gem.”
(2.) Sea water.—The salt obtained from this source is called Bay Salt.
300 X- HANDBOOK OF MODERN CEIEMISTRY.
The solution that remains after the extraction of the salt is called
“bittern.”
(3.) Salt springs; also rivers, lakes, soils, etc. i
Preparation.—The salt is crystallized from its solution, the details
of the process varying in different countries. In the case of salt
mines, it has been found more economical to pump water into the
mine, and to pump it up again when saturated with the salt, than to
raise the solid salt itself from the mine.
(a.) Sometimes the water is evaporated at once by boiling.
(3.) Sometimes the brine, if dilute, is first of all concentrated, by
allowing it to flow several times from a height over brushwood freely
exposed to the air (graduation), and when the solution has attained a
gravity of 1:14 effecting its further concentration by heat (France and
Germany).
(y.) In cold climates the salt water is run into open reservoirs, and
allowed to freeze. The solid ice, which contains very little salt, is then
removed, thereby concentrating the remaining solution, which is
finally evaporated to dryness (Russia).
(3.) In hot climates the sea-water is allowed to evaporate sponta-
neously in shallow reservoirs, when what is called “bay Salt ’’ is de-
posited. The salt prepared from sea-water always contains magnesic
chloride, which may to a certain extent be separated from the sodic
chloride by exposure to air, and by washing, owing to the greater
deliquescence of the magnesic chloride. The liquor remaining after
the sodic chloride is removed, is called “bittern,” and is employed as
a source of magnesia and bromine.
We may here note that every 1000 parts of sea-water contains
29:0 parts of Chloride of sodium (=4 ozs, of salt per gallon,
or 1 bushel in 300 to 350 gallons of water).
O'5 , , ,, Chloride of potassium.
3.0 , , ,, Chloride of magnesium.
2.5 , ,, Sulphate of magnesia.
1.5 , , ,, Sulphate of lime.
Properties.—Common salt is a crystalline (cubic) non-deliquescent
solid. The presence of magnesic chloride renders it deliquescent.
A clear colorless specimen of salt is diathermanous, that is, it allows
the heat rays to pass as well as the light rays. Water is non-diather-
manous, glass holding an intermediate position in this respect between
water and salt. Common salt is insoluble in absolute alcohol, but is
soluble in dilute alcohol and also in water (1 part in 3), and about
equally at all temperatures, a Saturated solution having a specific
gravity of 1205. The crystals decrepitate when heated. At a bright
red heat they fuse, and at a stronger heat vaporize.
Uses.—It is used for dietetic and culinary purposes, as e. g., for
curing meats, owing to its antiseptic action. It is also used in
SODIUM OXY-SALTS, - 301
agriculture, in earthenware glazing, etc., and also very largely in the
carbonate of soda manufacture.
(5.) Sodic Iodide (NaI). (Wide Potassic Jodide, to which it is closely
analogous.)
(6.) Sodic Bromide (NaBr). (Wide Potassic Bromide.)
SoDIUM OxY-SALTs.
(7.) Sodic Sulphate; Glauber's salt ( Na2SO,10H2O). This salt is
formed in the first stage of the sodic carbonate manufacture by the
action of sulphuric acid on common salt (see page 302), the product
being commonly known as “Salt cake.”
It occurs naturally in many waters, as in the Cheltenham springs;
in certain minerals, as Thénardite, Glauberite (Na2SO4,CaSO4), etc.;
and also as a common efflorescence on brick walls.
Properties.—A colorless salt, having a bitter taste and a purgative
action. It crystallizes in oblique rhomboid prisms, or in forms derived
therefrom. The crystals are efflorescent, giving off the whole of their
water at common temperatures. The salt melts in its own water of
crystallization when heated.
Its solubility in water is remarkable. A hot saturated solution, on
being cooled without disturbance and out of contact with air, does not
crystallize; whilst on the admission of air to the cold solution, its im-
mediate crystallization may be effected. The explanation of this cir-
cumstance is that probably the salt in the supersaturated solution exists
in the anhydrous form, whilst when it separates, it crystallizes out
with the ten molecules of water of crystallization. We must here
note that sodic sulphate has been prepared in two forms at least, their
solubilities differing very remarkably. Thus—
(a.) The solubility of the salt NazSO, decreases from 64.2° F.
(17.9° C.) to 217.5° F (103.1° C.).
(3.) The solubility of the salt Na. SO,10H2O increases up to 93.1°
F. (33.9°C.) (100 aq. dissolves 117-9 parts).
Sodic sulphate is soluble in hydrochloric acid, its solution being
accompanied with a great depression of temperature.
(8.) Hydric Sodic Sulphate; Acid sodic sulphate ; Bisulphate of
soda (NaHSO4).
Preparation.—By adding seven parts of sulphuric acid to ten parts
of the anhydrous normal salt, and evaporating.
Properties.—A non-deliquescent, very soluble, acid salt, forming
the neutral sulphate when heated.
(9.) Sodic Sulphite (Na2SO4,10H2O).
Preparation.—By passing S02 over crystals of Na2COs.
Properties.—The salt crystallizes in oblique prisms, which are
efflorescent and fuse at 118°F (45° C.). It is soluble in water (1 in
4), the solution having an alkaline reaction. It evolves sulphurous
302 EIANDBOOK OF MODERN CHEMISTRY.
acid when treated with HCl or with H2SO4. It is used as a bleach-
ing agent, and as an “antichlor.”
(10.) Hydric Sodic Sulphide, Acid sulphite or Bisulphite of soda
(NaHSOs), has also been prepared.
(11, 12.) Sodic Hyposulphite and Thiosulphate (see p. 271).
(13.) Sodic Carbonate; Common washing soda ; Scotch soda—
(Na2CO3,10H2O).
Preparation.—Before the year 1823, this salt was prepared from
the ashes of sea-weed, known as “kelp,” “barilla,” or “warec,” one-
fourth the weight of which consists of sodic carbonate. The kelp was
mixed with water, and the clear solution concentrated by heat. The
sodic carbonate crystallized out first, leaving the iodine compounds in
solution, owing to their much greater solubility.
Since 1823, sodic carbonate has been prepared from common salt
by the process of Lablanc. This process may be described as taking
place in three stages as follows:—
(a.) A mixture of common salt and oil of vitriol is first heated in a
reverberatory furnace, whereby sodic sulphate is formed. This con-
stitutes what is called “salt cake.”
2NaCl + H2SO, Na2SO4 + 2|HC1.
Sodic chloride + Sulphuric acid = Sodic sulphate + Hydrochloric acid.
(salt cake)
[It has been suggested to use sulphurous acid, steam and air, in
the place of sulphuric acid. (Hargreave.) 2NaCl--H2O+SO2+O=
Na2SO4+2HC].] -
(3.) The salt cake thus formed is now mixed with limestone and
small coal, and again heated. The following changes occur :—(1.)
The carbon reduces the sodic sulphate to sodic sulphide, carbonic
anhydride being set free (Na2SO4+C2–NaS+ 2CO.). (2.) The car-
bon acting on the calcic carbonate, sets free carbonic oxide and lime
(CaCO,--C=2CO+CaO). (3.) The lime reacts on the sodic sulphide
in the presence of carbonic anhydride, producing sodic carbonate,
which is soluble, and calcic sulphide, which is insoluble—
(Na2S--CaO + CO2=Na2CO3 + CaS).
The reaction in full may be thus stated : —
NaaSO4 + 4C + CaCO3 CaS + 4CO + NagCO3.
Sodic + Carbon + Calcic = Calcic + Carbonic + Sodic
sulphate carbonate sulphide oxide carbonate.
The black mass formed consists of an excess of chalk and coal,
together with caustic soda (formed by the action of the lime on the
sodic carbonate), calcic sulphide, and sodic carbonate. It constitutes
what is commonly known as “black ash ’’ or “ball soda.”
(y.) The black ash is now treated with water to dissolve out the
sodic carbonate. The clear solution is poured off, and evaporated to
dryness, the solid residue of sodic carbonate constituting what is
known as “soda ash.”
SODIUM OXY-SALTS, 303
Impurities of Soda Ash.-Sodic chloride, sodic sulphate, and sodic
hydrate. -
Purification of the Soda Ash.-The soda ash is first mixed with saw-
dust, and heated, whereby any sodic hydrate is converted into sodic
carbonate by the action of the carbonic anhydride, formed from the
burning of the carbonaceous matter. The mass is then treated with
water, and the filtered solution evaporated down and crystallized.
Very often, however, the clear solution of the “black ash,” is at
once concentrated by heat until the Na2CO3 is deposited, the mother
liquor, known as “red liquor,” being used in the preparation of sodic
hydrate (see page 299).
Waste Products.-Hydrochloric acid is set free in the formation
of the salt cake. If this were allowed to escape it would prove a
nuisance. Hence in alkali works, it is usually absorbed by means
of a wet coke scrubber. The liquid hydrochloric acid of commerce,
used largely in the manufacture of bleaching-powder, etc., is com-
monly prepared in this manner.
Soda or Alkali Waste.—It will be noted that nearly all the sulphur
of the sulphuric acid used, forms the insoluble calcic sulphide of
the black ash, which, together with the excess of coal and lime,
after its thorough exhaustion with water, forms the “soda,” “alkali,”
or “tank waste.” A part of this is now used in the preparation of
hyposulphite of soda (sodic thiosulphate), (see page 272), whilst the
sulphur of the remaining portion is recovered by blowing air in
such quantity through the moist material that a calcic persulphide
and thiosulphate may be formed (Mond’s Process). From this yellow
liquor the sulphur is thrown down by adding hydrochloric acid:—
(1.) 12CaS + 602 = 20aS3 + CaS2O3 + 9CaO.
Calcic + Oxygen = Calcic + Calcic + Calcic oxide.
Sulphide persulphide thiosulphate
(2.) 2CaS; + CaS,0s -- 6HC1 = 3CaCl2 + 3H2O + 6S.
Calcic + Calcic thio- + Hydrochloric = Calcic + Water + Sulphur.
persulphate sulphate acid chloride
Another process adopted for the recovery of the sulphur, is by adding
to the soda-waste the liquor from chlorine stills (containing MnOl,
and Fe2Cl6), whereby calcic chloride, and the sulphides of iron
and manganese are formed; these latter, on exposure to the air,
become converted into oxides with the consequent separation of the
sulphur :-
(1.), MnGla--Fe2Cl6 -- 4CaS = MnS + Fe:S, 4- 4CaCl,
S- ~~~ ^+ Calcic sul- = Manganese + Iron sul- + Calcic
Chlorine-still liquor phide Sulphide phide chloride.
(2.) 2MnS + Og = Mn,0s + S.; 2Fe2S3 + 20, = 2Fe-0, H- 3S,.
Manganese + Oxy- = Manganese-H Sul- Iron sul- + Oxy- = Iron + Sul-
sulphide gen oxide phur; phide gen oxide phur.
Properties,—Sodic carbonate forms efflorescent crystals, which
304 HANDBOOK OF MOIDERN CHEMISTRY.
melt when first heated in their water of crystallization, but ultimately
leave the anhydrous salt, Na2CO3. At a red heat this salt melts
without decomposing. It has an alkaline taste and reaction, and is
very soluble in water (1 in 2 at 60° F., and 1 in 1 at 212°F.).
(N.B. Sodic carbonate is an efflorescent salt, whilst potassic car-
bonate is a deliquescent salt.)
(14.) Hydric Sodic Carbonate; Bicarbonate of soda (NaHCO3).
Preparation.—By exposing the moist crystals of the normal salt
(Na2CO3) to the action of carbonic anhydride, or by saturating a solu-
tion of the salt with the gas. Considerable heat is evolved during
the process.
Properties.—Bicarbonate of soda is less soluble than the normal
salt (1 in 10 aq. at 50°F.). In preparing the salt from the carbonate
a sesquicarbonate is first formed, then a bicarbonate. Similarly by
heating a solution of the bicarbonate a sesquicarbonate is first formed
(1), and then a carbonate (2).
(1.) 4NaHCO3 = 2Na2CO3, H2CO3 + H2CO3.
(2) 2NaIICOs = Na2CO, + H2O + CO2.
The carbonate of soda used in medicine is a bicarbonate, in other
words a hydric sodic carbonate (NaHCO3). It is not so soluble as
the carbonate, and exhibits a very slightly alkaline reaction to tur-
meric, whereas the carbonate is very alkaline.
(15.) Sodic Nitrate; Cubic Nitre ; Chili saltpetre (NaNO3). Found
native. It crystallizes in rhombohedra, the crystals being deliques-
cent and very soluble (1 in 2 aq.). It fuses at 591°F. (310-5°C.) and
is decomposed at higher temperatures. It is used in the manufacture
of nitric and sulphuric acids, and also in the preparation of potassic
nitrate for gunpowder (see page 274). It is further employed as a
dressing for soils.
(16.) Sodic Biborate ; Boraa (Na2O, 2.B.O.s, 10H2O).
Preparation.—The crude borax (tincal), a compound of soda and
boracic acid, was originally imported from Thibet, where it occurs as
a natural production in the residue obtained from the evaporation of
the water of certain lakes. It is usually prepared at the present time
by fusing sodic carbonate with boracic acid, the latter acid expelling
the carbonic anhydride from the sodic carbonate. The residue is
then dissolved and crystallized.
Properties.—It forms hard clear prismatic efflorescent crystals, the
transparency of which is soon destroyed by exposure to air. The
solution (1 in 12 aq.) is alkaline. When heated the crystals at first
intumesce (swell up), then fuse to a colorless liquid, which, on cooling,
has the appearance of a glassy mass (vitrified borax). Fused borax
possesses the power of dissolving many metallic oxides. Hence its
use as a reagent in blowpipe analysis, the oxides imparting special
colors to the borax bead, by which they may be recognised. It is
SILICATES OF SODIUM. 305
also used for a similar reason, to remove any traces of oxide (or
tarnish) from the surface of metals before soldering. It is employed,
moreover, as a flux; also in enamelling (to render the enamels more
fusible), in fixing colors on porcelain, in glazing stoneware, and also
in medicine.
THE PHOSPHATES (see page 134).
(17.) Hydric Sodic Phosphate—Phosphate of soda-(NaHPO,
12H2O). -
Preparation.—By adding sodic carbonate to the tetrahydric calcic
phosphate obtained during the process of preparing phosphorus.
H.Ca2PO, 4-2Na2CO3=CaCO3 + H2O+ CO2 + Nag HPO,
Tetrahydric calcic + Sodic car--Calcic car--t-Water-HCarbonic anhy--i-Hydric sodic
phosphate bonate bonate dride phosphate.
P.O.EIo,Cao" + 2CONaos-COCao"+OH,-- CO2 +PONaoe Ho
Properties.—The crystals are rhombie, efflorescent, and soluble in
cold water (1 in 4).
Action of heat.—When heated to 99°F. (37.2°C.) the crystals melt in
their own water of crystallisation. Heated to 212°F. (100° C.) they
lose their 12 molecules of water, becoming Na2HPO,. At a red heat
they lose one more molecule of water, sodic pyrophosphate (Na, P.O.)
being formed. If free phosphoric acid (HPO.) be added to this salt
(Na, P.O.), the biphosphate of soda or sodic dihydric phosphate is formed
(NaH2PO4, H2O). Phosphate of soda has an acid reaction.
The tribasic phosphates of soda (and the biphosphate of soda) give
yellow precipitates with argentic nitrate.
(19.) Sodic Pyrophosphate (Na, P.O.,10H2O) (see above) crys-
tallises in prisms. Its solution is alkaline.
The tetrabasic pyrophosphate gives a white precipitate with argentic
nitrate, which is not changed by exposure to light.
(20.) Sodic Metaphosphate, or Monophosphate (NaPOs).
Preparation. — By heating either the sodic dihydric phosphate
(NaH2PO4) or microcosmic salt to redness.
Properties.—A non-crystalline, deliquescent, very soluble substance,
the solution having a feebly acid reaction.
The monobasic phosphate gives a white gelatinous precipitate with
argentic nitrate.
Silicates of Sodium.
Silica or silicic acid has the power of expelling carbonic anhydride
from its compounds. Hence various silicates may be formed by fusing
silica with sodic carbonate.
The salt Na.0,SiO2,911.0 (Futsche) may be prepared by fusing
2 parts of powdered flint with 3 parts of sodic carbonate.
The salt Na.0,36SiO. (Forchhammer) may be prepared by boiling
finely divided silica in a saturated solution of sodic carbonate.
X.
306 HANDBOOK OF MODERN CITEMISTRY.
There are, moreover, many other silicates. The silicate Na.0,4SiO, or
“soluble glass” is prepared by fusing 15 parts of sand with 8 parts of
sodic carbonate and 1 part of charcoal (Fuchs). The silica expels the
CO2, its liberation being assisted by the carbon which converts it
into carbonic oxide. The mass is insoluble in cold water, but is
soluble in hot (1 in 5 aq.) The solution is alkaline.
It is used for stone preservation, in fresco-painting ( Stereochromy),
as a dung substitute in calico-printing, etc.
Glass.
Glass is a compound of an alkaline silicate, and a silicate of an
alkaline earth, mixed with one or other of the metallic oxides. It is
not, however, a true chemical compound but a simple mechanical
mixture. The following table represents the percentage composition
of different glasses.

Crown for g
Window. Plate. optical *
nt.
purposes.
Silica .. g & * * & ſº tº 9 66-37 73.5 62.5 51 - 93
Potash. . & & * * tº º tº º tº tº 5-5 22° 5 13-77
Soda . . tº Q tº tº tº º tº gº 14-23 12-0 tº 4 *
Lime . . * @ tº e tº e • * I 1-86 5' 5 12-5 * &
Alumina tº a * * * & tº º 8- 16 3.5 2 - 5 0.47
Oxide of lead. . tº º * & tº º & & 9 gº & 9 33: 28
Oxide of iron and manganese tº e * * tº ſº & ºl 0-25
Soda always imparts a slightly green tinge to glass, which does not
occur with potash. A soda glass, however, is more fusible and more
brilliant than a potash glass.
Lime diminishes the fusibility of the glass, imparts no color, and
increases its hardness and lustre. If an excess be used, however, the
glass on cooling turns milky.
Lead increases the fusibility and the lustre of the glass, and renders
it softer.
Baryta is also said to increase its fusibility.
Window glass consists of the silicates of soda, lime and alumina.
100 parts of sand, 35 to 40 of chalk, 30 to 35 of soda ash, and 50 to
150 of “cullet” or broken glass, are first subjected to a low heat, so as
to expel any moisture present, and also to drive off a certain quantity of
carbonic acid to prevent subsequent frothing. The heat is then suffi-
ciently raised to effect the complete fusion of the materials. Some-
times sodic sulphate is used instead of sodic carbonate (soda ash), the
sulphuric anhydride being expelled by the silica, as SO3. Sometimes
a little charcoal is added, whereby the SOA is reduced to SO2, its
GLASS. - 307
expulsion being thus effected at a lower temperature. After melting,
the mixture is allowed to remain for the “glass gall,” or “Sandiver,”
or “scum ” (Na2SO, and NaCl) to collect, which is then skimmed off.
Plate-glass consists of the silicates of soda, lime and potash; 300
parts of pure white sand, 100 of sodic carbonate, 43 of slaked lime,
and 300 of fragments of glass are the proportions of the several con-
stituents employed in its manufacture. -
Crown-glass, for optical purposes, contains no soda, in order to avoid
the green tint that the alkali imparts to the glass. Sometimes a little
boracic acid is used in the place of a portion of the silica.
Wine-bottle and carboy glass consists of the alkaline silicates and
the silicates of lime and alumina, with oxide of iron. The constituents
are 100 parts of common red (ferruginous) sand, 80 of soap-maker's
waste, 80 of gas lime, 5 of clay, and 3 of rock salt.
Flint-glass (crystal).-The constituents of flint-glass are 300 parts of
pure white sand, 200 of minium (red oxide of lead), 100 of refined
pearlash, and 30 of nitre. The nitre is added in order to prevent the
reduction of the lead, by oxydizing any matters that might otherwise
effect it. The fusion of the materials is, for the same reason, carried
on in a closed pot. No soda is used because of the tint it imparts to
the glass, whilst lead is added in order to increase its fusibility and its
refractive and dispersive power. Crystal is easily scratched and is
disposed to tarnish and to change colour.
Bohemian glass consists chiefly of potassic and calcic silicates.
Devitrification.—Reaumur's porcelain glass is prepared by heating
certain kinds of glass, such as bottle-glass, or the soluble soda-glass
of Fuchs, to very nearly its melting-point, and then slowly cooling,
whereby it is changed into a hard, opaque, porcelain-like mass (devi-
trification), a change due to the separation and crystallization of the
silicates. Its original transparent state may be restored by fusion.
Such glass is less fusible than common glass, and is a fair conductor
of electricity.
Enamelling is effected by diffusing certain white opaque substances,
such as stannic or antimonious oxides through the glass.
Colouring.—This is effected by dissolving certain metallic oxides in
the glass. The glass generally used for this purpose contains a little
borax and about 53 per cent of oxide of lead (paste or strass).
Ferrous oxide imparts a green color; oxides of silver and antimony,
a yellow; finely-divided charcoal, a brownish yellow ; uranic oxide,
a greenish opalescent yellow ; cupric oxide (CuO) or chromic oxide
an emerald green; cuprous oxide (Cu30), a ruby-red; gold and
stannic oxide, a more brilliant ruby-red; manganic sesquioxide a
violet; oxide of cobalt, a blue; oxides of cobalt and manganese, a
black.
It will be remarked that whilst ferrous oxide imparts a green color
to glass, ferric oxide imparts no color. Hence a little nitre or arse-
308 HANDBOOK OF MODERN CHEMISTRY.
nious acid, or Pb2O4, is often added to the glass, in order to oxidize
any ferrous oxide that may be present. Similarly, the black oxide of
manganese is sometimes used, which converts the ferrous oxide into
ferric oxide, the manganese oxide becoming a protoxide, which,
like ferric oxide, imparts no color to the glass.
Painting on Glass is effected by painting with a very fusible glass, in
a state of fine powder mixed up with turpentine and the oxide requisite
to impart the color, on a somewhat non-fusible glass. A sufficient
heat is then applied to melt the fusible glass paint.
Colored Glass is generally flashed, that is, colored only on the
surface by dipping the uncolored glass into the colored glass pot.
Tests for Sodium Compounds.-(See ANALYTICAL TABLEs.)
LITHIUM (Li2).
Li'-7. Monad (LiCl–OLiH–). Specific gravity, 0.593. Fuses at
356°F. (180° C.).
History.—(Au00c, a stone). Lithia was discovered by Arfvedson
(1817). The metal was first prepared in small quantities by Davy,
and in bulk by Matthiessen (1855).
Natural History.-It is a widely, but sparingly-distributed metal.
It is found in all three kingdoms of nature. In the (a.) animal, it
occurs in milk and in human blood; in the (ſ3.) vegetable, in tobacco; in
the (y.) mineral, in all waters, also in lepidolite, petalite, triphane
(spodumene), triphylline, etc.
Preparation.—By the electrolysis of fused lithic chloride.
Properties. (a.) Physical. Lithium is a white metal, and is the
lightest metal known. It is very ductile and volatile, and burns
with a brilliant crimson flame.
(6.) Chemical. Its reactions are similar to those of sodium and po-
tassium, but it is less readily oxidized. Like sodium, it decomposes
water at ordinary temperatures, but it does not inflame.
Uses.—Its salts are used in gout as a solvent for uric acid.
LITHIUM CoMPOUNDs.
The Lithium compounds best known are the following :-
Lithia (Li2O); lithic hydrate (LiIIO) a body which rapidly corrodes
platinum ; lithic sulphate (LiSO, H2O) a crystalline soluble salt ;
trilithic phosphate (Lisp.O.) a salt soluble in dilute acids, but insoluble
in alkaline solutions or in solutions of alkaline phosphates; and lithic
carbonate (Li2CO3) a very sparingly soluble salt. •
Tests for the Salts of Lithium.
(1.) The salts commonly are fusible and deliquescent.
(2.) They communicate a red color to the blowpipe flame.
AMMONIUM. - 309
(3.) They give a non-continuous spectrum showing a crimson band
between B and C and a faint band in the orange.
(4.) They corrode platinum foil when heated upon it.
(5.) Potassic carbonate gives a white precipitate of lithic carbonate
in cold and very concentrated solutions.
(6.) Hydric disodic phosphate gives a white precipitate in a neutral
or an alkaline solution, soluble in acids and in ammonium salts.
CAESIUM, Cs=133; RUBIDIUM, Rb-85.4.
History.—These metals were discovered by Bunsen and Kirchhoff
(1860) by spectrum analysis.
Natural History.—They are found in the vegetable kingdom (tobacco,
coffee, grapes, beetroot), and in the mineral, as e.g., in many mineral
Waters.
Properties.—Casium gives two blue lines in the spectrum (easius
sky-blue.) Rubidium is a white, rapidly oxidizable metal evolving a
greenish-blue gas (Sp. Gr. 1:52°; fuses at 101.3 F., 38.5° C.) It is
known by its red spectrum lines (rubidus dark red.)
CoMPOUNDS OF CESIUM AND RUBIDIUM.
The compounds of caesium best known are as follows:—
Caesic oxide (caesia, Cs2O); capsic hydrate (CsPIO); capsic chloride
(CsCl); casic sulphate (Cs,SO), a body forming double salts with
sulphates of the class to which magnesic sulphate belongs; a hydric
caſsic sulphate (CsIISO4); capsic nitrate (CSNOs); capsie carbonate and an
acid carbonate (Cs. COs and HCsCOs).
Similar rubidium salts have also been prepared.
The peculiar spectra of caesium and rubidium constitute their
distinctive tests.
AMMONIUM (NH4)2.
Ammonium is a hypothetical metal, of which a supposed amalgam
has been prepared. (See page 221.)
Preparation,--(1). By electrolysing ammonic chloride, a globule of
mercury forming the negative terminal.
(2). By placing a potassic amalgam in a warm solution of ammonic
chloride.
In these cases the mercury swells enormously, owing, it is believed,
to the formation of an amalgam with the metal NH4. The ammonium
amalgam, however, rapidly decomposes into Hg, NHs and H, the two
last gases being in the proportion of 2NHs to H2.
The ammonium theory depends largely on the circumstance that
the combination of dry ammonia-gas (NHS) with the anhydrides,”
such as CO2,S03, etc., form a class called the ammonides, which have but
310 HANDBOOK OF MODERN CHEMISTRY.
a very slight resemblance indeed to the corresponding soda or potash
salts. Thus sulphuric ammonide [(NH3)2SO4] is a soluble crystalline
body, but its solution is not precipitated by baric chloride as true
sulphates are, nor by platinic chloride as true ammonium salts are.
By long boiling, however, the sulphuric ammonide [(NH3)2SO4] becomes
ammonio Sulphate [(NH4)2SO4] the change really consisting in the
assimilation of one molecule of water by two ammonia molecules
(i.e. 2NH3+ H2O=2NH40). In the case, however, of the hydracids,
a true ammonium salt (as NH,Cl) is formed independently of a water
molecule, the hydrogen of the hydracid itself supplying the hydrogen
atom required to form the ammonium radical.
Again, carbonic anhydride and dry ammonia-gas combine to form a
white volatile compound [(NH3)3CO2], which is ammonic carbonate
'minus a water molecule, and is regarded as an ammonic salt of carbamic
acid (H2CO3, or COHo.), a derivative of carbonic acid, where one of
amidogen (NH2) in the salt is substituted for one of the group hy-
droxyl of the acid. If both hydroxyl groups in the carbamic acid be
replaced by amidogen, a body called carbamide [(NH3)3CO] is then
formed.
Compounds of the Hypothetical Metal Ammonium.

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T 3'Or Inllla. * OTDall [8. & Tºo F. “º q)
Names. (general). (constitutional). £3. 3 : : i.
t- || > Qi.)
: P a C P+
Ammonic hydrate (am-
monia) . . . . . . (NH,)IIO AmEſo 35
Ammonic chloride (sal
ammoniac) NH,Cl Am Cl 53.5 1.578 || 31 78
Ammonic iodide .. NH, I Aml 145 11-72
Ammonic bromide NH, Br Ambr 98 17:34
( Diammonic sulphide . (NH,),S SAm, 68
. . Diammonic disulphide. (NH4),S, S,Ams 100
3 | Diammonic pentasul-
:S phide . . . . . . (NHA).S. Ss Am,
ric * g
3, Diammonic heptasul-
ū phide . . . . . . . . . (NHA),S, S,Am, 260
Ammonic hydric sul-
phide * † tº NH, HS SHAm 51
Ammonic sulphate (NH4)2SO, SO, Amo, 132 | 1.695 || 25.75
Hydric ammonic sul-
phate . . . . . . (NH.)HSO, S0, HoAmo 115
Sodic ammonic sulphate | NH, NaS0.2H2O
# (Ammonic carbonate (NH),CO, COAmo,
3 ) Ammonic sesquicarbon-
3 ate . . . . . . . . 2(NHA),0,300, 236
§ Ammonic bicarbonate.. NH, HCO, COHoAmo 79 || 1:586
Ammonic nitrate. . NH, NO, NO, Amo 80 || 1:635
Sodic ammonic hydric
# phosphate (microcos- - - -
mic salt) . . . . NaNH,III'0,4II,0|POHoAmoNao | 137
COMPOUNDS OF AMMONIUM. 311
&
(1.) Ammonic Hydrate.—Ammonia (H,NHO). This is an
aqueous solution of ammonia gas. When the liquid is heated,
ammonia is expelled. Hence, supposing the existence of a hydrate,
the affinity must be of a very feeble nature. -
(2.) Ammonic Chloride.-Sal ammoniac; Muriate of ammonia
(NH,Cl). -
Preparation.—By the combination of ammonia and hydrochloric
acid gases. In commerce it is prepared from gas liquor, which contains
ammonia (derived from the nitrogen of the coal) as a carbonate and as
a sulphide. The ammoniacal liquor is first neutralised with HCl, and
the salt crystallised out and purified by distillation, or else ammonia
gas is set free by heating the liquor with lime, the free ammonia
being conveyed into hydrochloric acid.
Properties.—It is a white solid, crystallising in cubes and octahedra.
It has no smell. It is slightly soluble in alcohol, but very soluble in
water (1 in 3 at 60° F., and 1 in 1 at 212°F.). It is slightly acid to
litmus. It is volatile by heat without fusing, undergoing a temporary
decomposition when heated to a certain temperature, into hydro-
chloric acid and ammonia (dissociation). Hence the vapor volume of
this, as well as of several other ammonium salts, is double that of
most compounds. The relative weight of the vapor is 13-3, so that
one molecule (53-5 parts) instead of occupying two volumes would
seem to occupy four.
(3, 4.) The Ammonic Iodide (NHAI) and Bromide (NH4Br) are
used in photography. They are both soluble salts, the former de-
composing rapidly by exposure to air.
(5-8.) Sulphide of Ammonium.—Diammonic sulphide or protosulphide
[(HºN)2S].
Preparation.—(1.) By distilling together ammonic chloride and
potassic sulphide ; and collecting the products in a cold receiver.
(2.) By mixing H2S with twice its volume of ammonia gas,
Properties.—It consists of colorless crystals. It is a very unstable
body, becoming at ordinary temperatures ammonia and ammonic-
hydric sulphide.
Diammonic Disulphide [(HAN).S.] is prepared by passing sulphur
vapor and ammonia gas through a red-hot porcelain tube. The
Crystals are yellow and transparent.
Boyle's fuming liquor, prepared by distilling sal-ammoniac with lime
and sulphur, is the hydrated diammonic sulphide. Its solution in water,
which dissolves sulphur freely, forms an Ammonic Pentasulphide
[(HAN)2S5], from which solution the sulphur may be obtained in
oblique rhombic prisms. A sulphide with the formula [(HºN).S.] has
been obtained. It is a red crystalline body.
(9.) Ammonic-hydric Sulphide, Hydrosulphate of ammonia
(NH.HS).
Preparation.—(1.) (As a solution.) By saturating a solution of am-
monia with sulphuretted hydrogen.
312 HANDBOOK OF MODERN CHEMISTRY.
(2.) In the anhydrous form by mixing two volumes of ammonia
with two of sulphuretted hydrogen.
Properties. – The anhydrous salt is colorless, transparent, very
volatile, subliming unchanged, and soluble in water.
The solution is at first colorless, but speedily becomes yellow by
absorbing oxygen, whereby ammonic disulphide and ammonic thio-
sulphate (hyposulphite) are formed.—
8H4NHS--50,–2ſ(H,N).S.]+2[(H,N).S.O.]+4H.O.
Finally sulphur is deposited, the solution then containing ammonic
hyposulphite, sulphite and sulphate.
The solution is largely used in the laboratory as a test reagent.
Two important facts should be remembered –
I. On the addition of an acid, (a.) the fresh solution gives off H2S,
the solution itself remaining clear :—
(3.) Whilst the old solution also gives off H2S, but the solution be-
comes turbid from the deposition of sulphur by the action of the acid
on the diammonic disulphide :-
(NH4)2S. -- 2FICl = 2NEI,C1 + H2S + S.
II. With acetate of lead.—(a.) The fresh solution gives a black pre-
cipitate of plumbic sulphide (PbS).
(3.) The old solution gives a red precipitate of plumbic persulphide.
(10.) Ammonic Sulphate [(HºN). SOJ. — Preparation. By dis-
tilling gas liquor with lime, and condensing the ammonia in sulphuric
acid. It is found native as mascagnine, and is also found on the
windows and furniture of rooms where gas is burnt.
Properties. – A crystalline salt, soluble in water (1 in 2 aq.). When
heated the crystals first decrepitate, then melt (284°F. or 140°C),
and finally decompose (500°F. or 260° C.), ammonic sulphate being
formed together with H2O, NHS, N, and SO2.
It is used as a manure, and also to render muslin non-inflam-
mable.
An acid or Hydric Ammonic Sulphate (H,N), H2SO, and a
Sodic Ammonic Sulphate (H4N)NaSO4,2H2O are also known.
(13-15.) Normal Ammonic Carbonate [(HAN)2CO3] is not known,
but probably exists in solution. -
Ammonic Sesquicarbonate or common carbonate of ammonia or
Preston Smelling salts [2(H3N).0,3CO2] is prepared by heating a mix-
ture of chalk and ammonic chloride (or sulphate). The sesquicar-
bonate formed is collected in a leaden vessel and afterwards purified
by sublimation.
6H,NC1+3CaCO, - 3CaCl, + 2H,N + H20+2|(H,N),0,3CO.].
Ammonic + Calcic = Calcic + Ammonia + Water-H Ammonic
chloride carbonate chloride Sesquicarbonate.
The salt smells strongly of ammonia, and is soluble in cold water
(1 in 3 aq.).
COMPOUNDS OF AMMONIUM. 313
On exposure to air the transparent sesquicarbonate gives off NHs
and CO2, and becomes opaque and crumbly, an ammonic bicarbonate being
formed. -
2(H.N).0,3CO2 = 2NEI, + CO2 + 2(HNHCO3)
Ammonic sesquicarbonate = Ammonia + Carbonic acid + Ammonic bicarbonate.
The bicarbonate is also formed by the action of boiling water on
the sesquicarbonate, or by acting with cold water on the sesqui-
carbonate. In this latter case a solution of the normal carbonate
is obtained, and the bicarbonate, a more sparingly soluble Salt (1 in
8 aq.) left.
16.-Ammonic Nitrate (H4NNO3) is prepared by neutralising
ammonic sesquicarbonate with nitric acid. It is a crystalline, deli-
quescent salt, soluble in water with the production of great cold.
On the application of heat it first melts (226 F. or 107.8° C.), and
then decomposes (at 482°F. or 250° C.), into water and nitrous oxide,
and at a greater heat into water, nitric oxide and nitrogen.
17.—Microcosmic Salt or Sodic Ammonic Hydric Phosphate
(Na, H, N, H., PO4,4IH2O) is the only ammonic phosphate of importance,
although phosphates of ammonia corresponding to the sodic phos-
phates are known.
Preparation.—By acting on a solution of 1 part of ammonic chlo-
ride with 6 parts of hydric disodic phosphate, sodic chloride being
also formed. The microcosmic salt is purified from the solution by
successive recrystallizations.
Properties.—It is very soluble. By heat the ammonia and water
are driven off, a sodic metaphosphate remaining. This compound
becomes a colorless glass at a red heat, and in this state dissolves
various metallic oxides, forming with them beads of different colors.
Hence its use in blow-pipe experiments.
Tests for Ammonium Compounds,-(See ANALYTICAL TABLEs.)
314 HANDBOOK OF MODERN CHEMISTRY.
CHAPTER XIII.
GROUP W.—THE METALS OF THE ALKALINE EARTHS.
BARIUM and its Compounds—STRoNTIUM and its Compounds—CALCIUM and its
Compounds—MAGNESIUM and its Compounds.


gº - - Electric
Atomic Atomic Specific tº ºr
Metal. | Symbol. Weight. Volume. Gravity. º
Barium .. e Լ Ra 137-0 34-25 4'00 * e
Strontium .. * * Sr 87.6 34°49 2'54 6-71
Calcium .. tº º Ca 40° 0 25-35 1-57 22° 14
Magnesium © tº Mg 24-0 13-77 1-74 25-47
Barium, strontium and calcium are distinguished from the members
of Group I., as follows:—
(1.) They are divalent elements.
(2.) They are heavier than water.
(3.) They decompose water less energetically.
(4.) Their oxides and sulphides are less soluble in water.
(5.) Their carbonates are insoluble in pure water, but are soluble
in water containing CO2.
(6.) Their sulphates, phosphates and oxalates are either entirely
or nearly insoluble.
Further note :-
(1.) They each form two oxides, of which one is basic and forms
a hydrate with water of the formula M"H2O2.
(2.) They each form one chloride M"Cl,
We class magnesium with the metals of the alkaline earths for
convenience, although its power of resisting oxidation at ordinary
temperatures, its volatility at high temperatures, the sparing solubility
of its oxide and sulphide, and the solubility of its sulphate, more
nearly ally it to zinc and cadmium.
BARIUM (Ba”-137.)
Atomic and molecular weight 137. Specific gravity 4-0. Fuses below a
red heat. Atomicity, dyad (Ba"Cla)
History.—Discovered by Sir H. Davy.
Natural History.—Found as heavy spar (Baš01) and Witherite
(BaCO3). - * “. .
COMPOUNDS OF BARIUM. 315
Preparation.—(1.) By electrolysing baric chloride, using mercury
for the negative pole, whereby an amalgam with barium is produced.
from which the mercury may be afterwards expelled by heat.
(2.) An amalgam of barium may also be formed by the action of a
sodium amalgam on a solution of baric chloride. -
(3.) By passing the vapour of potassium over red hot baric oxide
or chloride.
Properties.—A pale yellow, malleable metal, melting below a
red heat, quickly tarnishing in air, decomposing water at ordinary
temperatures (Ba-H2H2O=H2+BaFL.O.), and glass at a red heat.
All the barium compounds are soluble, colorless (if the acid be
colorless) and poisonous. Sodic or magnesic sulphates are the
proper antidotes.
Compounds of Barium.

Molecular Specific | Ba0 or =
Names Formula Formula weight of g: ºf jī
(common.) (constitutional.) amºus crystals. 100 parts.
1 | Baric oxide (baryta) Baſ'O Ba‘’O 153 5*456 100-00
2 , dioxide (per- O • X
oxide of barium) } Ba0, Bağ ! 169 90°53
3 Baric hydrate BaFI,0, Baho. 171 4-495 89.47
4 ,, chloride Bačijño | BadiºH, 20s 3-052 73-55
5 ,, sulphide BaS BaS 169 90-53
6 ,, disulphide .. BaS, Bağ ! 201 76-11
7 , sulphate BaS0, S0, Bao" 233 4-59 65-66
8 , nitrate Ba2NO, }#}Bao' 261 3-284 58-62
9 ,, carbonate .. BaCO, COBao" 197 4-3 77-67
OCl
O
10 , chlorate Ba(C10), Bao" 304 50 °32
O
OCl
CoMPOUNDS OF BARIUM WITH OxYGEN AND EYDRoxy L.
Baric oxide—Ba0.
Baric peroxide—BaO2.
Baric hydrate—BaFI2O2.
(1.) Baric oxide, Baryta (BaO), is the residue left on igniting
baric nitrate. It freely absorbs moisture and carbonic anhydride,
and slakes with water, forming baric hydrate.
(2.) Baric Peroxide, or Dioxide (BaO2) is prepared by heating
baric oxide in a current of oxygen, or with potassic chlorate. It is
used in the preparation of hydroxyl. When heated it gives off
oxygen, leaving Ba0.
316 HANDBOOK OF MODERN CHEMISTRY.
(3.) Baric Hydrate, Caustic baryta (BaFI.O.). Preparation. (1)
By the action of water on baryta (BaO). (2.) By boiling baric sul-
phide with cupric oxide (Bas-H CuO +OH2=BaBog-- CuS).
Properties.—It rapidly absorbs CO2. It is not decomposed by
heat. It is soluble in water (1 in 20 at 60° F., and 1 in 3 at 212°F),
but is almost insoluble in alcohol.
(4.) Baric Chloride (BaCl22H2O) is prepared by dissolving BaCO,
in HCl. It crystallises in flat prisms, which are soluble in pure
water (1 in 2 at 60°F.), but are much less soluble if the water con-
tains any free acid.
BARIUM OxYsALTs.
(7.) Baric Sulphate (BašO4) is found native. It is insoluble in
water, and in all acids except in boiling sulphuric acid. It is used by
artists as a paint (permanent white), and is employed as an adulterant
of white lead. Heated with carbon, it, in common with all sulphates,
becomes a sulphide.
(8.) Baric Nitrate (Ba2NO3) is prepared by the action of HNO3
on BaCO3. The crystals are octahedral, insoluble in alcohol, but
soluble in water (1 in 8 at 60° F., and 1 in 3 at 212° F.). When
heated it melts, leaving finally baric oxide (2BaN,06=2|Ba0+
2N2O4+O2). It is used for pyrotechny.
(9.) Baric Carbonate, Witherite (BaCO3), is prepared by the action
of an alkaline carbonate on a barium salt. It is insoluble in water con-
taining saline matter, almost insoluble in pure water, but soluble in
water containing CO2.
Tests for Barium Compounds.-(See ANALYTICAL TABLE.)
STRONTIUM (Sr"=87.5).
Atomic and Molecular weight, 87°5; Specific gravity, 2:54; Atomicity
dyad (Sr"Cl2).
History—Discovered by Sir II. Davy in 1808.
Natural History.—Found as strontianite (SrCOs) and as celestine
(SrSO).
Preparation.—Similar to the preparation of barium (see page 315).
Properties.—A white, or according to Matthiessen a dark yellow
metal, malleable, burning in air with a crimson flame, and decom-
posing water at common temperatures, with the evolution of hydrogen,
It is soluble in dilute but not in concentrated nitric acid.
CALCIUM. 317
Compounds of Strontium.

Atomic & -
Names. Formula Formula lº d;tº: Sr0 in
(common.) (constitutional.) salt. crystals. 100 parts.
1 Strontic oxide (strontia) SrO Sr0 103-6 4 - 611 100-0
2 ,, peroxide . . Sr0, sº 119:6 86-62
3 ,, hydrate . . . . Sr.H,0,2H,0 || Sr.PIo,80H, 121-6 1 - 396 85-19
4 , chloride . . . . SrC1,3}{20 SrC1,30H, 158-6 1 *603 65-32
5 , sulphate. . . . SrS0, SO,Sro” 183-6 3-9 56-43
6 , nitrate . . . . Sr2NO, | §§sto" 211 - 6 2-305
7 ,, carbonate . . SrCO, COSro” 147-6 3-65 70-19
(1.) Strontic Oxide.—Strontia (Sr0). Corresponds in all respects
to BaO (see page 315).
(2.) Strontic Peroxide (Sr02).
Preparation.—By the action of hydroxyl on strontic hydrate
(Sr.B.O.--H.O. =Sr0.4-2H2O). •
All the strontic salts are white if the acid with which the metal is
combined be colorless.
Tests for Strontium Compounds.
1. Strontium compounds color the blowpipe flame red. -
2. In the spectrum several bright bands are seen in the red and
orange, and a brilliant band in the blue.
3. Tests similar to barium compounds, excepting that
4. Silico-fluoric acid and sodic thiosulphate give no precipitate with
strontium salts. Strontic silico - fluoride (Sr.F., SiFi), unlike the
barium compound, is soluble in water.
For further Tests see ANALYTICAL TABLEs.
CALCIUM (Ca"=40).
Atomic weight, 40; Specific gravity, 1578; Atomicily, dyad (CaCl).
History.—Discovered by Sir Humphry Davy, 1808.
Natural History.—Found (a.) in the mineral kingdom, as marble,
limestone, calespar, etc. (CaCO3); and as gypsum, selenite, alabaster,
etc. (CaSO4); as a fluoride in fluorspar; as a phosphate in apatite,
phosphorite, etc.
(3.) In the animal kingdom it is found in bones as a phosphate, and
in eggshells, oystershells, etc., as a carbonate.
(y.) It is present in all vegetables.
Preparation.—(1.) By processes similar to those described for the
preparation of barium and strontium (see page 315).
318
HANDBOOK OF MODERN CHEMISTRY.
(2.) By igniting sodium with calcic iodide.
(3.) By heating an alloy of zinc and calcium (formed by fusing
together zinc, sodium, and calcic chloride) so as to volatilise the
zinc.
Properties.—A light yellow, very hard, malleable, ductile metal.
It melts at a red heat, tarnishes in air, and decomposes water.
It is
rapidly acted on by dilute acids, and burns when heated with a
brilliant white light.
Compounds of Calcium.

3
:
11
12
13
14
15
16
17
18
19
20
‘5 É
Names Formula Formula # E £ 35 | Specific Gravity | Ca or CaO
º (common). (constitutional). #### of the Crystal. in 100 parts.
B. :
Calcic oxide (quick
lime) * CaO CaO 56 3-18 Ca-71-43
Calcic peroxide CaO, { 30,
Calcic hydrate—
(slaked lime) . . CaB,0, CaFIo, 74 ſ 2-078 CaO=75.68
is e Crystallized 1-680 sºme º 'º #
Calcic chloride CaCl, CaCl, 111 |Fused 2' 485 Ca-36-03
,, bromide Cabra CaRr,
,, iodide Caſa CaL,
Calcic fluoride—
(fluor spar) CaF, Caf, 78 3-4 Ca-51 °28
Calcic sulphide CaS CaS 72 -
Calcic disulphide. . CaS, { §o.
Calcic pentasul-
hide . . . . CaS. CaS;
Calcic thiosulphate
(hyposulphite). CaS,0, SS" ().Cao”
Calcic hypochlorite CaCl2O, Ca(OCl)Cl
Calcic phosphide .. Ca,P,(?) tº º 142
Calcic sulphate— - A/ Crystallized 2:30 * * : * >
(gypsum) CaSO, S0,0ao 136 | §. 3.; CaO=41-18
sº º NO, tf Crystallized 1 '780
Calcic nitrate Ca2NO,4H.0 |} N öCao ,40H, 164 | sº 2° 24
Calcic carbonate—
(chalk) . . . . CaCO, COCao” 100 2.72 CaO=56:00
Tricalcic phosphate
(bone earth) . . Caº P,0s P,0,0ao",
Calcic phosphate -
(superphosphate) || Ca"H,2P0, P,0, Ho,Cao'
Calcic disilicide . Si,Ca
Calcic oxalate Cao,0,2H.0 || §Cao',20H, 128
Cox(POUNDs of CALCIUM witH OxYGEN AND HYDROXY.L.
... CaO.
... CaO.
... CaFI.O.
Calcic oxide
Calcic peroxide
Calcic hydrate
tº º ſº tº º º
e º 'º
TISES OF LIME. 319
(1.), Calcic Oxide; Lime, Quicklime (CaO). Preparation.—(1.) By
heating together coal and limestone (CaCO3); (2) Pure CaO may be
prepared by heating Carrara marble to redness for some hours in an
open fire.
Properties.—A white, caustic, infusible substance, combining rapidly
with water (slaking), by which process great heat is evolved. The
lime swells up during the process (live-lime), and finally crumbles to a
white powder, forming CaO, H2O, called slaked lime or solid calcie
hydrate. When exposed to the air, lime absorbs both moisture and
carbonic anhydride, becoming what is called “air-slaked” lime, a
compound represented by the formula (CaCO3, CaFI2O3).
(2.) Calcic Peroxide (CaO2) is prepared like Sr02 (see page 317.)
(3.) Calcic Hydrate, Slaked lime (CaFI2O.), is prepared by the
action of water on quick lime (CaO). When heated to a red heat,
H2O is expelled, and CaO remains.
A white creamy mass called “milk of lime” is produced when calcic
hydrate is diffused in water. Calcic hydrate is twice as soluble in
cold (1 in 700 or 0.5 gr. to 5.j.) as it is in hot water, the solution being
known as “lime-water,” which is an alkaline liquid, rapidly absorbing
CO2 from the air. By evaporating lime-water “in vacuo’’ a crys-
talline hydrate (CaFI2O3) may be obtained (Gay Lussac).
Uses of Lime.
Mortar, which is used for buildings exposed to the action of air only,
consists of lime and sand, the latter being added, as in the case of
pottery, to increase the cohesive power of the lime, and to prevent its
shrinking as it dries. Before the mortar is applied, the bricks are
wetted, in order to prevent their absorbing moisture too rapidly from
the mortar. It is not very clear why mortar dries. The surface, and
the surface only of the mortar becomes carbonated, whilst to a certain
extent combination takes place between the lime and the silica,
forming a calcic silicate.
Mortar, when exposed to the action of water, disintegrates. Hence
it cannot be used for sub-aqueous constructions.
Cements, or Hydraulic Mortars are employed for buildings exposed
to the action of water. They consist of a calcined mixture of carbonate
of lime and clay (10 to 30 per cent.), whereby calcic silicate and some
aluminic silicates (the silica being derived from the clay or lime) are
formed. The powdered calcined mass, when mixed with water,
solidifies, owing to the formation of hydrated double silicates and
aluminates, a substance being thus formed of great hardness, and
upon which water has no action.
The rapidity of solidification depends on the quantity of clay
present. If it contains 25 to 35 per cent., it hardens in a few hours,
and constitutes what is called Roman cement, a substance commonly
320 EIANDBOOK OF MODERN CHEMISTRY.
&
manufactured from the nodules of calcareo-argillaceous ironstone,
found in the London clay.
Portland cement consists of a calcined mixture of lime and mud (clay)
taken from the river Medway. The mass, when dry, has the appear-
ance of Portland stone.
Concrete is a mixture of hydraulic cement with gravel or coarsely
powdered pebbles. Scott's cement is lime, containing a small proportion
of calcic sulphate.
Lime is also used as a manure, for the purification of coal gas, and
for various other purposes.
(4.) Calcic Chloride (CaCl2).--Preparation. (1.) By the action of
HCl on CaCO3. The solution is evaporated to dryness, when
CaCl2,6H2O is obtained, which, at 390°F., becomes CaCl2,2H.0, and
above this heat CaCl2. (2.) It is also obtained, as a secondary pro-
duct, in the manufacture of ammonic carbonate (see page 312). Thus—
6H,NCI+3CaCO3 = 3Ca(Ol. 4-2ſ (HN).0,300.] + 2H N + H.O.
Properties.—A white, very deliquescent salt, soluble in alcohol and
in water, the saturated aqueous solution boiling at 355°F. (179.5°C.).
It absorbs ammonia freely.
Uses.—It is used in the laboratory in the solid form as a dessicant,
and its solution is employed as a bath to obtain a steady, continuous
temperature. The crystals mixed with ice form a powerful freezing
mixture.
(7.) Calcic Fluoride, Fluor spar (CaF2) is found as a mineral in
sea and in other water, and also in the bones and teeth of animals. It
is the source of all the fluorine compounds.
(8.) The Calcic Sulphides are mostly soluble. CaS forms one
of the principal constituents of the “soda waste” of the alkali works.
By exposure to air, it becomes calcic thiosulphate (hyposulphite),
(2CaS+ H20+2O3=CaFI2O2+ CaS,0s), and by the action of sodic
carbonate is converted into sodic thiosulphate (see page 272).
(14.) Calcic Sulphate (CaSO4) is found in nature as anhydrite
(CaSO4), and as gypsum, alabaster, selenite, etc., (CaSO4,2FI.O); also in
various waters (selenitic), constituting one source of permanent hardness.
Properties.—It occurs in flattened prisms (selenite) and in earthy
masses (gypsum). It is soluble in water (1 in 500–140 grs. per
gallon at 60°F.), its solubility being diminished by the presence of
calcic and magnesic chlorides. It is insoluble in alcohol and in
dilute nitric and hydrochloric acids.
Uses.—Plaster of Paris consists of finely-powdered gypsum calcined
at 500°F. (260° C.), so as to drive off the two molecules of water it
contains. When the calcined mass is mixed with water it rapidly
solidifies and expands, again combining with the two molecules of
water expelled by the previous heat. If “overburnt” this property
of recombination with water is destroyed. Ty exposure to air,
CALCIUM. 321
plaster of Paris deteriorates, owing to its absorbing moisture. Stucco
is plaster of Paris mixed with a solution of size, whilst various
cements are formed by its admixture with a solution of alum, borax,
etc., by which means the hardness of the mass, when set, is greatly
increased. Scagliola, or artificial marbles, are formed by the insertion
into the stucco of pieces of natural stone.
The “pearl hardener” of the paper-makers is freshly precipitated
calcic sulphate.
(15.) Calcic Nitrate (Ca2NO3,4H2O) is a crystalline deliquescent
salt, soluble in alcohol.
(16.) Calcic Carbonate (CaCO3) is found native, both in an un-
crystallized state, as limestone, chalk, oolite, etc., and also in minute
granular crystals (as marble), either colored with iron or manganese
oxides, or of a black tint, due to the presence of bituminous matter.
It also occurs in large six-sided crystals, as arragonite, and in rhom-
bohedral crystals, as Iceland or calc spar, etc.
In the animal kingdom it forms the chief constituent of corals, of
fish, and of egg-shells; and it enters largely into the formation of
bones. Pearls are also composed of it.
Properties.—A white, crystalline (dimorphous) body, almost in-
soluble in pure water (2 grs, in 1 gallon), but soluble in water con-
taining carbonic anhydride, from which solution it is deposited when
the gas is driven off. In this way the stalactites and stalagmites of
Derbyshire are formed, and also the tufa and travertine of volcanic
districts. It is decomposed by heating in air (CaCO3=CaO + CO2),
and also by the action of HCl, HNO3 or H.S.O.
It constitutes one and the chief cause of the temporary hardness of
water, that is, hardness removable by boiling (see p. 208). The depo-
sition of the lime and magnesic carbonates in boilers, constitutes what
is called “furring,” and renders a water containing an excess unsuit-
able for boiler purposes, The deposition, however, may be, in a great
measure, prevented by the addition to the water of a little soda ash
or ammonic chloride. In the latter case, ammonic carbonate is formed,
which volatilises along with the steam, a soluble calcic chloride
remaining. Dr. Clark has suggested a plan of softening hard waters
by adding a sufficiency of lime to combine with the carbonic acid
holding the carbonate of lime in solution, whereby the calcic car-
bonate pre-existent in the water and that formed by the union
of the carbonic acid and the additional lime, are precipitated together.
Calcic carbonate constitutes the basis of many building materials,
such as marble, Portland stone, Bath stone, magnesian limestone, of
which the Houses of Parliament are built. The decay of such stones
is dependent, in a town, on the action of sulphuric acid (produced
by burning coal), and of carbonic acid, as well as by mechanical dis-
integration occasioned by the expansion of the water in the pores of
the stone in the act of freezing.
Y
322 HANDBOOK OF MODERN CHEMISTRY.
(17-18.) Calcic Phosphates.—The Tricalcic phosphate (Cas P20s)
occurs native in osteolite, coprolite, etc. It is the principal ingredient of
bone-ash. Various calcic phosphates known as phosphorite, apatite, etc.,
are also found native. Calcic superphosphate (Ca"H,2PO) is formed
by treating bone-earth with oil of vitriol.
(20.) Calcic Oxalate (CaC2O4,2H2O) is a white insoluble body,
precipitated when ammonic oxalate is added to a lime solution. It is
insoluble in acetic acid, but is converted by heat into calcic carbonate
(CaC2O4–CaCO3 + CO). -
Chloride of Lime, or “Bleaching powder,” is prepared by passing
chlorine over slaked lime. The lime absorbs nearly half its weight of
chlorine. Formerly the compound was regarded as a mixture of
calcic chloride and hypochlorite. Thus—
2Ca（2O2 + 2Cl3 = CaCl2 + CaCl2O3 + 2 H2O.
Calcic hydrate + Chlorine = Beaching powder + Water.
But inasmuch as bleaching powder is not deliquescent (when well
made) and not soluble in alcohol as calcic chloride is, this compound is
now believed to be a definite chemical combination, viz., a calcic-chloro-
hypochlorite, Ca(OCl)Cl.
It is decomposed by water, by heat, by moist air (hypochlorous
acid being evolved), and by acids.
Tests for Lime and its compounds.
(See ANALYTICAL TABLEs.)
MAGNESIUM (Mg").
(Atomic and molecular weight, 24. Specific gravity, 1743. Atomicity,
dyad. (MgCl2). Fuses at a red heat). Its general properties, the
volatility of its chloride, the solubility of its sulphate, and the
isomorphism of its compounds with those of zinc, ally it, so far
as its general chemistry is concerned, to this metal, rather than
to the metals of the earths.
We consider it here for convenience.
History.-Prepared by Davy in 1808, and studied by Bussy in 1830.
Natural History.—It occurs (a) in the mineral kingdom as mag-
nesite (Mg,CO3), dolomite or magnesian limestone (Ca"Mg"2CO3),
as brucite (MgH2O2), and as boracite, hydroboracite, and pearl spar.
As a silicate it is found in the form of mica, asbestos, hornblende,
serpentine, olivine, steatite (soapstone or French chalk), meerschaum,
talc, etc. It occurs in most waters as a carbonate and a sulphate. (3.)
It is found in animals and vegetables in combination with carbonic,
phosphoric, and most organic acids.
Preparation.—(1.) By the electrolysis of fused magnesic chloride.
(Davy.)
(2.) By heating a mixture of metallic potassium and magnesic
chloride. (Bussy.)
(3.) By fusing a mixture of MgCl2, NaCl,Caſ', and Na.
MAGNESIUM. 823
Properties.—(a.) Physical. A white, hard, light, malleable, ductile
metal, melting at a red heat, and sufficiently volatile that if heated
in a hydrogen atmosphere it may be distilled. It is insoluble in cold
water, but is soluble in acidulated water and in ammonic chloride
(4NH4C1+Mg=2NH,Cl,MgCl2 + H2+2NH3).
(6.) Chemical. It decomposes warm but not cold water. It is not
easily affected by dry air, but is rapidly oxidized in moist air at
ordinary temperatures. It burns in air (forming MgO), the light
evolved being of great intensity, and highly actinic. It also burns in
chlorine, bromine, iodine, and in sulphur vapors. It combines, with
nitrogen at high temperatures to form a nitride (N2Mgs). It ignites
when placed in HCl, but is not acted on by cold nitro-sulphuric acid.
It reduces acid solutions of salts of many of the metals, hydrogen gas,
or, as in the case of arsenical and antimonial compounds, arseniu-
retted or antimoniuretted hydrogen, being evolved.
Uses.—It is used as a source of light in photography, the mag-
nesium spectrum being continuous and of high actinism.
Compounds of Magnesium.
S$ 3
B=## Anhydrous
SALTS Ordinary Constitutional ||3|E #| Specific Gravity |Salt contains
* Formula. Formula. ă = à of Crystals. Mg or MgO
.# <! 5 per cent.
§§
1 Magnesic oxide -
(magnesia) MgO MgO 40 3-6 Mg=60
2 Magnesic hydrate MgH20, MIgEIo,
with 6H,0.
3 , chloride MgCl2 MgCl, 95 | 1-562
anhydrous 2.177
4 , bromide MgRr, MgBr, 184
5 , nitride MgsNs
; $y .#. MgS MgS * 56 -
, Sulphate f/ Crystals 1-660 MgO=16-26
(Epsom salts), , MgSO4,7H,0 SOHo,Mgo",6OH, 120 } Anhydrous 2*706 || MgO=33-33
* Magnetic nitrate Mg3No.6B.0 |}{}Mg',60H, us 1-464
9 ,, carbonate MgCO COMgo” 84 3-056
(basic carbonate) MgCO,MgH.0, 3H,0
10 Hydric magnesic
phosphate H.Mg,"2P0,14H,0
11 Ammonic magnesic
phosphate (triple
phosphate) ..., |Mg",(H,N).2P0,,12H,0 274
12 Magnesic pyro-
phosphate Mg,F,0, P,0,Mgo”
13 Magnesic phos-
phate. . . . . . . Mgs P,0s P,0,Mgo"
14 Magnesic borate.. 3MgO,4B,0s Bs0,Mgo”
I , silicates
(various)
f
(1.) Magnesic Oxide
magnesium.
, Magnesia (MgO).
This is the only oxide of
324 HANDBOOK OF MODERN CHEMISTRY.
Preparation.—It may be prepared by burning magnesium in air, or
by igniting magnesic carbonate or nitrate in a crucible. It is a white
and almost insoluble powder. Like lime, baryta, and strontia, it
slakes with water; but, unlike them, it develops no heat in doing so.
The magnesic hydrate (MgH2O2) thus formed, slowly absorbs atmo-
spheric carbonic anhydride. The hydrate forms a compact mass like
plaster of Paris, and may be used for casts. Magnesic oxide, when
placed on turmeric paper and moistened, turns the paper brown.
(2.) Magnesic Hydrate (MgH2O2) occurs in nature as brucite,
and may be prepared, in addition to the above method, by precipi-
tating magnesic sulphate with potassic hydrate (MgSO,--2KHO=
K2SO4+MgH2O2). It is insoluble in water, and infusible by heat.
(3.) Magnesic Chloride (MgCl2) is found in sea water. It may
be prepared by acting on magnesia or magnesic carbonate with
hydrochloric acid. On evaporation to dryness, the MgCl2 is decom-
posed (MgCl2 + H2O=2|HC1-i-MgO). If ammonic chloride, however,
be added to the solution before it is evaporated, the double salt
(MgCl2,2NH,Cl) is formed, from which the NH,Cl may be volatilized,
leaving pure MgCl2 in a fused state.
It is a crystalline deliquescent substance, freely soluble in water
and in alcohol.
(4.) Magnesic Bromide (MgBr) is found in sea water and in
saline springs.
(5.) Magnesic Nitride (Mg3N2) may be produced by the direct
union of nitrogen and magnesium. It is a crystalline body, easily
decomposed by water (N.Mg3 + 3PI2O=2NH3+3MgO).
(6.) Magnesic Sulphide (MgS) is slightly soluble in water.
(7.) Magnesic Sulphate, Epsom salts (MgSO47 H2O), is found
native in small quantities in most waters, but in great abundance in
certain springs in the neighbourhood of Epsom.
Preparation.—By calcining dolomite (MgCa2CO3), a mixture is
formed of MgO and CaO. This residue, after being washed to ex-
tract some of the lime, is acted on with sulphuric acid, whereby
MgSO, and CaSO, are formed, the latter of which, being insoluble,
is precipitated. The magnesic sulphate may then be obtained from
the clear solution by evaporation.
It may also be prepared from the “bittern " of sea water (that is,
the liquor remaining after the extraction of the common salt), as
well as from the liquor of the alum works.
Properties.—A white crystalline (right rhombic prisms), bitter
tasted, slightly efflorescent salt. It is soluble in water (1 in 3 aq. at
60° F., and 1 in 1:5 aq. at 212°F.). By a heat of 212°F. (100° C.),
six of its water molecules may be driven off, whilst the seventh
molecule needs a very much higher temperature to effect its separa-
tion. This seventh molecule may be displaced by a molecule of an
anhydrous salt (such as K2SO4), a double salt being formed (such as
MAGNESIUM. 325
MgSO4, K2SO4,6H2O), having the same crystalline form as magnesic
sulphate. -
(9.) Magnesic Carbonate (MgCO2). — Natural History. Found
native as magnesite and (together with CaCO3) as dolomite.
Preparation.—Boiling solutions of K2CO3 and MgCl2 are mixed toge-
ther, and the precipitate formed dissolved in carbonic acid water.
From this solution the salt is deposited (Mg,CO3,3H2O) as the carbonic
anhydride escapes. “Magnesia alba” (MgCO3.H2O, MgH2O2) is pre-
pared by precipitating a magnesic sulphate solution with a sodic
carbonate solution.
(11.) Ammonic Magnesic Phosphate, Triple phosphate:
(Mg2(HAN)22PO4,12H2O) is an important salt, magnesia being
usually precipitated in analysis in this form. It is insoluble in water
containing free ammonia. On igniting the salt, magnesic pyro-
phosphate (Mg,F.O.) is formed, from which the quantity of mag-
nesia may be estimated.
Triple phosphate is a frequent constituent of urinary calculi.
(15.) The Magnesic Silicates are numerous. Tale (4MgO,5SiO2),
steatite (3MgO,4SiO2), meerschaum (2MgO,3SiO2,4H2O), and serpen-
tine (2C(MgFe)0, SiO2]MgO,2H2O) are a few illustrations of its more
common forms.
Tests.-(See ANALYTICAL TABLEs.)
326 HANDROOK OF MODERN CHEMISTRY.
CHAPTER XIV.
THE METALS OF GROUP IV.
MANGANESE and its Compounds—ZING and its Compounds — CoRALT and its
Compounds–NICKEL and its Compounds—URANIUM and its Compounds—INDIUM
and its Compounds.
MANGANESE (Mn=55).
Specific gravity 7-0 to 8:1. Atomicity, dyad, tetrad, and herad, also a
pseudo-triad and an octad; a dyad as in Manganous compounds (MnO ;
MnSO4), and a tetrad (although apparently a triad) in Manganic
compounds (Mn2O3 ; Mn2Cl6).
History.—Manganese was used in early times, although its nature
was not understood, to color glass. The oxide was recognised by
Scheele in 1774, and the metal obtained by Gahn in 1780.
Natural History.—Manganese is not found in a free state. It
occurs as an oa;ide in hausmannite, Mn2O4, braunite, Mn2O3, and pyro-
lusite, MnO2; as a sulphide in manganese blende, MnS; as a carbonate
in manganese spar, MnOOs; and as a silicate in red manganese,
MnSiO3. It is found in the ashes of plants.
Preparation.—(1.) By reducing manganous carbonate with char-
coal.
(2.) By the electrolysis of manganous chloride.
(3.) By the action of sodium on manganic fluoride.
(4.) By reducing the oxide with carbon in a crucible of caustic
lime. (Deville.)
Properties.—(a.) Physical. A greyish-white or reddish metal, brittle,
but so extremely hard that it will scratch steel. It is feebly magnetic,
and very difficult to fuse.
(6.) Chemical. It is readily oxidized when exposed to the air. It
decomposes water at ordinary temperatures, liberating hydrogen. It
has a great attraction for carbon.
Uses.—It is mixed with iron for the purpose of hardening it.
CoMPOUNDS OF MANGANESE AND OxYGEN.
MnO, Mn2O3, and MnO, exist in a free state; MnO, and Mn2O,
have never been isolated.
Chemically, it is to be noted that—
MnO is a powerful base.
Mn2O3 is feebly basic.
MANGANESE.
327
Mn30,
MnO2
MnO,
Mn30,
| are anhydrides.
Compounds of Manganese.
} are indifferent oxides, that is, are neither basic nor acid.

|
$– o, i
3 + 3 −.
Ordinary Constitutional ſº ##| Specific Mn
SALTS. Formula. Formula. # § # Gravity. per cent.
= P =
<
1 Manganous oxide (protoxide) Mn’O IMnO 71 77°46
2 95 hydrate MnH,0, MnHo, 61-79
3 g | Manganic oxide (sesquioxide) || Mn"20"a MnOMino” 158 4-82 69.62
4; ,, red oxide MnO, Mn,0, #3Mno" 229 4.72 72-05
5° Manganic dioxide (peroxide) Mnºo, MnO, 87 4'94 63-22
6 Manganic anhydride MnO, º MnO, 103 53-39
7 lfermanganic anhydride MnviiO, (?) 222
83 ( Manganous chloride MnO1, MnCl, 126 2-01 43' 65
9; ) Manganic chloride MnCl, MnCl, 197 27-9]
103 | Dimanganic hexachloride Mn2Cl6 | # 823 34-05
C 3 3-1 Of
| 1 Manganous sulphate MnSO,7H,0|SOHo,Mno",60H, 151 i. 36.42
12 Manganous carbonate . . MnOO, COMno” 115 47-82
(1.) Mangamous Oxide, Protoacide of Manganese (MnO).
Preparation.—(1.) Anhydrous. By igniting manganous carbonate in
a current of hydrogen.
(2.) As a hydrate (MnH2O2).
manganous salt.
By the addition of an alkali to a
Properties.—Manganous oxide has an olive-green color, and rapidly
absorbs oxygen.
on exposure to air.
It is a powerful base.
(3.) Manganic Oxide, Sesquioaide of Manganese (Mn2O3).
Natural History.—Found native as braunite (Mn2O3), and as manganite
(Mn20s,H2O).
The hydrate is white, but turns brown immediately
Its salts are flesh-colored.
Preparation (as a hydrate).- By first passing chlorine through water
in which manganous carbonate (MnCOs) is suspended, and subse-
quently removing the excess of carbonate with dilute nitric acid.
Properties.—A brown substance, decomposed by heat (6Mn2O3=
4Mn3O4+O2).
It colors glass violet (amethyst).
and isomorphous with alumina and ferric oxide.
nese alum ” manganic sulphate displaces aluminic sulphate—
(*so }
Mn23SO,
Ol'
Alg 3SO1
24H2O )
Its salts are red, and are decomposed by heat.
Action of Acids.-Strong sulphuric acid, when heated, decomposes
It is a weak base,
Thus in “manga-
328 HANDBOOK OF MODERN CHEMISTRY.
it, liberating oxygen, and forming a manganous sulphate; dilute
sulphuric acid dissolves it ; nitric acid decomposes it into MnO and
MnO2, dissolving the former oxide; hydrochloric acid evolves chlorine
when heated with it.
(4.) Red Manganese Oxide (Mn30,) occurs native as “haus-
mannite,” and may be prepared by heating any of the manganese
oxides in the open air. It does not form salts. Fused borax and glass
dissolve it, acquiring an amethyst color.
(5.) Manganic Dioxide; binoaide, pervaside, or black oxide of man-
ganese (MnO2).
Natural History.—Found native in a crystalline state as “pyro-
lusite, and in an amorphous form as “psilomelane.” It occurs as a
hydrate in “wad "and “varvicite” (Mn2O,2MnO2, H2O).
Preparation.—(1.) Anhydrous. By calcining the nitrate.
(2.) As a hydrate. (a.) By acting on potassic permanganate with
an acid.
(3.) By heating Mn4O4 with nitric acid.
(y.) By adding chloride of lime to a solution of a manganous salt.
Properties.—(a.) Physical. A black substance, insoluble in water.
It is a good conductor of electricity. It is decomposed by heat
(3MnO2=Mn4O4+O2).
(3.) Chemical. MnO, is an indifferent oxide, that is, it is neither
acid nor basic. Heated with sulphuric acid oxygen is evolved, and a
manganous sulphate formed (2MnO2+2H2SO4–2MnSO, +2H2O+ O.).
With hydrochloric acid chlorine is set free, and a manganous chloride
formed. Nitric acid is without action upon it. Manganic dioxide is
largely used for the preparation of the chlorine required in the manu-
facture of bleaching-powder. Inasmuch as MnO, usually contains iron,
the residual liquor also contains mixed manganous and ferric chlorides.
I'rom this liquor the manganous chloride may be again converted
into oxide by adding a little lime to the mixed solution, which pre-
cipitates the per-chloride of iron without decomposing the proto-
chloride of manganese, peroxides being weaker bases than protoxides
(Fe2Cl6+3Ca()=Fe2O3 + 3CaCl2). The manganese may now be thrown
down with chalk as a carbonate from the solution (MnCl2 + CaCO3=
MnOOs+ CaCl2), which is then roasted at 600°F., and the MnO2 re-
produced. (Dunlop.) -
(6.) Manganic Acid (H.MnO,-121)—The manganates. The free
acid is not known. Potassic manganate (mineral chameleon) (KAMnO4)
and sodic manganate (Na,MnO4) are prepared by fusing together
caustic potash or soda respectively, with manganese dioxide. The
solutions when evaporated in vacuo over sulphuric acid yield green
crystals. When these are dissolved in pure water, or in water con-
taining a trace of acid (the manganates being less stable in an acid
than in an alkaline solution), the salts are decomposed, the color of
the liquid changing from green to red, due to the formation of potassic
IMANGANESE, 329
or sodic permanganate, a black precipitate of manganese dioxide
being thrown down (3R,MnO,--2H2O=1K.,Mn2Os--MnO2 + 2K2H2O2).
The sodic manganate constitutes “Condy's green disinfecting fluid,” the
action of which depends on the ease with which the manganates yield
their oxygen to organic matter. “Cassel green” is a baric manganate
(Ba''MnO4).
(7) Permanganic Acid (H.Mn2O3).-The permanganates.
Preparation.—(1) A potassic permanganate is formed by the action
of heat on an intimate mixture of manganese dioxide (4 parts), potassic
chlorate (3-5 parts), and potassic hydrate (5 parts), whereby a potassic
manganate is formed, which may be dissolved out with water.
Carbonic anhydride is then passed through the green solution, until
it becomes red (3K2MnO4+ 2CO2=K.Mn2Oa-i-2K2CO3 + MnO2). The
clear liquid decanted from the precipitate is then evaporated to a
small bulk, and the potassic permanganate crystallised out (Béchamp).
By treating the crystals with sulphuric acid, permanganic acid rises
as a violet vapor, and may be condensed to a dark liquid.
(2.) A solution of the acid may also be prepared by decomposing
baric permanganate with dilute sulphuric acid.
Potassic permanganate crystals appear red by transmitted, and dark
green by reflected light. When heated they yield oxygen. All the
permanganates (excepting the silver salt) are soluble in water, their
solutions being of a red color. This color is discharged by sul-
phurous acid, by neutral solutions of the sulphides and pentathionates,
by acid solutions of the sulphates, hyposulphites, arsenites, nitrites,
etc., and by acid solutions of mercurous, ferrous, stannous, and anti-
monious salts, the permanganic acid being reduced to the colorless
manganous oxide.
The permanganates are not so unstable as the manganates, never-
theless they readily yield their oxygen to organic matter, the per-
manganic acid first becoming manganic acid, and the manganese
being ultimately reduced to the state of a hydrated manganic dioxide
(Condy's red disinfecting liquid).
(8.) Manganous Chloride; Protochloride of manganese (MnO],).
Occurrence and Preparation.—It occurs mixed with ferric chloride
in the residual liquor obtained during the preparation of chlorine. It
may be separated by evaporating the clear filtrate to dryness and
igniting, by which means the iron salt is either volatilized or con-
verted by the remaining water into the insoluble sesquioxide. On
treating the mass with water the manganous chloride may be dissolved
out.
The salt is pink, deliquescent, soluble in water and alcohol, and
fusible at a red heat.
(9.) Manganic Chloride (Mn2Cl6), a brown substance decomposed
by heat (Mn2Cl6=2MnCl2+Cl2). Manganic tetrachloride (MnCl,), and
Manganic orychloride (MnCl2O2, Rose), (termed Manganic perchloride
3 30 HANDBOOK OF MODERN CHEMISTRY.
(Mn2Cl2) by Dumas), a yellowish condensible gas obtained by dis-
solving potassic permanganate in sulphuric acid, and adding fused
Sodic chloride to the solution, have also been described.
(1.1.). Mangamous Sulphate (MnSO,7H2O).
Preparation.—Manganic dioxide is first heated with sulphuric acid,
the solution evaporated to dryness, and the residue ignited in order to
decompose any ferric sulphate present. By acting on this residue
with Water, pure manganese sulphate is dissolved, and the insoluble
ferric oxide left.
Properties.—A rose-colored soluble salt used by the dyer in pro-
ducing blacks and browns.
(12.) Mangamous Carbonate (MnOO3) is found native as “man-
ganese spar,” and may be prepared as a hydrate (2MnCOs, H.O) by
precipitating MnOlz with an alkaline carbonate. -
Tests.-(See ANALYTICAL TABLEs.)
ZINC (Zn").
Atomic and Molecular weight, 65. Specific gravity, 6-8-7-2. Atomicity
dyad (") as ZnO ; ZnCl2.
History.—The metal was known (as “Spelter") in the thirteenth
century. It was described by Paracelsus.
Natural History.—It has never been found native. It occurs as
a carbonate (ZnCO3) in Calamine, as a sulphide in blende, as an
oacide (ZnO) associated with iron and manganese oxides, in red zinc
ore, and as a silicate in “electric calamine” or zinc glass (Williamite).
Preparation.—(A.) The ore is first brought into the state of oxide
either (a) by calcining the carbonate or (3) by roasting the sulphide.
Thus—
(a.) ZnCO3 (calamine) = ZnO + CO2.
(3.) 22nS (blende) + 3O2 = 22n() + 2SO4.
(B.) The oxide is now heated with powdered coal, either, as in
Silesia, in an earthen retort, or, as in England, in a crucible closed
with a luted lid, into the bottom of which an exit pipe is fitted,
through and down which the zinc distils (distillation per descensum).
ZnO + C = Zn + CO.
Impurities and purification.—Of the impurities of zinc the principal
are zinc oaſide, lead, iron, tin, antimony, arsenic, copper, and cadmium.
Zinc oaside is separated by melting the metal and skimming off the
dross which collects on the surface, the ingots thus prepared being
known commercially as “spelter.” The presence of lead interferes
with rolling the zinc. The greater specific gravity of lead (Pb-114;
Zn=7|14) enables us to extract a portion of the lead from the mixed
metal by simply melting the alloy, the upper part of the melted mass
containing not more than 1.2 per cent. of lead.
Its separation from cadmium and arsenicum is commonly effected
ZINC. 33 1
during its preparation. These metals being more volatile than zinc
distil over first, and burn at the mouth of the tube with a brown
flame (brown blaze). The distillation of the pure zinc is determined by
the flame assuming a bluish-white color (blue blaze).
The pure metal may be prepared by igniting pure zincic carbonate,
and distilling the oxide formed with sugar charcoal.
Properties.-(a.) Physical. A light, hard, bluish-white crystalline
metal. It melts at 773°F. (41.2°C.), boils at 1,904°F. (1,040°C.), and
volatilizes at a red heat. At ordinary temperatures it is brittle ; between
212° and 302°F. (100° and 150° C.) it is both ductile and malleable,
whilst at 410°F. (210°C.) it again becomes brittle.
(3.) Chemical. Zinc burns in air with a greenish-white flame, zincic
oxide (ZnO) “nil album,” or philosopher’s wool being formed. The
metal rapidly tarnishes in moist air, the zincic oxide formed protecting
the metal underneath from further change. Cold water has no action
upon it, but the metal decomposes steam (Zn-H H2O=ZnO--H2). The
haloid elements, in the presence of moisture, act freely upon it. All
the acids attack it at ordinary temperatures. Solutions of the caustio
alkalies act readily upon it, evolving hydrogen, zincic oxide, which
is soluble in the alkaline solution, being formed (Zn-i-2KHO=
ZnO, K20+ H2). - -
Zinc is a powerful base; placed in many metallic solutions, it pre-
cipitates the metals, and in their stead is itself dissolved.
Hydrogen is commonly prepared by the action of dilute sulphuric
acid on zinc. If pure zinc be used for this purpose, the evolution of
hydrogen soon ceases, from the metal becoming covered with hydrogen
globules. If a piece of copper be now introduced into the mixture,
the copper (which is electro-negative towards the zinc) attracts the
electro-positive hydrogen, and thus effects a continuous liberation of
the gas.
Uses.—-Zinc is employed in building operations, as a substitute for
lead, its advantage being its comparative lightness. Although not
malleable at common temperature, it is perfectly malleable at 212°F.
(100°C.). Galvanized iron consists of iron coated with zinc, whereby
we obtain the strength of the iron, which is much greater than that
of zinc, together with the preservative action of the zinc, any ZnO
formed, itself acting as a protective varnish. It is prepared by dip-
ping clean iron into melted zinc covered with sal-ammoniac. By this
means the surface of the melted zinc is kept free from oxidation, zinc
oxide being soluble in NH4Cl. If this were not done the zincic oxide
adhering to the iron plate in the act of dipping would prevent its
becoming uniformly coated. Zinc forms an alloy with iron and
Copper (brass), which alloy, with nickel, constitutes German silver.
332
HANDBOOK OF MODERN CHEMISTRY.
Compounds of Zinc,

§ 3 ; º Specifi = º Or
Formula Formula ### ~ pecinc nu per
SALTS. (Common). (Constitutional). |#### Gravity of cent. of
5 § 5 #| Crystal. Anhydrous
== #3 Salt.
1. Zincic oxide. . . . . . ZnO ZnO 81 5:612 Zn = 80-24
2. , hydrated oxide.. ZnH.0, ZnHo, 99 Zn = 65-65
3. , chloride . . . . ZnCl, ZnCl, 136 2.753 |Zn = 47.79
4. , sulphide º ZnS ZnS 97 4 - 1 Zn == 67.01
5 sulphate (white w/ Anhyd. 3-681|, t;
” “j”. ZnS0,7H,0|SOHo,Zno",6OH, 161 } Č. .2n = 40.87
6. , carbonate . . ZnCO, COZno" 125 4'4 ZnO= 64-8
(1.) Zincic Oxide (ZnO=81) is prepared by burning zinc in air.
It is employed as a pigment (zinc-white) in the place of white lead,
its advantage being that it is not blackened by sulphuretted hydrogen,
and that its use does not affect the health of workpeople; whilst its
disadvantage is, that it more easily peels off on account of its not com-
bining chemically like oxide of lead with the oil. When heated the
White oxide turns yellow, but it becomes white again as it cools. It
is soluble in acids.
(2.) The Hydrated Oxide (ZnH2O2) is obtained by acting on
solutions of zinc salts with potassic hydrate (ZnSO,--2KHO
=ZnH2O2+ K2SO4), the precipitate being soluble in excess of the
precipitant.
(3.) Zincic Chloride (ZnCl2) is prepared either by dissolving zinc
in hydrochloric acid, or by heating the metal in chlorine. By evapo-
rating the solution, the chloride may be obtained as a white, deli-
quescent, fusible, corrosive solid. It is freely soluble in water and in
alcohol. It absorbs ammonia gas freely. It distils at a red heat. It
forms, with zincic oxide, a number of oxy-chlorides.
The solution (known as Burnett's Disinfecting Fluid) is a powerful
antiseptic and deodorizer, from its capability of absorbing the offensive
products of putrefaction. With the alkaline chlorides it forms double
salts, the zincic ammonic chloride (2H4NCl,ZnCl2) being used as a flux
in soldering, to remove the film of oxide from the surface of metals,
such as zinc, iron or copper.
(4.) Zincic Sulphide (ZnS=97) occurs native as blende, either
in masses, or in dark-colored crystals (rhombic dodecahedra). It
may be obtained as a white hydrated sulphide by the action of hydric-
ammonic sulphide on a solution of a zinc salt.
(5.) Zincic Sulphate (white vitriol, ZnSO,7H2O).
Preparation.—By roasting zincic sulphide at a low temperature. [If
roasted at a high temperature an oxide would be formed.] The mass is
then dissolved in water and crystallised. It is also found as a residue
in the common process of preparing hydrogen.
COBALT. 333
Properties.—A white, crystalline (four-sided prisms), efflorescent salt,
soluble in water (1 in 2:5 aq. at 60° F., and 1 in 1 at 212°F.). When
heated it melts in its own water of crystallisation. At 212°F. it gives
up 6H,0, and at 400°F. it becomes anhydrous. With potassic and
ammonic sulphates it forms double salts, such as Zn}{2(SO4)2,6EI2O,
these salts being isomorphous with the corresponding magnesium salts.
White vitriol is used in calico printing, and in medicine as an emetic.
(6.) Zincic Carbonate (ZnCO,-125) is found native as calamine,
so called from its tendency to form reed-like masses. The body
termed “electric calamine * is a silicate.
When a soluble carbonate is added to a solution of a zinc salt, a
hydrated zincic oxycarbonate is formed (8/n9,3CO2,6H2O), which is
soluble in ammonic carbonate, but not in the carbonates of soda or
potash.
Tests.--(See ANALYTICAL TABLEs.)
COBALT (Co").
Atomic weight, 59. Specific gravity, 8-95. Atomicily dyad, as in cobaltous
compounds (Co"O; Co"SO4), and tetrad (although apparently triad)
ſ CoECls
|
l Co-Cla
History.—Since the sixteenth century, roasted cobalt ores have
been used for producing a blue glass. The metal was discovered by
Brandt (1733).
Natural History.—It is never met with in a free state in nature,
except in meteoric iron. It occurs as an arsenide as “tin white cobalt.”
(CoAs,), and as an arsenio-sulphide in cobalt glance (CoAsS). Its ores
commonly contain nickel, copper, iron, manganese, etc.
Preparation.—By heating cobaltic oxalate (CoC.O.).
Properties.—(a.) Physical. A white, hard metal, ductile and
magnetic. It is very infusible, and possesses great tenacity.
(6.) Chemical. —It oxidises by exposure to air. The mineral acids
act on it freely. -
(1.) Cobaltous Oxide.—Protoxide of Cobalt (Co"O).
Preparation.—The hydrate (CoH2O2) is formed by precipitating
cobaltous sulphate with sodic carbonate. If the precipitate be ignited,
it leaves cobaltous oxide (CoO).
Properties.—A brown colored body, becoming the black cobaltic
oxide (Co3O4) when first heated, but is reconverted into cobaltous
oxide by a greater heat. It is soluble in acids, the solution being
blue when concentrated, and pink when dilute. It is used for paint-
ing on porcelain. “ Thenard's blue” is a compound of cobalt with
alumina. “Zaffre’ is a roasted mixture of cobalt ore and sand.
“Rinman's green '' is a compound of the oxides of cobalt and zinc.
“Smalt ’’ is powdered glass colored by oxide of cobalt (see page 335).
=CO2Cl6.
in cobaltic compounds
334
HANDBOOK OF MODERN CHEMISTRY.
Compounds of Cobalt.
H , | s 3
cºś 3–5 ||—|
SAILTS General Constitutional T º, 3 E-3 § Co
e Formula. Formula. 33 |#. EF3 per cent.
C 2- 3 -º dº p
3% ºf
1. Cobaltous oxide (protoxide) COO CO ''() 75 78-66
2. Hydrated cobaltous oxide.. CoEI,0, CoEIo, 93 63'44
COO
3. Cobaltic oxide (sesquioxide) Co,03 | O 166 71.08
COO
4. Cobaltoso-cobaltic oxide . . Co0,00,0, | §Coo" 241 73-44
5. Cobaltous chloride Co"Cl, CoCl, 130 45° 38
6. Cobaltic chloride Co.,Cls } §: 331 35' 64
7. protosulphide CoS Čos" 91 64-83
8. Sulphides sesquisulphide Co., Sa
9. disulphide CoS, CoS, 123 -
10. Cobaltous sulphate Co"SO,7H,0 | SOHo,Coo",60H, 155 || 3:531 º:
11. Cobaltous nitrate . . Co2NO,6EI,0 | §§Coo"GOH, 183 1-83 32-24
5000,200,4BI,0 2
12. Cobaltous carbonates. . 4000,200,5H,0
( 3CoCO3,2PI,0
(3) Cobaltic Oxide, or sesquioride of cobalt (Co.,03).
Preparation.—(1.) As a hydrate (Co3O3, 3}{2O). By passing chlorine
through water in which hydrated cobaltous oxide is suspended
(3CoH.O. + Cl2= Cog H606 + CoCl2).
(2.) Anhydrous.-By igniting the hydrate at a gentle heat.
Properties.—A black, insoluble substance.
it becomes (CoO,Cog03).
gradually becoming salts of the protoxide.
(5.) Cobaltous Chloride (CoCl2).
Preparation.—(1.) By passing chlorine over the metal.
At a high temperature
It is a feeble base, the acid solutions
(2.) By dissolving the oxide in hydrochloric acid.
Properties.—The anhydrous cobaltous chloride is blue, and the
hydrate CoCl2,6H.0 is red. The “blue sympathetic ink" is a dilute
solution of this salt, the change of color depending on different degrees
of hydration. The addition of traces of zinc, iron or copper chlorides,
varies the tints produced.
(6.) Cobaltic Chloride (Co.Clo) is prepared by saturating CoCl2
with chlorine.
(11.) Cobaltous Nitrate (Co2NO3,6H2O).
Preparation.—By dissolving the oxide in nitric acid. -
Properties.—It is used as a blow-pipe reagent. When a zinc com-
TNICKEL, 335
pound is moistened with it and heated it turns green, a magnesium
compound turning pink, and an aluminium compound blue.
By treating cobaltous salts protected from the air with ammonia,
crystallizable rose-coloured compounds (ammonio-cobaltous salts) are
formed, as, e.g., (CoCl2,6NH3,3B.O). If this mixture be exposed to
the air the solution absorbs oxygen, and brown compounds (peroa'idized
ammonio-cobalt salts) of a very complex nature result, consisting of
ammonia and various oxides of cobalt.
Tests for Cobalt.—(See ANALYTICAL TABLEs.)
NICKEL (Ni").
Atomic weight, 59. Specific gravity, 8'7. Atomicity dyad, as in nickelous
compounds (NiCl2), and tetrad (although apparently triad) in nickelic
compounds, as Ni2O3.
History.—Discovered by Cronstedt (1751).
Natural History.—It is found as an arsenide, as kupfernickel
(NiAs) and arsenical nickel (NiAsa); and also as an arsenio-sulphide
as grey nickel ore or nickel glance (NiAs2, NiS). It occurs in
meteorites. It is always associated in nature with cobalt.
Preparation.—(1.) By roasting cobalt ore, an oxide of cobalt is
formed. When this is fused with quartz and potassic silicate, it forms
a blue glass (smalt), consisting of a mixture of the silicates of cobalt
and potash. The fused metallic residue which collects at the bottom
of the crucible, constitutes “speiss,” a mixture of the sulphides and
arsenides of nickel, iron, and copper. From this residue metallic
nickel is obtained.
(2.) By igniting the oxalate.
Properties.-(a.) Physical. A hard, silvery-white metal, ductile
and malleable, more fusible but of greater tenacity than iron. It is
somewhat magnetic, a property it loses when heated to 626°F.
(330°C.). Specific gravity, 8:8.
(6.) Chemical. It oxidizes when heated in air. Nitric acid dis-
solves it readily, and hydrochloric and dilute sulphuric acids slowly,
hydrogen being evolved. It is acted on by chlorine and bromine.
Uses.—For rendering brass (an alloy of copper and zinc) white
(German silver, packſong, tutenag).
(1, 2.) Nickelous Oxide.—Protocide of Nickel (NiO).
Preparation.—(1.) (Anhydrous). By the ignition of the nitrate or car-
bonate. -
(2.) As a hydrate (NiII.O.). By adding potassic hydrate to a solu-
tion of nickel salts.
Properties.—The hydrate, as well as its solution in acids, is green.
It is soluble in ammonia and in ammonic chloride, but is insoluble in
sodic and potassic hydrates.
336
FIANDBOOK OF MODERN CHEMISTRY.
Compounds of Nickel.


- º # 3 &
Ordinary Constitutional | #3p | #.5 -
SALTS. Formula. Formula. º #3 Ni
3* | #5
1. Nickelous oxide (protoxide) NiO NiO 75 5.75 78-67
2. Hydrated nickelous oxide.. NiH,0, NiHo, 93 63'44
NiO
3. Sesquioxide of nickel Ni,0s | O 166 71.08
NiO
4. Nickelous chloride tº e NiCl, NiCl, 130 45° 38
5. subsulphide .. Ni,S 'Ni',S 150
6. | Sulphides | protosulphide NiS NiS 91 64'83
7. disulphide NiS, NiiyS, 123
8. Nickelous sulphate NiSO4,7H,0 SOHo, Nio",6H,0|| 155 || 2:037| 38-06
9. Nickelous nitrate . Ni2Noºn,0|| §§Nio",6H,0| 183 32'24
10. Nickelous carbonate . . NiCO, doNio” 119 49.57
(3.) The Sesquioxide of Nickel (Ni2O3) forms no salts with acids.
It is decomposed by heat.
(6.) Protosulphide of Nickel (NiS) occurs native as “millerite ”
> y
or “capillary pyrites,
of an alkaline sulphide on a salt of nickel.
(8.) Nickelous Sulphate (NiSO4,7H2O).
Preparation.—By dissolving the metal, or NiO, or NiCOs, in sul-
phuric acid.
and is precipitated as a hydrate by the action
Properties.—A green crystalline salt (rhombic prisms), soluble in
water (1 in 3 aq. at 60°F), and insoluble in alcohol.
It forms double
salts with potassic and ammonic sulphates, which are isomorphous
with the corresponding magnesium salts—
(Niso, |
Atomic weight, 240,
K2SO,
(NH4)2SO,
Tests, (See ANALYTICAL TABLEs).
6H,0)
URANIUM (U).
UCl4), and hea'ad in Uranic compounds (as UOs).
History.—Discovered by Klaproth.
Natural History.—It occurs as an oride (pitchblende, UO, U20s
with Cu, Pb, Fe, As, etc.), and as a phosphate (uranite and chalcolite).
Preparation,-By decomposing the chloride with metallic sodium
OT potassium.
Atomicity, tetrad in Uranous compounds (as UO2;
Properties.—A greyish metal. It is not oxidized by air or by water
at common temperatures, but burns in air when heated. It is soluble
INDIUM. 337
*-
in sulphuric and in hydrochloric acids. It combines energetically with
sulphur and chlorine.
Uses.—In enamel painting, and for coloring glass for optical and
electrical purposes.
Compounds of Uranium.

o P.
Ordinar Constitutional | Molecular | ##
SALTS. }. Formula. Weight. #. 3
apº
1. Uranous oxide (protoxide) U0, TJO 256
2. Uranic oxide (sesquioxide)
or Uranyl oxide . . . . UO, UO, 288
3. suboxide . . U.0 U20, 528
4. | Other oxides | black oxide U.o. to
5. green oxide 3 S-'8 7-31
6. Uranous chloride (proto-
chloride) . . . . . . UCl,
7. Uranium oxychlorid * & U0,0],
8. Uranic nitrate . . . . . . UO2(NO2),6H,0
Tranium forms two classes of compounds — uranous and wranic
salts. Uranic oxide can act both as base and acid, forming in the
latter case the compounds called uranates, which have the general
composition M'30,2UOs. -
REACTIONS OF URANIUM CoMPOUNDS.
To the borax bead uranium imparts a yellow color in the oxidizing
flame, and a green color in the reducing flame.
Solution.—(A.) Uranous Compounds (generally green).
(1.) Alkalies, a gelatinous brown ppt. (UO2, H2O), becoming, after a
time yellow (UO3). -
(2.) Ammonic Sulphide, a black ppt. (uranous sulphide).
(B.) Uranic Compounds (yellow).
(1.) Ammonia, a yellow ppt. of ammonic uranate.
(2.) Ammonic Sulphide, a yellowish brown ppt.
To detect uranium in a mineral, dissolve the mineral in nitric acid,
dilute with water, boil with an excess of sodic carbonate, filter, and
precipitate the U3O3 with potassic hydrate.
INDIUM (In").
Atomic weight, 113-4. Specific gravity, 7-4. Fuses at 349°F. (176° C.).
Atomicity (""), triad as in InCls.
History.—Discovered by Reich and Richter in the Freiberg zinc
blende (1863) by its peculiar spectrum, viz., the occurrence of two
bright lines in the blue and indigo.
Natural History.—Indium is found in zinc blende and in other
zinc ores, and also in the flue dust of zinc furnaces.
Extraction.—The blende is first acted upon with a quantity of
dilute sulphuric acid, insufficient to effect its complete solution. The
Z
338 HANDBOOK OF MODERN CHEMISTRY. ,
undissolved residue is then dissolved in nitric acid, and the lead,
and cadmium precipitated from the solution by sulphuretted hy-
drogen. After filtering and boiling (to expel the H2S) baric car-
bonate is added to the filtrate, when the indic oxide (In 203) is preci-
pitated. This is dissolved in hydrochloric acid, and an excess of am-
monia added. The White hydrated oxide (Ing|Hø06) is thus thrown
down, and may be reduced by heating in a stream of hydrogen.
Properties.—Indium is a white or lead-like metal, non-crystalline,
Soft, and ductile. It is less volatile than zinc or cadmium. It burns at
a red heat with a violet flame, forming the yellow indic owide (In,0),
but it does not oxidize readily below a red heat. It dissolves in
acids.
Sulphuretted hydrogen precipitates in neutral solutions, or in solu-
tions containing acetic acid, a yellow-coloured sulphide (IngS3). The
alkalies and their carbonates give white precipitates.
Compounds of Indium.

# +5 # # 5.
Common Constitutional #3 ##
SALTS, Formula. Formula. 3:##, #. 3
o tº--~!
: > = | 73
<d
In O
Indic oxide (yellow oxide) In,03 O 274'8
In O
º º In Cl -
Indic chloride . . . . . . In 2016 }#}. 439'8
[Bromide and iodide
analogous to chloride).
In S
Indic sulphide . . . . . . In,Sa | S 322.8
In S
Indic nitrate . . . . . . In,6NO,9H,0. 598-8
Indic sulphate . . . . . . In (SO.),9B.0 |S,0In,0",90H, 514-8
Indic sulphite . . . . . . 2In,0s,3S0,8H,0 741-6
Reactions of Indium Compounds.
1. The metal is precipitated from the solution of a salt, by the
action of metallic zinc or cadmium. The peculiar spectrum of indium
has been referred to. -
2. Boil with an excess of acid sodic sulphite; a precipitate is formed
of sulphite of indium (2Ing04,380,8 H2O).
3. Sulphuretted hydrogen; a yellow precipitate (IngSs) in neutral
solutions, or in solutions containing acetic acid.
4. Alkaline hydrates and carbonates ; a white precipitate (IngHé06),
soluble in excess of ammonic carbonate, or of the fixed alkaline hy-
drates. -
5. Heated on charcoal, a ductile metallic bead of the metal may be
obtained.
339
CHAPTER XV.
GROUP IV.—THE METALS OF THE EARTHS.
IRON AND CHROMIUM.
ALUMINIUM (Al” = 27-5)—GLUCINUM (G" = 9.5)—YTTRIUM (Y" = 61-7)—ERBIUM
(E” = 112-6) – CERIUM (Ce".= 92) — LANTHANUM (La" = 92) – DIDxMIUM
(Di" = 96)—THoRINUM (Th" = 238)—ZIRCONIUM (Zr" = 89-5).
IRoN and its Compounds—CHROMIUM and its Compounds.
ALUMINIUM (Al = 27-5).
Specific gravity, 2-6. Fuses at 842°F. (450° C.). Atomicity tetrad, and
also pseudo-triad.
History.--Discovered by Wöhler, 1828.
Natural History.—Next to silica, aluminium, as clay (silicate of
alumina), is the most abundant of minerals. It has been found in
certain cryptogamous plants, but practically it can scarcely be re-
garded as a constituent either of animals or vegetables.
Preparation.—(1.) By decomposing aluminic chloride (Al2Cl6)
with sodium or potassium (Wöhler).
(2.) By the electrolysis of the double chloride of sodium and alu-
minium (2NaCl, Al2Cl6).
(3.) (Commercial.) By heating bauxite (a mineral containing 60 per
cent. of Al2O3) with soda ash, whereby an aluminate of soda is pro-
duced (3Na2O, Al2O3). On adding HCl to the solution of this com-
pound, alumina is precipitated as a hydrate (Al2O3,3EI2O). This pre-
cipitate is now mixed with common salt and carbon, and chlorine
passed over the heated mixture, a sodic aluminic chloride distilling
over (2NaCl, Al2Cl6). This compound is then heated with metallic
sodium, when metallic aluminium and sodic chloride are formed.
Properties.—(a.) Physical. A white malleable ductile metal,
crystallizing in regular octahedra. It conducts electricity with about
one third the power of silver. It is a very light metal (2-5 Sp. Gr.),
remarkably sonorous, and slightly magnetic. It melts when heated,
but is not volatile.
(3.) Chemical. It does not oxidise readily either in steam or in
hot or cold air, it being the lightest metal known difficult of oxidation.
It burns in oxygen (forming Al2O3), and in the vapor of sulphur (forming
Al,Ss). Sulphuretted hydrogen is without action upon it; hence its
value for ornaments. Nitric acid does not attack it when cold, and
but very slightly even when boiling. Hydrochloric acid, cold or hot,
dissolves it freely (Ale--6HCl=Al2Cl6+3H3). Alkalies act energeti-
cally upon it, liberating hydrogen. It combines with carbon and with
340 HANDBOOK OF MODERN CHEMISTRY. '
silica. It forms alloys with silver, iron and copper (aluminium
bronze), but neither alloys itself with lead, nor forms an amalgam
with mercury.
Compounds of Aluminium.


- *- 2 rº -
F l F 1 5 : 5 # 3 Bº
OTDOlllla, OTDOllia, 3.5.5 3 ###| = Al,0, or
SALTS. (Common). (Constitutional.) #### #: P. Al percent.
===3% º
tº w - A10
1. Aluminic oxide
2. Aluminic chloride Al...Cl 'Al"Cl, 268 Al = 20°52
- wº ". -**2 G "Al"Cl, *
3. ,, bromide. Al, Brg }º. 535 Al = 10:28
4. , , iodide. . . Al...Is | º 817 Al = 6-73
3
5. 2 3 fluoride .
AlS -
6. 2 3 sulphide. Al,SA | 151 Al = 36'42
A1S
T
7. Trisodic aluminate Nagál,0s { #Nº. 289 Al = 19:03
“3
8. Aluminic sulphate. Al,3S0,,18H,0 S,0sA],0", 1801.I., 343 1.671 || Al,0– 30:02
ſ S0, Ko-
9. Potassic aluminic SO, - - e º * A wº
sulphate ...; K.,Al,4S0,24H,0 | gºal,04240H, 5172 1726|Al,0= 1991
SO, Ko–J
10. Aluminic phosphates Al,P,0s P,0,Al,Ov 245 Al,03– 42:04
11. 73 silicates. .
(1.) Aluminic Oxide,-Alumina (Al2O3). This is the only oxide
of aluminium. It occurs native as “corundum ” (the next hardest
body to diamond), as “emery,” as the “ruby’’ and “sapphire"
(colored with a chromium salt), as the “spinelle’’ (MgO, Al2O3), and
the “topaz” (a compound of alumina, silica, and aluminic fluoride).
Diaspore (Al2O3.H2O) and Gibbsite (Al2O3,3EI2O) are native hydrates.
Preparation.—(1.) (As a hydrate, Al2O3,3LI2O) By adding ammonia
to an alum solution.
(2.) (Anhydrous.) By the ignition of pure ammonia alum.
Properties.—The hydrate (Al.. EIGO6) when first precipitated is a bulky
transparent gelatinous precipitate, contracting as it dries to a
gummy hygroscopic mass This mass when ignited loses its water,
and absorbs a large quantity of heat, on account of which property it
is used for the purpose of filling the spaces between the iron plates of
fire-proof safes. Before being dried the hydrate is very soluble both
in hydrochloric acid and in potassic hydrate solutions; but after dry-
ing it is almost insoluble in either the one or the other. It fuses by
heat, forming a colorless transparent mass.
Alumina is capable of acting both as a base and as an acid. Thus,
ALUMINIUM. 341
º:
as a base it forms salts with acids, such as aluminic Sulphate, all of
which salts have an acid reaction, and are easily decomposed. As an
acid it combines with basic oxides, forming a class of salts known as
the aluminates. Thus the spinelle ruby is a magnesic aluminate
(MgO, Al2O3), gahnite a zincic aluminate (ZnO, Al2O3). A potassic
aluminate has also been obtained (K2O, Al2O3).
Alumina combines with silica to form clay.
Aluminic hydrate combines with certain organic coloring matters,
forming a class of pigments called “lakes.” Thus alum is used as a
mordant to fix coloring matters on calico.
(2.)—Aluminic Chloride,-(Al2Cl6). Specific gravity of vapor, 9:27.
Preparation.—(1.) By passing chlorine over a mixture of carbon and
alumina heated to redness (Al2O3 + Cs+ 3Cl2=Al2Cl6+3CO).
(2.) By heating clay in a mixture of hydrochloric acid gas and the
vapor of carbonic disulphide.
[NOTE.—Aluminic chloride cannot be prepared by dissolving Al2O3
in HCl and evaporating. A hydrate of aluminic chloride is formed
in solution (Al2Cl6,12H2O), but this on evaporation evolves HCl,
leaving Al2Os.]
Properties.—A yellow, crystalline, deliquescent body, emitting
fumes of HCl when exposed to the air. It is soluble in alcohol, and
dissolves with a hissing noise in water. It melts and sublimes when
heated. It combines with ammonia, with phosphoretted hydrogen,
and with sulphuretted hydrogen.
“Chloralum ” is an impure aluminic chloride.
(5.)—Aluminic Fluoride.—(Al2F6) is found native as cryolite
(6NaF,Al,F6), and as topaz 2(Al2O3,SiO2), Al2OssiR,).
(8.)—Aluminic Sulphate.—(Alg880, 18H2O) may be obtained by
dissolving alumina in sulphuric acid. It is prepared commercially
by heating-clay with sulphuric acid. The clear solution, after being
first freed from iron by potassic ferrocyanide, and afterwards eva-
porated to a syrup, is known to the dyers as “concentrated alum,”
or when reduced to the solid state as “cake alum.” The crystals
are exceedingly soluble.
(9.)—Potassic Aluminic Sulphate—Alum (K. Ala#SO,24H2O).
Natural History.—Found native in volcanic districts, produced by
the action of volcanic sulphuric acid on the aluminium compounds of
the rocks. -
Preparation.—(1.) (a.) “Alum shale,” a compound of aluminic
silicate, iron disulphide, and bituminous matters, is first roasted,
whereby one-half of the sulphur of the FeS2 becomes oxidized. Thus,
2FeS2 + 3O2 = 2FeS + 2SOs. **
Ferric disulphide + Oxygen = Ferrous sulphide + Sulphuric anhydride.
(6.) When water is added to the residue, the SOs becomes H2SO,
which immediately decomposes the aluminic silicate forming aluminic
sulphate.
342 HANDBOOK OF MODERN CHEMISTRY.
(y.) By exposure to air the ferrous sulphide becomes ferrous
sulphate.
(6.) When the mass is lixiviated, a solution results (called crude
alum liquor), containing alumina and ferrous sulphate, and also
probably some magnesic sulphate.
(e.) Part of the ferrous sulphate is now removed by crystallization.
(...) Potassic chloride (in the form of soap boilers' waste, or the
refuse of glass houses or of saltpetre refineries) is now added to the
solution, whereby any ferrous sulphate is decomposed, and a soluble
ferrous chloride, together with potassic sulphate, formed.
2E Cl + FeSO, - FeCl, + R2SO4.
Potassic chloride + Ferrous sulphate = Ferrous chloride + Potassic sulphate.
(m.) The potassic sulphate as soon as formed, combines with the
aluminic sulphate to form “potash alum,” which being sparingly
soluble in cold water is deposited from the solution as “alum meal"
or ‘‘ alum flour.” This is afterwards washed with cold water to re-
move adherent iron. It is subsequently crystallized.
Very frequently ammonic sulphate (from gas liquor) is used
instead of potassic chloride, in which case ammonia alum is formed,
(NH4)2Al4SO,24H2O.
If sodic sulphate be employed, soda alum is formed, Nagal. ASO,24H2O.
Thus we may obtain by the employment of different reagents a series
of alums, some of which we have tabulated as follows:–
Potash alum tº - - • * * ... R3Al34SO4,24]H.O.
Soda alum • e tº - tº º ... Nagal.,4SO,24EI.O.
Ammonia alum ... tº º º ... (HºN)2Al44SO,24H2O.
Iron alum tº e º tº ºr tº ... K2RecºSO1,24II,0.
Chrome alum ... tº ſº º ... K2Cr,4SO4, 24H2O.
Manganese alum... tº º º ... K.Mn24SO,24H2O.
Further, a silver-alum, a caesium-alum, and a thallium-alum may
be obtained.
(2.) By burning “alum stone.” The alum thus prepared is known
as “Roman alum.”
Properties.—Alum is a white, crystalline (octahedra) astringent-
tasted body, soluble in water (1 in 18 aq., at 60°F., and 1 in l at 212°
F.). Its solution has an acid reaction, and dissolves iron and zinc
with the evolution of hydrogen. When alum is first heated, it melts
in its own water of crystallization. At 392°F. (200°C.) the water
evaporates, and the residue swells up to a white infusible and insoluble
mass called burnt alum (K2Al44SO4). By ignition, some of the acid of
this alum may be expelled. It is but little affected by exposure to
air. Homberg's pyrophorus is a mixture of alum and sugar, carbonized
out of contact with air.
Alum is largely used in dyeing, in the preparation of skins, and in
medicine.
CLAY. 343
*-
We have in the alums a marked illustration of isomorphism, that is
of bodies of different chemical composition, crystallizing in the same
form. Potash alum forms white octahedra; chrome alum, dark red
octahedra ; iron alum, violet octahedra, etc.
(10.) Aluminic Phosphates are found as natural minerals, as, e.g.,
turquoise, which is a hydrated phosphate, colored with copper and
iron (2A),0s, P.O.,5H2O); wavellite, 3(4Al2O3,3P,0s, 18H2O), Alg|F6;
lazulite (a double phosphate, colored with phosphate of iron), etc.
(11.) Aluminic Silicates.—These are both numerous and compli-
cated. Their complication arises from the frequent replacement of
Al2O, by the isomorphous body, Fe2O3, other metals present being
similarly exchanged for their isomorphous representatives.
A few of these silicates are stated in the following table :-
Garnet (Ca, Al,Mg,Fe and Mn).. 3(CaMgFeMn)0(AIFe)2033SiO2:
Chlorite (Ál,Mg, etc.) . . . . . 4(MgFe)0, AlFe),0s,2SiO2,3H2O.
Basalt (Ca,Mg) . . . . . . . . 4(CaMgFe)05SiO.
Cyanite, Diothene . . . . . . Al2O3, SiO2, ..
Analcime. (Na,Al) . . . . . . Na.0, Al2O3:4SiO2,2B40.
Zeolites | Stilbite (Ca,Al) . . . . . . . . CaO, Al2O3,6SiO2,6H2O.
Prehnite (Ca,Al) . . . . . . . . 2Ca(), Al,03,3SiO2H2O.
Potash * Felspar (orthocluse) K,
Sodium 3 y (albite) Na. s r *
Felspar Lithium 3 y (petalite) i.” 0, Al,0a,6SiO2.
Calcium ,, (Labradorite) Ca
Uniaxial (Mg and Al) [4(MgRFe)0,(Al Fe),03,4SiO.].
. . , \ K in excess K Y-T- * ** - A.--
l Biaxial | Li in excess (Lepidolite) |(}, Fe) 0.8(AFe),0,6sio,
Slate is an aluminic silicate of varied composition. Roofing slate is
an argillaceous rock; mica slate contains mica, and hornblende slate,
hornblende. Granite and gneiss consist of quartz, felspar and mica;
porphyry is a felspar, so also is basalt, the latter containing crystals of
augite. Dolerite, greenstone, diorite, trachyte, fuller's earth, pumice stone,
which, in a melted state, is called volcanic glass, or obsidian, are also
aluminic silicates.
Iapis lazuli or native ultramarine consists of a silicate of alumina
mixed with lime, soda, sulphuric acid, sulphur and iron. The cause
of its blue color is not well understood. Artificial ultramarine is pre-
pared by heating together a mixture of 100 parts of kaolin, 100
of sodic carbonate, 160 of sulphur, and 12 of carbon. A green body
results, which, on being further roasted with fresh sulphur, forms a
brilliant blue mass. Ultramarine is bleached by acids and by chlo-
rine. It is often used as the coloring matter for blue paper, which
consequently becomes white when dipped in an acid.
Mica
Clay.
Formation.—The disintegration of granite rocks which consist of
quartz, feldspar and mica, is both mechanical and chemical. By the
action of air and by the expansion of the water in the rock during
* Pericline is an admixture of potash and soda felspar,
344 HANDBOOK OF MODERN CHEMISTRY.
congelation, it is gradually broken down. From this debris, water
containing carbonic acid dissolves the potash, leaving quartz and sili-
cate of alumina. These bodies are afterwards mechanically separated
by water owing to their different gravities, the silicate of alumina
being comparatively light. This, when deposited, constitutes clay
(Al2O3,2SiO2,2H2O).
Composition of clay.—This varies considerably, as the following
diagram shows:–

Washed Kaolin. Stour- º
^– bridge Pipe Sandy Blue Brick
~. TY | Fire Clay. Clay. Clay. Clay.
Chinese. S.Yrieix. Cornish. Clay.
Silica. 50-5 48-37 46'32 64-10 53-66 66.68 46' 38 49-44
Alumina ... 33.7 34°95 39.74 23: 15 32" ()0 26' 08. 38'04 34-26
Qxide of iron. . 1.8 1' 26 0-27 1-85 1:35 1 ''26 1'04 7-74
Lime º - *- 0 °36 -- 0.40 0.84 1 - 20 1'48
* d 0-8 trace 0-44 0.95 trace trace trace 5'14
Otash or soda. 1 9 2:40 - iº - -
Water 11-2 12.62 } 12-67 || 10-00 | 12 08 5-14 || 13:57 | 1.94
99.9 99-60 99.80 | 100'05 99°49 || 100'00 100-23 100.00
From MILLER.
Loam is a clay containing ferric oxide, whilst marl is a clay con-
taining carbonate of lime. Umber, red-bole, ochre and sienna, are also
clays containing various iron and manganese oxides.
Properties.—A tenacious mass, insoluble in, but capable of diffu-
sion through water, very plastic, but shrinking when dried. It has a
characteristic odor, and possesses great absorbent powers. It conse-
quently retains the ammonia from manure when placed on the earth,
storing it up for the vital functions of the plant. It also purifies
water impregnated with organic impurities when passed through
it. (Way.)
Clay is decomposed by sulphuric acid (see Preparation of Alum),
but is very slowly acted upon either by hydrochloric or by nitric acids.
After clay has been ignited, no acid, except hydrofluoric acid, has the
least action upon it. It is slightly soluble in a solution of potassic
hydrate, but becomes very soluble in water after its fusion with
potassic hydrate.
Porcelain and Pottery.
Clay is employed in the manufacture of all kinds of pottery.
Although plastic, it shrinks considerably when baked. To prevent
this shrinking, sand, chalk, or bone-ash is mixed with the clay, but
inasmuch as this has a tendency to disintegrate it, it is necessary
afterwards to glaze it with some substance capable of vitrification, in
order to cement the whole together and form it into a compact mass.
This is the whole principle of the manufacture of pottery.
PORCELAIN AND POTTERY. 345
(1.) Bricks, coarse tiles, pipes, etc., are made from common clay,
of which there are three kinds, (a.) marly or chalky clay *, used for
pale bricks; (6.) potter's clay, used for bricks and tiles; (y.) fire clay,
which is nearly free from lime.
Process.-The clay is dug up in the autumn, and exposed to the air
(weathered). The stones present in the clay are either crushed in a
mill or are removed by puddling or other means. This done, the clay
is mixed with sand and well kneaded. The mass is then ready to be
fashioned into shape by hand or machinery, the articles so formed
being first dried in the air, afterwards fired in kilns, and finally
glazed with a mixture of clay and litharge, or iron Scarf, etc.
The red color of bricks and tiles is due to the carbonate of iron
present in common clay becoming converted into peroxide (Fe2O3) by
the action of atmospheric oxygen.
(2.) Common earthenware.—One of three kinds of clay is employed
in its manufacture, viz., (a) Dorsetshire clay, (3) Devonshire clay (blue
clay), or (y) pipe clay.
The clay is first of all cleansed by machinery, and reduced to a
state of pap. It is then run through fine sieves. To prevent after-
contraction and unequal drying, it is mixed with a pap of ground
flints, the mixture being called “slip ’’ (1 part of flints to 5 parts of
clay). This flint-pap is prepared by subjecting flints from the chalk
to an intense heat, suddenly quenching them with water, and finally
grinding them into a pap. The mixed mass of sand and clay is now
cut into square blocks, and kept for Some months in a damp place.
In this way any organic matter present becomes oxidised, thus re-
ducing the sulphates to sulphides. When required, the “slip” is
kneaded by beating it on a board, so as to effect its perfect incorpora-
tion, and the removal of all air bubbles. This kneading process in
England is effected both by machinery and by hand labor. In France
it is done with mallets; in Egypt by the treading of men; and in
China by the treading of cattle. The article, after being roughly
fashioned is partially dried, at a temperature varying from 80° to 90°
F., and then further finished,—handles attached, etc. It is afterwards
baked in kilns, placed in cases called “Saggars,” when it becomes con-
verted into a porous earthenware called “biscuit.” The freshly-struck
pattern, printed on wet soaped paper with a mixture of some metallic
oxide and boiled oil, is now placed on the “biscuit,” and well rubbed
with a flannel rubber, so that the “biscuit” may completely remove
the impression from the paper. As soon as the design is absorbed by
the “biscuit,” the paper is removed by wetting with a sponge.
The “biscuit” is now dipped into a weak alkaline lye, in order to
saponify the oil, and is afterwards glazed with some fusible material,
such as a mixture of white lead, Cornish stone, ground flints, ground
* A marl is a clay containing a considerable quantity of calcic carbonate. If the
alumina be in excess it is an aluminous marl, if the chalk, a calcareous marl.
346 HANDBOOK OF MODERN CHEMISTRY.
glass, chalk felspar, silicate of alumina and potash, and borax. It is
finally baked or “fired" in the kiln, whereby the glaze is fused. -
The colors on the earthenware are produced by various metallic
oxides (see page 307), which form a colored glass with the glaze, whilst
the metallic lustres are produced by gold, platinum, copper, brass, etc.
(3.) Porcelain is a finer variety of pottery It is of two kinds; (a.)
The hard porcelain, such as is made at Sevres, Dresden, etc., is manu-
factured from kaolin, a very pure white clay, obtained from China,
Cornwall, S. Yrieix near Limoges, etc., and from china stone, which
consists of the silicates of alumina, potash and lime. The glaze used
is a mixture of felspar and quartz, suspended in water in which the
article is dipped. (3.) The soft variety of porcelain as made in
England contains bone earth.
The details of its manufacture are in all respects similar to that
already described.
Wedgwood is a fine description of stoneware.
Salt Glazing, which is largely used in the preparation of stoneware,
etc., is effected by throwing common salt into the furnace containing
the heated articles, previously dipped into a mixture of sand and
water. The salt volatilizes, and is decomposed by the sand on the
hot surface of the ware. A fusible impervious silicate is thus formed
as a glaze, hydrochloric acid escaping as vapor with the excess of salt
(H2O+2NaCl-H SiO2=2|HCl·H Na2O, SiO2).
Tests.-(See ANALYTICAL TABLES.)
GLUCINUMI. Beryllium (G'=9-5. Specific gravity 2:1).
History and Preparations.—Glucinum is found combined with
silica and alumina in the emerald (3GO, Al2O3,6SiO2), also in the beryl,
colored with chromium, and in the chryso-beryl (GO, Al2O3). The metal
may be prepared by a similar process to that described in preparing
aluminium. &
Properties, LA white, fusible, malleable metal. It does not burn
in air, oxygen, or in sulphur, but it combines readily with chlorine,
iodine, and silicon. It does not decompose steam. It is soluble in
dilute sulphuric and in hydrochloric acids, but is insoluble in nitric
acid. It is dissolved with the evolution of hydrogen by a solution of
KHO. It forms one oxide (GO). Its salts are colorless, sweet
(y\vkūc), and acid to litmus.
YTTRIUM (Y=617); ERBIUM (Er-112-6).
These are rare metals found in gadolinite. They form the oxides
yttria (YO) and erbia (Ero–128-6).
CERIUM (Ce=92).
Cerium is found in cerite (a silicate of cerium) and in brown
apatite. Its oxalate is useful for the relief of the sickness of
pregnancy.
iron. 347
LANTHANUM (La-902).
Lanthanum is also found in cerite. It forms one oxide (LaC),
which is buff-colored.
DIDYMIUM (Di-96).
Didymium is also found in cerite. It forms one oxide (DiO).
THORINUM (Th–231.5. Specific gravity 7-8).
Thorinum was discovered by Berzelius (1829) in the mineral
thorite. It is prepared by reducing the chloride with potassium.
It is a grey powder, incapable of decomposing water, but burning in
air, forming thorina (ThC). Specific gravity=9:4). It is not acted
on by the caustic alkalies, but is soluble in most acids.
ZIRCONIUM (Zr-89-6. Specific gravity 4:15).
Zirconium is found in nature as an oxide (Zirconia, ZrO2), and also
combined with silicic acid in zircon and in hyacinth (ZrO2, SiO2).
Properties.—Like silicium, to which it is closely allied, it exists in
three states—(1.) an amorphous state, which burns when heated in
the air below redness, forming zirconia (ZrO2); (2.) a crystalline state,
which requires the oxy-hydrogen heat to fire it; and (3.) the graphoidal
state.
Zirconium has never been fused. It decomposes water slowly at
the boiling point. It is acted on by hydrofluoric acid with the evolu-
tion of hydrogen, and also by aqua regia. It is insoluble in dilute
sulphuric or hydrochloric acids.
It forms one oxide, zirconia (ZrO2=121-5. Specific gravity 4:5)
which, unlike alumina, is insoluble in the caustic alkalies. It is
soluble in potassic carbonate. It acts both as a base and as an acid,
in the latter case forming the compounds called zirconates (as Na,
ZrO3).
Zirconic chloride (ZrOly-231-5) and zirconic fluoride (ZrF.) have
been prepared.
IRON (Fe"=56).
Atomic weight, 56. Specific gravity, 7-8. Atomicity dyad ("), as in
Ferrous salts (Fe"Cle; Fe"SO.), and tetrad (iv) in Ferric salts, although
- FeCls
apparently a triad, thus, =FeaCl6.
feCls
Natural History. —Found native in meteorites, together with
Ni, Co, Mn, Cu, etc., and is also found accompanying platinum ores.
In combination it occurs in great abundance in numerous ores, as
follows :-
348 EIANDBOOK OF MODERN CHEMISTRY.
Iron Ores.
-- 4 Specific
Common Names—Locality. Formula. ë.
and Composition.
of Ore.
Magnetic iron ore ; Loadstone; Iron-sand -
(India) . . - ſº 4 º' $ 4, ! Fe,0, 5-09
Red haematite (Cornwall). (Red ochre con- 5-0
tains clay) * * a tº & © tº a Fe, O ſ {)
Specular iron; Fer oligiste; Iron glance €303 5.2
(Elba, Russia, Sweden) |
Brown haematite; Pea iron ore ; yellow -
ochre (France).. * * ſº tº y gº a 2Fe,0,3H,0 3-9
Spathic iron (Saxony) is tº tº e tº º FeCO, 3-8
Clay ironstone (Great Britain, America) . . FeCO2, with clay. 2-7 to 3° 47
FeCO2, with bituminous
| matters (20 to 30 per
cent.)
Iron pyrites .. * * * - - e. * { FeS,
Siliceous ironstone (Northampton) ſº e Fe,0, and FeCO,
| 2Fe03,3}{20, and a
ferric phosphate.
Black-band (Scotland)
Bog iron ore..
The following table from Bloxam, compiled from analyses given
in Percy (“On Iron and Steel,”) shows the composition of most of the
English iron ores:—

Oxide of Phosphoric | Bisulphide
Iron. º º
Manganese. acid. of iron.
In 100 parts.
Max. Min. Max. | Min. Max. | Min. | Max. | Min.
|
#

Clay iron stone from
coal measures . . . 43-30 | 20.95 || 3:30 || 0:46 l'42 || 0-07 || 1:21 tº º 77
Clay iron stone from
the Lias . . . . . 49-17 | 17-34 || 1:30 tº e 5-05 tº e 1 - 60 tº e 12
Brown haematite . . 63-04 || 1 l'98 || 1:60 trace || 3:17 * * 0-30 | . . 23
Red haematite . . . 69' 10 47.47 || 1 13 | trace trace trace || 0-06 2 º' 5
Spathic ore . . . . 49-78 13.98 || 12-64 1.93 || 0:22 tº gº 0 11 tº º 6
Magnetic ore. . . . 57:01 0° 14 0 - 10 0-07 l
Preparation.—In England iron is usually manufactured from
clay iron-stone.
(a.) The broken ore is first roasted or calcined, either in kilns, like lime-
kilns, or in heaps exposed to the open air, whereby water, carbonic
anhydride, and some sulphur is expelled, and an impure ferric oxide
obtained. -
(3.) This calcined ore is now smelted in the blast furnace.
The iron blast furnace is a brick building, some 50 or 60 feet high,
closed at the bottom, and open at the top for the reception of the
charge. Air is forced into the bottom of the furnace through three
air-pipes or tuyères, whereby a high temperature is maintained. At
IRON. z 349
the bottom certain tap-holes are placed, through which the melted iron
may be let out, as well as other holes to allow the overflow of the
slag. -
The furnace is charged with layers of calcined iron ore, small-coal
and limestone, fresh layers being introduced as required.
Principle of the blast furnace.—The coal burns at the expense of the
oxygen of the air supplied through the air-pipes. The CO2 thus
formed passes over the hot fuel, and taking up more carbon becomes
CO. This carbonic oxide coming into contact with the red-hot oxide
of iron, becomes oxidized at the expense of its oxygen, leaving the
iron in a metallic state. The heated iron, as it sinks in the furnace,
combines with a little carbon, and so forms fusible “cast iron,”
which, in the hottest part of the furnace, reduces the silica and
the phosphates, and combines with the silicon and phosphorus set
free.
The limestone (CaCO3), when heated, parts with its CO2, leaving lime
(CaO). This combines with the infusible clay (silicate of alumina)
and with other impurities in the melted iron, to form a readily
fusible double silicate of lime and alumina, which, owing to its less
gravity, floats on the surface of the melted iron, and solidifies, when
cold, to “a slag.” [This limestone is called “a flua, ’’ because it makes
the clay flow (fluo).]
Thus the melted metal, with the fused slag swimming on its
surface, collects on the hearth of the furnace. The slag is allowed to
run out of openings in the upper part of the hearth, whilst the metal
is drawn off from below into sand-channels, each channel of iron
being called “a pig’” (“pig-iron’’). The iron thus obtained is known
as “cast-iron.”
The gas issuing from the chimney of the furnace is highly inflam-
mable and poisonous. The following represents its percentage com-
position:—
Nitrogen $ tº $ & & 55-35 vols.
Carbonic oxide & ſº & 25-97 ,,
Hydrogen ... • * * 6-73 , ,
Carbonic acid * & © 7-77 ,
Marsh gas ... tº is ſº 3.75 ,,
Olefiant gas ... * * * 0.43 , = 100:00 vols.
The air, previous to its being supplied to the furnace through the
“tuyères,” is usually heated to 600°F. (315.5°C.) by this furnace gas.
This constitutes what is called the “hot blast.” In this way a great
loss of heat is prevented. It is stated, however, that “hot blast iron’’
is of inferior quality to “cold blast iron,” as the iron both receives and
retains a larger quantity of impurities.
Cast iron (pig iron) contains about 2 to 5 per cent, of carbon, but it
is not a pure carbide (Fe,C).
350 HANDBOOK OF MODERN CHEMISTRY.
Composition of Cast Iron (Percy).
Maximum. Minimum.
Carbon * * * 4'81 & e - 1:04 per cent.
Silicon a º º 4.77 tº tº º 0.08 ,,
Sulphur Q - e. 1-06 tº e & 0:00 ,,
Phosphorus ... 1.87 e - tº trace , ,
Manganese ... 6:08 Cº-º º trace , ,
Iron ... ... 81°41 ... 98-88 ,,
There are several varieties of cast iron known in commerce. In
white iron (the color of which is due to manganese) the carbon exists
in chemical combination with the metal (Sp. Gr. 7:53). In grey iron
a portion of the carbon is present in an uncombined state (Sp. Gr.
6:92). Mottled iron is an intermediate variety between white and grey
iron. Cast iron fuses at about 3000°F, (1648.8° C.). It is hard, non-
elastic, and brittle. It cannot be welded.
Wrought iron.—Cast iron is changed into wrought iron by the pro-
cesses of “refining ” and “puddling.”
Reftning is for the purpose of effecting the removal from the iron of
the carbon, silicon, sulphur, and phosphorus. The melted metal is
subjected to the action of a current of air, whereby the silicon and a
part of the carbon become oxidised. The silica unites with the oxide
of iron produced simultaneously, to form a fusible slag.
Puddling.—The puddling furnace is a reverberatory furnace ; its
use is rendered necessary by the circumstance that the metal becomes
less fusible as it approaches purity. The fused metal is well stirred
or “puddled,” so that the oxidation of the impurities may be effected
by their actual contact with oxide of iron. The metal is then well
hammered, in order to squeeze out the liquid slag. This hammered
mass constitutes wrought iron.
The Bessemer process was invented to save the great manual labor
involved in the ordinary puddling operation. It consists in burning
out the carbon and silicon with an air blast, and then supplying
carbon by the addition of sufficient cast iron (spiegel-eisen) to convert
the whole into steel.
Wrought iron is soft, elastic, malleable and ductile. It is very
difficult to melt, but is capable of being welded. It is magnetic.
Steel is prepared by embedding bars of wrought iron in charcoal
and heating them for several days at 2000°F. (1093-3°C.) (Cementa-
tion). From the fibrous structure peculiar to wrought iron, the metal
gradually assumes the granular structure peculiar to steel. This change
is due to the iron throughout the mass becoming combined with about
1 per cent. of carbon. The transference of this carbon is believed to
be effected by the formation in the first instance of carbonic oxide, half
IRON. 351
of the carbon of which is taken up by the iron (200–C=CO2), the
CO, formed becoming again converted into CO by taking up more
carbon. Graham has shown that iron has the power of absorbing or
“occluding ” six or eight times its volume of carbonic oxide.
The unevenness of the blistered steel thus formed is remedied by
hammering, whereby shear steel is produced. When this is heated to
redness, and suddenly cooled by dipping into water or into oil, the
steel is rendered very hard, brittle and elastic, its volume being
slightly increased. By a process of tempering, that is, by again
heating and cooling the steel, it is prepared for the various purposes
for which it is required, the temper depending on the temperature of
the metal when dipped, and on the rapidity of cooling. Heated to
430° F (221° C.), and cooled slowly (called tempering to the yellow), the
steel becomes very hard, and is used for knives, etc.; but if heated to
550° F (287.8° C), and then cooled (called tempering to the blue), it
becomes highly elastic, and is used for watch springs, etc.
Case hardening, or the superficial conversion of soft iron articles into
steel, is effected by heating them in contact with bone-dust, or other sub-
stance containing carbon, and then chilling them by dipping into Water.
Steel, unlike iron, retains magnetism. Hence it is used in the
manufacture of permanent magnets. A steel blade may be known
from an iron blade by placing upon it a drop of dilute nitric aeid.
A dark stain will be produced on the face of the steel blade, from the
separation of the carbon, whilst a green stain will result in the case of
the iron blade.
Impurities.-These are carbon (0-2 to 0.5 per cent.) (the presence
of which increases the hardness of the iron), silicon, sulphur, phosphorus
and arsenic. The presence of the last four bodies is very objectionable.
Properties, (a.) Physical. Bar iron is a hard, grey, lustrous
metal; pure iron is soft and silvery. It has no smell unless it be
rubbed. Its texture is fibrous. Its specific gravity is about 7-7.
When heated it first becomes pasty, and in this condition may be
welded.” At a greater temperature it may be fused. At a red
heat it is both ductile and malleable. It expands slightly at the
moment of cooling. Compared with other metals its tenacity is enor-
mous, but its conductivity for heat and electricity is comparatively
small. It is, in common with nickel and cobalt, but in a far higher
degree than these metals, remarkably magnetic. A red heat, how-
ever, destroys its magnetism, although it recovers it again on cooling.
Its magnetism, however, is not permanent, unless the iron be combined
with carbon, as in steel, or with oaygen, as in Fes04, or with sulphur, as
in Fes S, or FerSs, but combined with oxygen or sulphur in pro-
portions other than these, the metal is not magnetic at all.
* In “welding,” the two pieces of pasty metal are first covered with sand. This acts
as a flux to the oxide, thus enabling two absolutely clean surfaces to be brought into
contact. The slag of silica and oxide of iron formed is forced out by the hammering.
352 HANDIBOOK OF MODERN CHEMISTRY.
(6.) Chemical. Action of Air and Oxygen.—Dry air has very little
action on polished iron, but the metal rapidly rusts in moist air,
forming 2Fe2O3,3B.O. The presence of carbonic anhydride ex-
pedites the rusting process by the formation of a carbonate of iron
(Fe+H2O+ CO2=FeCO3+H.), which is soluble in water containing
CO2, but is precipitated from its solution by the absorption of oxygen
(4 FeCO3 + Og=2Fe2O3+4CO2). Once started, the rusting process
proceeds rapidly, owing to the hygroscopicity of the iron oxide.
Rust always contains ammonia, formed by the direct union of the
nascent hydrogen with atmospheric nitrogen. The contact of a nail
with a wet cloth causes a diffused iron-mould stain, due to the
formation of the carbonate of iron. Similarly the black streaks pro-
duced after a short time when iron nails have been driven into an
oak fence are due to the action of the tannic acid of the oak on the
solution of the carbonate of iron formed in the manner already
indicated. When heated to a high temperature, iron burns in oxygen
brilliantly, throwing out numerous scintillations. In a state of
minute subdivision it fires on mere exposure to air.
Action of Water.—Iron is not acted on by water, when the water is
free from air, but it is rapidly attacked by common water containing
dissolved air, more especially if the water be exposed to air at the
time of its contact with the iron. (For the action, see above.) The
presence of a free alkali, or of an alkaline earth, or of an alkaline
carbonate, interferes with this action. At a red heat iron decomposes
water (4H20+3Fe=Fe3O4-i-4H2).
Chlorine, bromine, and iodine, in the presence of water, combine
rapidly with iron at ordinary temperatures.
Action of Acids.-Hot or cold concentrated sulphuric acid has a
slight action on iron, SO2 being liberated, whilst the dilute acid acts
rapidly, evolving hydrogen. Ordinary nitric acid acts energetically
upon the metal, N.O., being evolved. If, however, the iron be first
dipped in nitric acid of specific gravity 1:45, which is without action
upon it, and then, without being wiped, placed in dilute nitric
acid, the latter will be found to have no action on the metal. A
similar change in the iron may also be effected by touching it, when
immersed in a nitric acid of specific gravity 1:35, with a piece of gold
or platinum, when the previous energetic action of the acid instantly
ceases (passive iron). Hydrochloric acid acts freely on it, hydrogen
being set free. Carbonic acid, dissolved in water freed from air, also
rapidly attacks it, with the evolution of hydrogen. Thus, in most
chalybeate waters the iron exists as a ferrous carbonate dissolved in
water containing CO2, a rusty deposit of oxide being formed when
the water is freely exposed to the action of the air.
IRON.
353
Compounds of Iron.
2-, *- 2 *:::: .
3 & 3 || 3 °.g.
Common Constitutional ||3:52: 3 35; Fe0 in
Formula. Formula. #:###| ###| || 100 parts.
==3 | *5°
# 1. Ferrous oxide (protoxide Fe0 Fe O 72 100
i of iron) . . . . . . *
2. g. Ferric oxide (per- or red Fe0
2. f | Ferric oxide (per- or re Fe’’’.O O 160 Fe=70-0
º: oxide) . . . . . . . . 2 - 3 Fe O
º:
3. c. |Magnetic or black oxide Fe0 ra. ..., & Jºy
º, ºr * * | Fe,0, or (Fe0, Fe,0) }#}Feo 232 5-09 Fe=72:41
4. Ferric acid º e º o H,Fe0, Fe0, Ho, 122 Fe=45'90
- p • 2. 528 :
5. 3 (Ferrous chloride (proto- Z / O 7 | º -* * * *
ſ: chloride) . . . . . . | FeCl, Fe"Cl, 127 l º Fe=44'09
- O *
6.3 | Ferric chloride (per- or 4. 'Fe’’’C]. tº º * * * : **
C sesquichloride) . . . . | Fe,Cls #Sºci: 3.25 Fe=34.46
7. (Bromides and Fluorides Febr., and Fe, Brs
similar to Chlorides) . . FeF, and Fe, F,
8. Ferrous iodide . . . . Feſ.,4H,0 Fe"I, 310 2-873 | Fe=18-06
9 Nitrides of iron ſ Fe,N, 252
. TV ILITIOI&S . . . . ) Fe,N 1S2
10. Ferrous sulphide (proto- + º - º
* ſº gº FeS FeS SS Fe=63-63
lif Fº (bisul- | FeS, FeS, 120 4'98 || Fe=46'66
3. 7 Fe,S,(?) ‘Fe'.S, 176
TE Fe,S, 20S
12.* | Other sulphides . . . . Fe,S, 296
Fe, Ss 64S 4-65
tº FeSAs (Mispickel) 6-13
13. § ( Ferrous sulphate (proto- Rºi º ºr y / : ; * º
*; ſº º } FeSO,7H,0 SOHo,Feo",60H, 152 1-857 25-90
14. E . Ferric sulphate (persul- f f f i > §
& V phate) º º º Fe",3S0, S,0s Fe,0" 400 Fe=28.00
• § Ferrous nitrate . . . . Fe2NO,6EI,0 | §§Feo",60H, 180 Fe=31. 11
- # Ferric nitrate . . . . . . Fe",6NOA, 12H,0 2
º Ferrous carbonate (proto- Tory'' * } =
carbonate) * e º º l FeCO, COFeo 116 62-07
Ferrous hydric phosphate Fe"HPO,
Ferric phosphate . . . . Fe",P,0s,4H,0 P.O.Fe,ovi,40H, 302 Fe=37-08
Ferrous oxalate 2FeC,0,3EI,0 | §Feo",30H 2 144 Fe=38-88
CoMPOUNDs of IRON witH Oxy GEN (O).
Ferrous oxide FeO.
Ferric oxide ... * - - * * * FesOs.
Magnetic or black oxide of iron Fes04.
Ferric acid Ho Fe04.
unknown in the free state.
Preparation (as a hydrate, Ferſ.O.).
(1.) Ferrous Oxide.—Protoxide of iron (Fe0).
This body is almost
By precipitating a solution of
a ferrous salt with an alkali, care being taken that the water in which
the ferrous salt is dissolved is entirely free from air.
A. A


354 FIANDBOOK OF MODERN CHEMISTRY.
Properties.—The white hydrated ferrous oxide rapidly absorbs
oxygen from the air, becoming the green hydrate of the magnetic
oxide, and finally the brown hydrated peroxide. It is a powerful
base, forming ferrous salts (protosalts of iron). These salts are of a
green color, and rapidly oxidize when exposed to the air. It is used
to stain glass a green color.
(2.) Ferric Oxide.—Red oacide ; Sesquioacide or peroacide of iron
(Fe2O3), (colcothar ; jeweller’s rouge; Venetian red; crocus of Mars;
etc.). It is found native as hamatite, specular iron, bloodstone, etc.
Preparation (anhydrous).—(1.) By the ignition of ferrous sulphate
(2FeSO4–Fe2O3+SO2+SO3).
(2.) (As a hydrate, Fe2O3,3EI2O). By acting on a solution of
ferric chloride with an excess of ammonia.
Properties.—The hydrate is soluble in acids. When dried and
heated to 608°F. (320°C.) it parts with its water, and forms Fe2O3.
If this be heated to redness it exhibits a sudden glow, contracts in
bulk, and, although its composition remains unaltered (the change
being molecular), it becomes insoluble in acids. Heated to whiteness
oxygen is evolved, and a magnetic oxide formed (3Fe2O3=2Fe30,--O).
With acids it forms ferric salts (persalts of iron), which are non-
crystalline and deliquescent, of a reddish colour, having an astringent
taste and an acid reaction.
Like alumina, with which it is isomorphous, it can, although in a
lesser degree, act the part of a feeble acid to strong bases, as, e.g.,
in the compound 4CaO, Fe2O3.
Uses.—Ferric oxide is found in all soils. It serves as a carrier of
air to organic matter, whereby CO2 is prepared for the plant. The
ferrous oxide thus formed is again oxidized to ferric oxide, and so
fitted once more to perform the same process. The hydrated ferric
oxide is largely used as a means of purifying coal-gas from sul-
phuretted hydrogen, (Fe2O3.H2O)+3H2S=(Fe2S3, H.O) +3H2O. The
hydrated ferric sulphide formed is oxidized (“revivified”) by exposure
to air, considerable heat accompanying the process (2FeS2, H20+30.
=2Fe,0s, H20+3S.). The ferric oxide thus reproduced may be again
and again employed, until the free sulphur formed has accumulated
in such quantity as to impair the power of the oxide to absorb the gas.
(3.) Magnetic Oxide of Iron.— Black oacide (Fe3O4 or Fe0, Fe2O3).
The latter formula is believed to be the correct one, minerals being
known which have the same crystalline form, but where the iron is
displaced by other metals, e.g., spinelle (MgO, Al2O3). It occurs native
as loadstone, and is the chief constituent of the black scales falling
from the anvil during the working of Wrought iron.
Preparation.—(1) By burning iron in Oxygen; (2) By passing steam
over hot iron filings; (3) By boiling freshly precipitated hydrated
ferric oxide with an excess of iron turnings in water.
(4.) As a hydrate, by adding ammonia to a mixture of equivalent
parts of ferrous and ferric sulphate, and boiling.
IRON. 355
Properties.—The black oxide is fusible at high temperatures. It is
soluble in nitric and in hydrochloric acids; but it does not form defi-
nite salts with acids, but simply mixtures of ferrous and ferric salts.
(4.) Ferric Acid (H2Fe(),) exists only in combination as ferrates.
A potassic ferrate solution (K. Fe0) is prepared either by dissolving
in water an ignited mixture of ferric oxide and nitre, or by passing
chlorine through a solution of potash (30 parts of KHO in 50 parts of
H2O) in which 1 part of freshly-precipitated hydrated ferric oxide is
suspended (Fe2O3 + 3Cl2 + 10KHO=6|KC1-1-2 K.Fe0,--5EL20). It is
very soluble in water, but is insoluble in a strong potash solution.
Its aqueous solution has a fine purple color. It rapidly decomposes
(2K2Fe04=2K2O+Fe2O3 + 3O), oxygen being evolved and ferric
oxide precipitated. The presence of organic matter or the application
of heat decomposes it immediately.
CoMPOUNDs of IRON AND CHLORINE.
Ferrous chloride ... t is a • * * ... FeCl2.
Ferric chloride tº Q - & s tº ... Fe2Cl6.
(5.) Ferrous Chloride, Protochloride of iron (FeCl·).
Preparation.—(1.) By passing dry hydrochloric acid gas over red-
hot iron (Fe+2HCl=FeCl2 + H2).
(2.) By heating ferric chloride in hydrogen (Fe2Cl6+ H2=2FeCl2+
2HCl).
(3.) (As a hydrate, crystals=FeCle, 4H2O). By dissolving iron in
hydrochloric acid.
Properties.—The crystals are deliquescent, of a green color, and
very soluble in water and in alcohol. By heating in air they are
decomposed into Fe2O3 and Cl. They rapidly oxidize, even by mere
exposure to air.
(6.) Ferric Chloride; Perchloride, Sesquichloride, or Trichloride of
Iron (Fe2Cl6).
Preparation.—(1) (Anhydrous, Fe2Cl6). By the action of chlorine on
red-hot iron.
(2.) (As a hydrate, Fe2Cl6,6H2O). By dissolving ferric oxide in hy-
drochloric acid.
(3.) By passing chlorine through a solution of ferrous chloride.
Properties.—The anhydrous salt is very deliquescent, and rapidly
combines with water, its solution becoming red. The hydrate is a red
crystalline body, decomposed by heat into Fe,0s and HCl. Hence
the anhydrous salt cannot be prepared from the hydrate. It forms a
double salt with ammonic chloride.
Uses.—In solution it is used as a disinfectant, on account of the
ease with which it yields chlorine to organic matter, becoming itself
reduced to ferrous chloride. It is used in medicine and in the labo-
*atory. Its solution freely dissolves freshly precipitated ferric hydrate,
forming ferric oxychloride.
356 HANDBOOK OF MODERN CEIEMISTRY.
1.
(8.) Ferrous Iodide (FeI2).
Preparation. By digesting iron and iodine in water.
Properties.—It decomposes by exposure to air, and is hence com-
monly prescribed in medicine in the form of a syrup, by which means
its oxidation is retarded.
(10.) Ferrous Sulphide ; Protosulphide or sulphide of iron (FeS).
Preparation. (1.) (Anhydrous). By the contact of sulphur with
white-hot iron. -
(2.) (As a hydrate.) By precipitating a ferrous salt with an alkaline
sulph-hydrate (2REIS-H-FeSO4+ H2O=IFeS, H2O + H2S--K2SO4).
Properties.—The anhydrous compound is insoluble in water and in
the alkalies, but is soluble in dilute sulphuric or hydrochloric acids,
H2S being evolved. When heated in the air it first becomes FeSO4,
this compound being itself decomposed at a higher temperature. The
hydrate rapidly absorbs oxygen when exposed to the air, forming the
the red ferric oxide and free sulphur.
(11.) Ferric Disulphide (FeS2) is found native in all rocks as
pyrites (mundic), and is probably formed by the deoxidation of fer-
rous sulphate by organic matter. By exposure to air some varieties
(such as marcasite) rapidly absorb oxygen, forming ferrous sulphate.
It is a hard body not attracted by the magnet. It is not acted on
either by cold sulphuric or by hydrochloric acids. By heat sulphur
is driven off, and magnetic pyrites (Fe3S4) formed. On account of this
property, iron pyrites is largely used in the manufacture of sulphuric
acid. (See page 152.)
Iron Oxy-Salts.
(13.) Ferrous Sulphate.—Protosulphate of iron; copperas: green
vitriol; iron vitriol (FeSO4).
Preparation.—(1.) By acting on iron with dilute sulphuric acid and
crystallizing (FeSO4,7B...,0). [Other hydrates of FeSO, have also
been obtained].
(2.) By the oxidation of iron pyrites (FeS2) by contact with air and
moisture. (See above).
Properties. – A green efflorescent, crystalline (rhomboidal) salt,
soluble in alcohol and in water (1 in 2 aq. at 60°F. ; 3.7 in 1 aq. at
194°F.; 3-3 in 1 aq, at 212°F.). At a moderate heat the salt becomes
white, losing at the same time six molecules of its water. At 500°F.
(260° C.) the seventh molecule of water escapes, whilst at a red heat the
salt itself is decomposed (2FeSO =Fe2O3+SO2+SO3). The prepara-
tion of Nordhausen sulphuric acid from ferrous sulphate, depends on the
circumstance that it is practically impossible to render the sulphate in
large bulk perfectly anhydrous, and that therefore the little water
remaining in the salt distils over along with the SOs. The residue
(Fe2O,) left in the retort when the process is complete is called
coloothar.
CHROMIUM. 357
By exposing a solution of the salt to air, a brown liquid results,
due to the formation of a normal and basic ferric sulphate, the former
remaining in solution and the latter being precipitated (10BesO4+ Og
=3(Fe,0,3S03)+2Fe,0s,SO.). A similar result occurs by the ex-
posure of the solid crystals to air. The aqueous solution of the salt
rapidly absorbs nitric oxide. It forms double salts (isomorphous
with the magnesic salts), with potassic and ammonic sulphate.
Uses.—In the laboratory it is used as a reducing agent, as, e. g., to
precipitate metallic gold from its solutions. In the arts it is used in
the manufacture of black dyes and of ink, by the action of tannic
acid infusions upon it.
(14.) Ferric Sulphate. — Persulphate or sesquisulphate of iron
(Fe",3S0,), is found native in Chili, as coquimbite (Fe23SO,9EI2O).
Preparation. — By adding the necessary quantity of H2SO4 to
Fe''SO, to convert it into Fe23SO4. The mixture is then boiled, the
iron being afterwards peroxided by the cautious addition of nitric
acid.
Properties.—A non-crystalline, yellow body.
(15.) Ferrous Nitrate (Fe2NO3,6H2O) is prepared by the action of
cold dilute nitric acid on ferrous sulphide ; whilst
(16.) Ferric Nitrate (Fe"26NOs, 12H2O) is prepared by the action
of nitric acid (specific gravity 1-2) on metallic iron.
[N.B.—Fuming Nitric Acid (specific gravity 1-5) has no action on
iron. (See Passive Iron, p. 352.) -
(17.) Ferrous Carbonate, Protocarbonate of iron (FeCOs), is found
native as spathic iron ore, and as clay iron ore. It is the iron salt
commonly found in mineral waters, retained in solution by the car-
bonic acid dissolved in the water, from which it is precipitated by the
action of oxygen, as a red rusty deposit of hydrated ferric oxide.
This deposit is frequently seen on the ground in the neighbourhood
of chalybeate springs.
Preparation.—By mixing together solutions of an alkaline carbonate
and a ferrous salt.
Properties.—The hydrate formed as above, is a white body, evolving
CO2 and absorbing O (becoming 2 Fe0s,3EI2O) by mere exposure to
8.1L.
(20.) The Iron Oxalates are found native (Humboldtite or iron-
resin), and may also be produced as lemon-yellow precipitates, by
precipitating ferrous Sulphate with ammonic oxalate.
Tests.-(See ANALYTICAL TABLEs).
CHROMIUM (Cr).
Atomic weight, 52-5. Specific gravity, 7-01. Atomicity; dyad, tetrad,
- and hea'ad, also a pseudo-triad and octad (CrO,CrO3).
History.-Obtained by Vauquelin (1797), from lead chromate.
358
HANDEOOK OF MODERN CHEMISTRY.
Natural History.—It is found as chrome-iron-slate (Fe0,0r.0),
and also as lead-chromate (PbCrO.). *
Preparation.—(1.) By heating the oxide with charcoal.
(2.) By the action of metallic-sodium or potassium on chromic
chloride.
Properties.—(a.) Physical. A hard, crystalline (octahedra), highly
infusible metal.
(3) Chemical—It is not oxidized by heating in the open air. It is
not acted on by any acid except hydrofluoric acid, but is converted
into a chromate by ignition with the hydrated alkalies.
Compounds of Chromium.
Atomic Weight, Cr 52.

k- º
Formula | # | 35 | Cr
COMPOUNDS. Formula (Constitu- E; # per
(Common). tional .# 3 || 3, § t
ional). : E 5.5 cent.
1. ſ Chromous oxide (protoxide). . CrO CrO 68-0 76-47
CrO
2. § | Chromic oxide (sesquioxide). . Cr,0s | O 152-0 || 5°21 68°42
# < CrO
3. C | Chromous dichromic tetroxide CrO,Cr,0, } §§ CrO" | 220-0 70-90
4. Chromic dioxide CrO,
5. U Chromic anhydride CrO, Cry O, 100.0: 2-676|| 52.00
6. ſ ( Potassic chromate K,CrO, CrO.Ko, 1942| 2.682| 26-77
7. Potassic dichromate . . K2Cr,0, Cr,0, Ko, 294-2 || 2:624| 35-35
8. Potassic trichromate . . K2Cr,010 Cr,0sko, 394-2 39.57
9. . Potassic tetrachromate K2Cr,015 Cr,0m Ko, 494.2 42-08
10. 3 l (Sodic chromate . . . . Na,óño.iofi,o Örö Nao. ió20 32°09
11. # < { Hydric sodic chromate 2(NaHCrO.),H,0
12. 3 ) Ammonic dichromate (NH4)2CrO,
13.5 | Baric chromate BaCrO, CrO.Bao” 253.0 20-55
14.9° (Plumbic chromate is º PbCrO, CrO.Pbo” 323-0|| 5:653| 16-09
15. | Basic plumbic chromate . . 2PbO,Oro, 6-266
16, Argentic chromate. . . . . . Ag.,CrO. CrO2Ago, 5-77 23-21
17. Argentic dichromate . . . . Ag20,20rC's
18. 2 ( Chromous chloride. . . ; hio. CrCl, % 123-0 42'27
19. § W Chromic chloride (sesquichlo- 'Cr"Cl, & &
# *** hio Cr2Cl6 }%; alſo 32-80
20. -- || Chromic oxy-dichloride (chlo- * RS > - -
à jº . • ? } CrC1,0, CrO,C), 155-0 | 1.92 || 33-54
21. Chromic sulphide . . Cr,S, - 200.0 52-00
22. Chromic sulphate . . . . Cr,3S0, S,00r,0" | 392.0 26'53
23. Chromic nitrate Cr,6NO,
(1.) Chromous Oxide (CrO) is only known as a hydrate (CrH2O2),
It is produced by adding potassic hydrate to a solution of chro-
mous chloride.
CrO,CroC)3.
(2.) Chromic Oxide,-Sesquioxide of chromium (Cr2O3).
It absorbs oxygen with great energy, forming
It is a feeble base.
CFIROMIUM. 359
Preparation.—If a solution of potassic dichromate, acidulated with
sulphuric acid, be boiled with alcohol, or if a current of SO2 be
passed through a solution of the dichromate, the chromic acid loses
half its oxygen, and a chromic sulphate is formed. On adding
ammonia to this solution, the hydrated sesquioxide (Cr2H606) is
precipitated, which on ignition leaves Cr2O3:
Properties.—Chromic oxide has a brilliant green color, which is
unaffected by heat, and is, consequently, largely used in enamel painting.
It constitutes the green coloring matter of the emerald. “Guignét's
green” has the composition CryEI500.
The hydrate forms two sets of salts with acids, one of which is
green and non-crystalline, and the other violet and crystalline.
The anhydrous sesquioxide is insoluble in acids.
(3.) Chromic Anhydride (Chromic acid) (CrO3).
Preparation.—By adding an excess of sulphuric acid to a strong
solution of potassic bichromate, and Crystallizing.
Properties.—Chromic anhydride crystallizes in needle-shaped crys-
tals, which are deliquescent, and soluble in water. It is decomposed
by heat with the evolution of oxygen. It is a powerful oxidizing
body (4CrO3=2Cr2O3 + 3O2), and is used as an agent in bleaching
certain oils. Heated with hydrochloric acid, chlorine is liberated ;
when heated with sulphuric acid, oxygen is set free. The color of
the ruby is believed to be due to the presence of a trace of chromic
acid.
(4.) Potassic Chromate (K2CrO4).
Preparation.—(1.) By adding potassic carbonate to a solution of
potassic dichromate.
(2.) By fusing a chromium compound with potassic carbonate.
(3.) (See below.)
Properties.—A yellow crystalline salt, soluble in water (1 in 2 aq.
at 60°F.), the solution having an alkaline reaction. It fuses by
heat, becoming red without decomposing.
(5.) Potassic Dichromate or anhydrochromate. —Bichromate of
Potash (K.Cr2O7).
Preparation.—(1.) By the action of sulphuric acid on potassic
chromate.
(2.) Commercially the salt is prepared as follows:–Powdered
chrome ironstone is heated in air with chalk and potassic carbonate,
The ferrous oxide is thus changed into the insoluble ferric oxide, and
the chromic oxide (Cr2O3) into chromic acid (CrOs), which forms, with
the potash, potassic chromate (K2CrO4). The mass is then acted on
with water, and the clear Solution mixed with nitric acid and
crystallized :-
2(K.CrO4) + 2HNO3 = K3Cr,07 + 2KNO3 + H2O.
Potassic chromate + Nitric acid = Potassic dichromate + Potassie nitrate + Water.
Properties.—A red crystalline salt. It fuses at a moderate heat, but
360 HANDBOOK OF MODERN CHEMISTRY.
is decomposed when the heat approaches redness, with the evolution
of oxygen. It is soluble in water (1 in 10 aq. at 60°F.).
(12.) Plumbic Chromate.- Chromate of lead; Chrome yellow
(PbCrO4). This body is found native as red lead ore (Siberia).
Preparation.—By the action of lead acetate on potassic chromate.
Properties.—A yellow poisonous pigment. When heated it turns
brown, and evolves oxygen (8PbCrO4–4(PbCrO.PbO)+2Cr,03+30.).
It is insoluble in water and in acids, but is soluble in an excess of
potassic hydrate.
Uses.—In the arts it is used as a yellow pigment, and in the
laboratory as a source of oxygen in organic combustion analysis.
(13.) Basic Plumbic Chromate.-Orange chrome (2PbO,CrO3).
Preparation.—By boiling together lime and plumbic chromate :—
2(PbO,CrO3) + CaO = 2PbO,CrO, + CaCrO4.
Plumbic carbonate + Lime = Basic plumbic chromate + Calcic chromate.
Properties.—A Scarlet pigment. It is used in calico printing, the
fabric being first dyed with plumbic chromate and afterwards boiled
in lime-water.
(16.) Chromous Chloride (CrCl3).
Preparation.—By heating chromic chloride in a current of dry
hydrogen.
Properties.—A white substance, the aqueous solution of which is
blue, but becomes green by exposure to air. It is a powerful re-
ducing agent.
(17.) Chromic Chloride.-Sesquichloride of chromium (Cr2Cl6).
Preparation— (1.) (Anhydrous.) By passing dry chlorine over a
heated mixture of chromic oxide and charcoal. The CrgCl6 collects as
a violet sublimate in the cool part of the tube.
(2.) (As a hydrate).-(a) By dissolving chromic hydrate in hydro-
chloric acid; or (3) by boiling either chromic acid, or the lead or silver
chromate, with hydrochloric acid and some reducing agent such as
alcohol, SO2, etc.
Properties.—Insoluble in acids or in cold or boiling water. If a
trace of chromous chloride be added to the salt suspended in
water, it becomes soluble, great heat being evolved in the act of
solution.
The Fluorides of Chromium (Crſ'; and CrºPs) have been pre-
pared.
(18.) Chromic Oxydichloride.—Chlorochromic acid (CrCl2O3).
Preparation.—By distilling sulphuric acid with a fused mixture of
common salt and hydric potassic chromate :-
R2Cr,0; + 4NaCl + 3H.S.O. = K,SO, -- 2NagSO, + 3H2O +
2CrCl2O2.
Properties.—A red liquid (Sp. Gr. 1:92) emitting suffocating red
fumes (Sp. Gr. of vapor, 5.52). It catches fire when dropped into
TITANIUM. 361
alcohol, or into a solution of ammonia. It is decomposed by
water. g * * *
(19.) Chromic Sesquisulphide (Cr2S3) has been obtained. Chro-
mium, however, has but little affinity for sulphur.
(20.) Chromic Sulphate (CrºSO.).-There are three varieties of
chromic sulphates:—
(a.) A green sulphate (Cr,3S0,5H2O), which is soluble in alcohol
and is non-crystalline. It is prepared either (a) by boiling hydrated
chromic oxide with sulphuric acid, or (3) by boiling a solution of the
violet sulphate, or (y) by heating the crystals of the violet Sulphate to
212° F (100° C.).
(3.) A violet sulphate (Cr:3S0,,15H2O), which is insoluble in alcohol
and is crystalline. It is prepared by digesting the dried hydrated
sesquioxide with sulphuric acid at ordinary temperatures. With
potassic sulphate it forms chrome alum (K2Cr,4SO,24EI2O, Sp. Gr.
1-826).
º A red sulphate (Cr,3S03). A crystalline salt, insoluble either
in alcohol, in water, or in acids (even in aqua regia). It is prepared
by heating the green or the red variety to 698°F. (370°C.).
Tests.-(See ANALYTICAL TABLES.)
TITANIUM (Ti).
Atomic weight, 50. Specific gravity, 5-3. Atomicity dyad and tetrad (TiO;
TiCl,).
History.--Discovered by Gregor ( 1791).
Natural History.-It is never found free, but occurs in titaniferous
iron (as in iron sand); also as titanic anhydride (TiO2), in rutile,
anatase, Brookite, etc. -
Prepapation.—(1.) By heating titanic oxide (TiO2) with charcoal.
(2.) By heating sodium in the vapor of titanic chloride.
Properties.—A dark green substance. It burns with vivid sein-
tillations in air and oxygen, and in burning absorbs both oxygen and
nitrogen. Hydrochloric acid dissolves it, with the evolution of
hydrogen. It has a great affinity for nitrogen. If a mixture of
charcoal and titanic anhydride be heated, and whilst hot introduced into
a jar of nitrogen, the nitrogen will be absorbed, and CO be formed.
If ammonia gas be passed over red-hot titanic anhydride, the violet
titanium dinitride (TiNa) is formed; or if ammonia be passed over
4H3N,TiCl3, the nitride TisN, results.
In iron furnaces certain crystals are frequently found adhering to
the slag, which consist of a mixture of cyanide and nitride of titanium
(TiCya,3TisN.) (Wöhler). They are extremely hard, almost absolutely
infusible, and have a specific gravity of 5-3. They are insoluble in
any acid, except in a mixture of nitric and hydrofluoric acids.
BIANDBOOK OF MODERN CEIEMISTRY.
Compounds of Titanium.
Formula Formula Molecular Specific | Ti per
NAMES. (Common.)|(Constitutional.) Weight. Gravity. cent.
1. . (Titanous oxide—Protoxide
3 of titanium . . . . . . . TiO TiO 66 75-75
2.E { Sesquioxide of titanium . . Ti,0s 148
3.5 || Titanic oxide or anhydride TiO, TiO, 82 60-97
4. T \Titanic acid . . . . | TiO, H,0 TiOHo, 100 50-00
5.3 (Dititanic hexachloride Ti,Cls } # 3.13 31.95
6.8 | Titanic chloride (tetra- 3
5 chloride) . . . . . . TiCl, TiCl, 192 || 1:760 26-04
3 (r.... . & g TiE
7.; ) Dititanic hexafluoride Ti,F, | Tirº 214 46.72
8. § {Titanic fluoride TiF, Tir. 126 39.68
ſº
9. Titanic sulphide TiS", TiS", 114 43.86
10. Dititanic dinitride . . Ti,N, } #Nº. 128 78-12
11. Trititanic tetranitride Ti,N”, 206 72°81
CoMPOUNDS OF TITANIUM AND OxygłN.
Titanous oxide * * * is e > TiO.
Sesquioxide of titanium Ti2O3.
Titanic oxide TiO2.
(1.) Titanous Oxide.—Protoxide of titanium (TiO) is a black pow-
der, and may be obtained by heating TiO2 in a crucible lined with
charcoal (?).
(2.) Sesquioxide of Titanium (Ti2O3) is obtained as a dark brown
precipitate on adding ammonia to a hydrochloric acid solution of
titanic acid after digestion with metallic copper at 122°F. (50°C.). It
rapidly absorbs oxygen from the air.
(3.) Titanic Oxide,-Dioacide; titanic anhydride; titanic acid (TiO2).
This body occurs native as rutile (Specific gravity, 4'25. Crystals,
brown needle-prisms), anatase (Specific gravity, 3-9. Crystals, blue
transparent octahedra), and Brookite (Specific gravity, 4:13. Crystals,
right rhombic prisms). It also occurs in combination with oxide of iron
(iron sand).
Preparation.—Powdered “ rutile,” or “iron sand,” is first fused
with potassic carbonate. After the fused mass has been treated with
hot water, the residue (an acid potassic titanate) is dissolved in hydro-
chloric acid, and the solution evaporated to dryness. In this way
the titanic oxide and any silica present are converted into insoluble
modifications. This residue is now fused with acid potassic sulphate,
whereby a yellow mass is obtained having the composition TiO2,SOs,
and which, being soluble, may be separated from the silica by treat-
TITANIUM. 363
ment with cold water. On boiling the solution, the titanic oxide is
precipitated as a white powder. By continuous heating this white
powder becomes anhydrous, its color changing to black, its specific
gravity likewise increasing. It moreover becomes insoluble in all
acids, except in hydrofluoric and in boiling sulphuric acids. Fused
with potash, it forms a yellow potassic titanate, which is soluble in
hydrochloric acid, from which solution titanic oxide may be pre-
cipitated as a hydrate on adding ammonic carbonate.
Titanic oxide (hydrate) is yellow when hot and white when cold.
It is soluble in hydrochloric and sulphuric acids (thus distinguishing
it from silica). It is insoluble in a solution of potassic hydrate, but
forms a titanate when fused with potash. The potassic titanate is
decomposed by water, an acid potassic titanate being formed which
is soluble in hydrochloric acid, from which solution hydrated titanic
acid (TiO2, H2O) may be precipitated by ammonia.
The titanates may be represented either as 2M'20,TiO2(=M',TiO,),
CoMPOUNDS OF TITANIUM AND CHLoRINE.
Titanous chloride... e - © e C & * G - TiCls.
Titanic chloride ... . ... & E tº tº tº a TiClt.
(4.) Titanous Chloride (TiCls) forms lustrous violet-colored
crystals, prepared by heating titanic chloride in hydrogen.
(5.) Titanic Chloride,-Tetrachloride of titanium (TiCl,) is prepared
by passing chlorine over a red-hot mixture of titanic oxide and char-
coal. It is a volatile colorless liquid (Specific gravity of vapor, 6.836;
of liquid, 1761, at 32°F.) It boils at 275°F. (135°C.). It is decom-
posed by an excess of water.
REACTION OF TITANIUM CoMPOUNDs.
(A.) Titanous compounds.
Ammonic Carbonate.—A blue ppt., changing to brown and then to
green.
(B.) Titanic compounds (titanic acid dissolved in HCl).
(1.) Ammonia, a white ppt.
(2.) Infusion of galls, an orange-coloured ppt.
(3.) Potassic ferrocyanide, a brown ppt.
(4.) The boraa bead, or microcosmic salt, gives in the inner blowpipe
flame a yellow bead when hot, which changes to violet as it cools.
364 HANDBOOK OF MODERN OBEMISTRY.
CHAPTER XVI.
METALS OF GROUP II.
A.—METALS WHOSE SULPHIDES ARE INSoLUBLE IN THE ALKALINE
SULPHIDEs.
CoPPER and its Componnds—BIsMUTH and its Compounds—CADMIUM-Compounds
With Oxygen, with the Haloids, and with Sulphur — PALLADIUM and its Com-
pounds—RHODIUM and its Compounds—OSMIUM and its Compounds—RUTHENIUM
and its Compounds. º
B-METALS WHOSE SULPHIDES ARE SOLUBLE IN THE ALKALINE
SULPHIDEs,
TIN and its Compounds—ANTIMony and its Compounds—ARSENIC and its Com-
pounds – GoLD and its Compounds—PLATINUM and its Compounds — Bases
produced by the action of Ammonia on the Chlorides of Platinum—MoLYBDENUM
and its Compounds. -
COPPER (Cu"—634).
Atomic weight and Molecular weight, 63-4. Specific Gravity, 8-9. Fuses,
1996°F. (1091° C.). Atomicity, dyad, as in Cupric Salts, Cu"Cle;
Pseudo-monad as in Cuprous Salts, ("Cu'2Cl2).
Natural History.—Copper is found native both in masses and in
crystals, not unfrequently associated with silver. The common
copper Ores are a sulphide of copper and iron, called “copper
pyrites,” or “yellow copper ore ” (Cu2S,Fe2S3), a cuprous sulphide,
or “copper glance ’’ (Cu2S), a cuprous oxide or “red copper ore,” or
“ruby ore ” (Cu2O). Copper is also found as cupric oxide or “black
oxide ’’ (CuO), and as malachite, the green malachite having the com-
position represented by the formula (CuCO3, CuO, H2O), and the blue
malachite (2CuCOs, CuO, H2O).
Preparation.—From copper pyrites (Cu3S,Fe2S3) (Copper smelting).
The ore is sorted, that is, those pieces rich in copper are picked out
and broken up, whilst the part less rich in metal is powdered and
sifted.
(1.) Calcination of ore.—The ore is first calcined or roasted, whereby
the arsenic and part of the sulphur are volatilized as As2O3 and SO2,
cuprous sulphide with some oxide, and ferric oxide (converted from
the ferric sulphide) with some sulphide, remaining. The ferric sul-
phide is far more easily oxidised than the cuprous Sulphide. Hence
the chief part of the Cu2S remains unaltered.
[The fumes given off during roasting are called “copper Smoke,”
COPPER. 365
and contain As, As2O3, SOA, SO2, and HF, the latter being derived
from the fluor spar contained in the ore.]
(2.) Fusion for coarse metal.—The calcined ore is now mixed with
sand, and with a slag containing a quantity of silicate, fluor spar
being added if necessary, to increase the fluidity of the slag. The
mixture is now intensely heated in the “ore furnace.” The following
changes occur:—The cuprous oxide acts on the ferric sulphide present,
cuprous sulphide and ferric oxide being formed. But inasmuch as
there is more ferric sulphide in the ore than can be oxidized by the
cuprous oxide present, the excess of the fused ferric sulphide, toge-
ther with the cuprous sulphide, sink to the bottom of the furnace to
form what is called the “mat'' or “coarse metal’’ (=CuFeS2). This
coarse metal is granulated by being run off into water whilst in a
liquid state.
The ferric oxide present combines with the silica to form a fusible
slag (silicate of iron) (FeSiO3), which is used for building purposes.
(3.) Calcination of the coarse metal.-The coarse metal is now cal-
cined, whereby any sulphide of iron present is converted into
oxide.
(4.) Fusion for white metal.—The roasted coarse metal is now fused
with silica, and with an ore rich in cupric oxide, whereby any
unchanged iron sulphide is converted into oxide. The whole of the
iron which is now present as ferric oxide combines with the silica to
form a fusible slag, the “mat,” or “regulus of white metal,” or the
“fine metal,” as it is now called, being nearly pure cuprous sulphide
(Cu2S).
Sometimes the roasting is carried further, so that a portion of the
Cu2S becomes reduced. This reduced portion sinks to the bottom,
along with most of the foreign metals present, these parting with their
sulphur more readily than the copper. Hence the upper part of the
ingot is always the purest, and is known as “best selected copper,”
whilst the under portion, containing the impurities, is known as “tile
copper.” -
(5.) Roasting for blistered copper.—The fine metal (Cu2S) is now roasted,
whereby some of the copper becomes converted into CuO, the sulphur
escaping as SO2. Hence the mass after roasting consists of Cu2S and
CuO. The temperature is now raised, when mutual decomposition
occurs between the cuprous sulphide and the cupric oxide, metallic
copper and sulphurous anhydride (which escapes) being formed
(Cu,S+2CuO=SO.--4Cu). This copper is called “pimple,” or
“blistered copper,” blisters being formed upon it, by the escape of the
last portions of the SO2.
(6.) Refining.—This is effected by melting the copper, so as to oxidise
the last traces of sulphur and of foreign metals, such as Fe, Sn, Pb,
etc., present. Some cuprous oxide (Cu,0) is produced during the
process, a part of which forms a slag with any sand present, whilst
366 IIANDBOOK OF MODERN CHEMISTRY.
another part is dissolved by the metallic copper. The presence of this
cuprous oxide in copper renders the metal brittle (“dry copper”).
(7.) Toughening (poling). —After the removal of the slag, some anthra-
cite is thrown on the surface of the melted metal, to prevent it
becoming further oxidised. It is then well stirred with a pole of
young wood (poled), the combustible gases given off by the wood,
burning at the expense of any oxide present in the liquid metal. The
presence of a little suboxide in the metal is said to render it tough.
Hence “over-poling ” (that is when the whole of the cuprous oxide is
removed), or “under-poling” (that is where too much is left), are
both to be avoided. When the copper is properly poled it is known
as “tough cake.”
In the preparation of copper from the oxide, or from the carbonate,
all that is necessary is to reduce a mixture of the copper salt with
carbon and silica, in a wind furnace.
A pure copper may be obtained by electrolysis, or by heating the
oxide in a current of hydrogen.
Impurities.—Sulphur (which injures the malleability of the copper),
arsenic, phosphorus (which increases its hardness), tin, antimony,
nickel, bismuth, silver, and selenium, are the ordinary impurities.
Properties.—(a.) Physical. A red metal, having a metallic taste
and a peculiar smell. It is found native, and may be prepared
artificially both in cubes and in octahedra. It is very heavy (Sp. Gr.
8:9), hard, ductile, malleable, and sonorous. It fuses at 1996° F.
(1091° C.), and at a white heat is said to be slightly volatile. It is a
good conductor both of heat and electricity.
(6.) Chemical.—Copper is not affected by air, dry or moist, at
ordinary temperatures, but it oxidises rapidly in air at a red heat,
black scales of cupric oxide (CuO) pealing off from the surface of the
metal. When finely divided it burns like tinder. In the oxyhydrogen
blowpipe the metal burns, rendering the flame green. It is unacted
upon by pure water, nor indeed has a current of steam any action
on the red-hot metal. When placed in solutions of chlorides, as
in sea-water, copper becomes coated with the green oacychloride
(CuCl2,3CuO,4EI2O). Copper vessels are, therefore, dangerous for
culinary purposes, inasmuch as a certain quantity of the metal is
certain to be dissolved when solutions of common salt or acids (such
as vinegar, rhubarb, etc.), or liquids containing fatty and oily matters,
are boiled in contact with the metal.
Nitric acid and boiling sulphuric acid dissolve it. With the former
nitric oxide (N2O2) is evolved, and with the latter sulphurous anhy-
dride (SO2). Liquid hydrochloric acid acts upon the metal when
finely divided, evolving hydrogen. When a current of hydrochloric
acid gas is passed over the red-hot metal, hydrogen is set free, and
cuprous chloride (Cu2Cl2) is formed. Ammonia dissolves copper, but
the fixed alkalies have very little action upon it. It combines with
COPPER.
367
*
chlorine energetically, thin leaves of metallic copper catching fire as
soon as they are exposed to the action of the gas.
Uses.—For coinage; for sheathing ships; for alloys. The composi-
tion of certain alloys is stated in the following table, taken from
Bloxam.
Copper. Zinc. Tin. Iron. Nickel. Aluminium.
Brass . . . . . . . . . 64 - 0 36.0
Muntz metal. . 60 to 70 40 to 30
German silver . . . . 51 - 0 30 - 5 * sº-sº 18.5
Aich (or Gedge's) metal 60- 0 38-2 *ºs 1-8
Sterro Imetal. . . . . . 55-0 42'4 0-8 1-8
IBell metal 78-0 *ºms 22-0
Speculum metal . 66-6 *-* 33-4
Bronze metal 80-0 4 - 0 16-0
Gun metal 90 - 5 * 9 - 5
Bronze coinage 95-0 1-0 4 - 0
Aluminium bronze 90- 0 - sm - 10 - 0
Compounds of Copper.
# * # 3 * | P ti
COMPOUNDS. Formula Fºrmula, ſº # of dºo
(General). (Constitutional). 3 # #3 £5 in the Salts.
= ~ :
1. Cuprous hydride º e Cu, H., } § 128.8 Cu = 98.44
2. 3 (Cuprous quadrantoxide Cu,0
3. # Cuprous oxide (red oxide). . Cu,0 'Cu’,O 142-8 Cu = 88-79
4. Ś (Cupric oxide (black oxide) CuO Cu 79°4 || 6-5 Cu = 79-85
5. Cuprous hydrate tº º 4Cu,0, H.0 4"Cu',0,0H,
; º: hydrate . . . . . . . . . Cuff,0, CüHo,
g(ºut ºnlº Cu,Cl, "Cu',Cl, 197-8 || 3:37 Cu = 64-10
; 'g ſºil. º: CuCl, CuCl, 134-4 || 3:05 | Cu = 47-17
... r- ydrated cupric oxychlo-
5 l ride of copper. . . . . . CuCl2,3Cubſ,0,
[Corresponding bromides
and iodides have been
prepared.]
º a. º ...; tº ſº tº wº CusN, 408-4 Cu = 93-14
'# \ º upº º Cu,S "Cu'.S” 158-8 5-5 Cu = 79-84
2.3 ) Qupric sulphide. • . . . . CuS CULS’’ 95.4 3-8 | Cu = 66°45
3, 5 ( Cupric pentasulphide CuSs
4. Cupric phosphide .. Cu, P., P.Cu”, 252.2 Cu = 75-41
& §: Selenide . . . . . . * *
* * * * * | cuso,5II.0 Soho Cuo",40H, 1594 || 2:26 Guo – 31.84
7. Cupric nitrate . . . . . . . Cu2NO,6H,0 | §§Guo",40H, 1874 Cu = 33-83
8. Hydrated oxy-carbonate of §Cuo"
9 : dº º € º } 2CuCO,CuH,0, {{#ºcuo" 344-2 || 3-8 Cu = 55-22
#). Hydrated dibasic c &
ºl.” carbon } CuCOs, CuFI,0, CO(OCullo), 220-8 || 3-9 Cu = 57.42
0. Dicuori rbonate (mvso.
* * * @sº } 20u0,00, CCuo", 202'S Cu = 62-52

368 . BIANDBOOK OF MOIDERN CEIEMISTRY.
CoMPOUND of CoPPER AND EIYDROGEN.
Cuprous hydride & ſº º tº gº º ... Cug|Hz.
(1.) Cuprous Hydride (Cu,FL)
Preparation.—By heating a cupric sulphate solution with hypo-
phosphorous acid to 140°F. (60°C.).
Properties.—A black powder, evolving hydrogen when heated. It
catches fire when exposed to the action of chlorine. Hydrochloric
acid forms with it cuprous chloride, the combination being accom-
panied by the evolution of hydrogen (Cu, H2+2HCl=Cu2Cl2+2H2)
CoMPOUNDS OF COPPER AND OxYGEN.
Cuprous quadrantoxide ... is e tº tº ſº tº ... Cu2O.
Cuprous oxide (red oxide) & º º • * > ... Cu2O.
Cupric oxide (black oxide) © tº sº. tº gº ... CuO.
(2.) Cuprous Quadrantoxide (Cu30). This oxide is only known
as a green hydrate, and may be prepared by digesting in closed
vessels, a cupric salt with an excess of stannous chloride dissolved in
a large excess of potassic hydrate. }
(3.) Cuprous Oxide, Suboa;ide or red oacide of copper (Cu,0).
Molecular weight=1428. Specific gravity, 5-7. Found native in octa-
hedral crystals.
Preparation.—(1.) By boiling grape sugar in a solution of cupric
sulphate, containing an excess of potassic hydrate.
(2.) By igniting a mixture of 5 parts of cupric oxide (CuO) and
4 parts of copper filings.
(3.) By boiling a mixed solution of cupric sulphate, sodic sulphite,
and sodic carbonate (2CuSO4+2Na2CO3 + Nag'SO3=Cu2O+ 3Na2SO4+
2CO2).
(4.) By acting on an ammoniacal solution of cupric oxide with
metallic copper, air being excluded, the blue solution of CuO becoming
the colorless solution of Cu2O (Cu + CuO=Cu2O).
(5.) As a hydrate (4Cu20, H.O.) By decomposing cuprous chloride
with potassic hydrate.
Properties.—(a.) Physical. A reddish-yellow powder.
(6.) Chemical. In the moist state it is slowly oxidized by air. It is
a feeble base. There are no cuprous Oxy-salts (except sulphites and
certain double sulphites), the oxy-acids decomposing cuprous oxide,
and forming a mixture of a cupric salt and metallic copper. Thus
nitric acid converts cuprous oxide into cupric nitrate, and hydro-
chloric acid into cuprous chloride (Cu2Cl2). It is soluble in ammonia,
the solution being colorless, but in the presence of a mere trace of
oxygen the solution turns blue from the formation of cupric oxide.
It is slightly soluble in metallic copper, which it renders what is
called “dry” or “brittle.”
CoPPER AND CHLORINE. 369
Uses.—For stained glass, to which it imparts a fine red color.
(5.) Cupric Oxide; Copper monocide; black oride of copper (CuO).
Molecular weight, 79°4. Specific gravity, 6'5.
Preparation.—(1.) By heating the metal in air.
(2.) By the ignition of cupric nitrate or carbonate (2Cu2NO3=
2CuO +2N2O4+O2).
(3.) (As a hydrate, Cu, H2O2). By adding potassic hydrate in excess,
to a solution of a cupric salt. The hydrate (blue) becomes anhydrous
(black) by boiling in water.
Properties.—(a.) Physical. The hydrate (CuII,02) has a light blue
color, but the anhydrous compound is black. Heat has no effect upon
it. It is insoluble in water, but is soluble in oils and fats. Hence
the danger of copper for culinary purposes.
(3.) Chemical.—Cupric oxide is a hygroscopic body, absorbing
water freely from the air, although not soluble in water. It is
soluble in most acids, forming cupric salts that are isomorphous with
magnesic salts. It combines when fused with the fixed alkalies. The
hydrate is soluble in ammonia water, forming a blue solution, having
the property of dissolving cellulose, which cellulose is reprecipitated
from the solution by an acid. The blue solution is also formed when
copper filings are shaken up in an ammonia solution in the presence
of air, a portion of the ammonia becoming oxidised simultaneously
with the copper, white fumes of ammonic nitrite being formed. It is
decomposed when heated in hydrogen with the evolution of heat and
light.
Uses.—In organic combustion analysis to furnish oxygen. It is
used to stain glass a fine green color.
CoMPOUNDS OF COPPER AND CHLORINE.
Cuprous chloride ... ge e a tº a º ... Cu2Cl2.
Cupric chloride © º º gº tº tº & & e ... CuCl2.
(7.) Cuprous Chloride.—Subchloride of copper (Cu2Cl2 or "Cu'2Cl2).
Molr. Wt.=197-8. Specific gravity, 3-3.
* Preparation.—(1.) By the action of hydrochloric acid on copper in
the presence of air (20 us+4HCl·HO2=2Cu2Cl2+2EI2O).
(2.) By distilling one part of copper filings with two parts of mer-
curic chloride.
(3.) By boiling together cupric chloride and sugar.
(4.) By heating dry cupric chloride in a current of dry ammonia.
(5.) By the action of stannous chloride on a cupric salt (2CuCl2
+ SnCl2=Cu2Cl2 + SnCl4).
Properties.—(a.) Physical. A white compound, turning grey when
moistened and exposed to light. It may be obtained in tetrahedral
crystals. It fuses when heated to a yellow mass. It is insoluble in
Water.
R B
370 HANDBOOK OF MODERN CHEMISTRY.
(6.) Chemical. Hydrochloric acid dissolves it. The colorless solu-
tion thus formed throws down cuprous chloride on the addition of
Water. The acid solution readily absorbs carbonic oxide, from which
solution the crystalline compound (4Cu2Cl2,3C0,7B.O) may be ob-
tained. It also absorbs oxygen, when the solution becomes brown and
deposits a green cupric oxychloride (CuCl2,3Cu0,4H2O), known as
“Brunswick green.” This latter substance is also found native (ataca-
mite). - -
Ammonia solution dissolves it, forming (air being excluded) a
colorless liquid. This solution rapidly absorbs oxygen, when it becomes
deep blue. It gives a red precipitate with acetylene, for which it
constitutes a delicate test. With argentic nitrate it deposits silver, the
ammonia holding the silver chloride and copper nitrate in solution
Cu2Cl2+4AgNO3=2(Cu2NO3)4-2AgCl4-Aga.
Cuprous chloride is soluble in potassic chloride, forming with it
the double salt (4KCl,Cu2Cl2). It is also soluble in ammonic chloride,
white dodecahedral crystals of Cu2Cl2 (NH3)2 being deposited from
the fresh solution, or, if after prolonged exposure to air, blue cubical
crystals of Cu"Cl2(NH3)2,2NH,Cl.
(8.) Cupric Chloride,-Chloride of copper (CuCl2).
Preparation.—(1.) By dissolving cupric oxide in hydrochloric acid
and crystallizing (=CuCl2,2H2O).
(2.) By the spontaneous combustion of copper in chlorine.
Properties.—Green deliquescent crystals (specific gravity, 2-5), be-
coming blue when dried. The salt fuses and is decomposed by heat into
chlorine and cuprous chloride. It is very soluble both in alcohol and
in water, the aqueous solution being green when concentrated and
blue when dilute. The spirit solution burns with a green flame. It
forms double salts with the alkaline chlorides.
Cuprous Bromide or subbromide of copper (Cu, Bra) and Cupric
Bromide (Cubra), Cuprous Iodide or subiodide of copper (Cuºſº, H2O),
a white insoluble powder, and Cupric Iodide (CuI2), have been
prepared.
(10.) Tricupric Nitride (Cuºng).
Preparation.—By passing ammonia gas over cupric oxide heated
to 482°F. (250° C.).
The nitride is a dark green powder.
CoMPOUNDS OF COPPER AND SULPHUR.
Cuprous sulphide e ºr * s e e * - tº Cu2S.
Cupric sulphide tº e º © e a º º º CuS.
Cupric pentasulphide © sº is e tº e CuSg.
(11.) Cuprous Sulphide.-Subsulphide of copper (the “fine metal"
of the copper smelter) (Cu,S). This body is found native in six-sided
prisms, as “copper glance” or “Redruthite.” Copper pyrites is a
cuprous-ferric-sulphide (Cu,S,Fe2S3).
CUPRIC OXYSALT8. 3.71
Preparation.—By melting together three parts of sulphur and eight
of copper.
Properties.—Fusible by heat (Sp. Gr. 5-5). Soluble (with decompo-
sition) in nitric acid and in aqua regia, but insoluble in hydrochloric
acid.
(12.) Cupric Sulphide.—Sulphide of copper (CuS). Found native
as “indigo copper,” “blue copper,” or “covellin.”
Preparation.—(As a hydrate.) By precipitating cupric salts with
sulphuretted hydrogen.
Properties.—The hydrated cupric sulphide, by exposure to air,
rapidly becomes sulphate. It is soluble in nitric acid.
(13.) Cupric Pentasulphide (CuSs).
Preparation.—By decomposing a cupric salt with an alkaline penta-
sulphide.
Properties.—A black precipitate, insoluble in potassic carbonate.
(14.) Cupric Phosphide.—Phosphide of copper (Cu,Fe).
Preparation.—By boiling phosphorus in a cupric sulphate solution.
Properties.—A black substance, decomposed by heat (30ug|P2–
Cu6P2+2.P.). Phosphoretted hydrogen is evolved when it is added
to a solution of potassic cyanide.
Cupric 0xysalts.
(16.) Cupric Sulphate.—Sulphate of copper; blue vitriol; blue stone;
blue copperas (CuSO4,5II2O).
Molecular weight, 159:4+90. Specific gravity, crystals, 2.25. Anhy-
drous, 3-63. -
Preparation—(1.) By dissolving the metal or its oxide in sulphuric
acid.
(2.) By oxidising the sulphide.
(3.) As a secondary product in the refining of silver (vide silver);
a cupric sulphate being formed from the copper plates used to throw
down the silver from its solution as a sulphate.
Properties.—It is found in the form of transparent, blue, doubly
oblique crystals (CuSO4,5EI,0). When these are heated to 212°F.
(100° C.) they become CuSO4, H20, and at 392°F. (200° C.) the salt
changes to a white anhydrous powder (CuSO4). (This last H2O
molecule is regarded as water of constitution, the rest as water of
crystallisation.) The anhydrous white salt combines energetically
with water, the blue salt being thereby formed and great heat evolved.
At a high temperature it is converted into cupric oxide, oxygen and
sulphurous anhydride being evolved.
The crystals are insoluble in alcohol, but soluble in water (1 in 4 at
60° F., 1 in 2 at 212°F.). The solution is acid.
Potassic hydrate, added to a solution of the salt, throws down a blue
hydrated cupric oxide or “blue verditer” (CuII.O.). The powdered
372 HANDBOOK OF MODERN CHEMISTRY.
crystals rapidly absorb hydrochloric acid gas, with evolution of heat.
The anhydrous salt rapidly absorbs ammonia gas, forming CuSO4,5EIAN
(Rose). With the sulphates of ammonium and potassium, cupric
sulphate forms double salts, isomorphous with the corresponding
magnesium salts—
( Cºho, | (so), 6H.0).
Several basic cupric sulphates are known: of these may be mention-
ed a tribasic sulphate, CuSO4,2OuPI,02, and brochantite, CuSO4,3CuPI2O2.
The ammonio-sulphate of copper (CuSO4,4NH2,H2O) is formed when
a solution of cupric sulphate containing an excess of ammonia is care-
fully evaporated to dryness.
(17.) Cupric Nitrate (Cu2NO3,6EI,0).
Preparation.—By dissolving copper in nitric acid.
Properties.—A blue crystalline deliquescent salt, soluble in alcohol,
decomposed by a slight heat into an insoluble basic nitrate (Cu2NO3,
3Cubſ2O3), and by an intense heat into the black oxide (CuO).
Cupric Arsenite or Scheele's green (CuIHAsO3) is a green powder,
prepared by the action of an alkaline arsenite on a cupric salt. A
mixture of cupric arsenite and acetate (3CuAS304,0u2C3H3O3) consti-
tutes “Schweinfurt green.”
Basic phosphates of copper are found native as tagilite and libethenite.
The cupric carbonates known, are a hydrated oacycarbonate or “chessy-
lite ” (2011C03,CuPI.O., ; Sp. Gr. 3.8), and a hydrated dibasic carbonate
or “malachite” (CuCOs, CuFI.O., ; Sp. Gr. 37). “Mineral green”
has the same composition as this latter compound, and is prepared by
acting on a solution of cupric sulphate with sodic carbonate. If the
precipitate be boiled in the solution, CuO is formed.
Reactions of Copper.—(See ANALYTICAL TABLE.)
BISMUTH (Bi’”).
Atomic weight, 210. Specific gravity, 9.83. Fuses at 507-2°F. (264° C).
Atomicity, Triad (as in bismuthous compounds) (Bi"Cls); and Pentad
(as in bismuthic compounds (Bi",03).
Natural History.—Bismuth is commonly found in a free state,
but it also occurs as an oaside (Bi,0s) as “bismuth ochre,” and as a
sulphide (BioS3) as “bismuth glance.” These two last minerals are
I’8.I'ê.
Preparation .—By simple fusion of the ore in inclined iron cylinders.
Thus prepared, bismuth usually contains certain impurities, such as
arsenic, sulphur, and silver, the latter being frequently extracted by
cupellation.
BISMUTEI. 373
Properties,—(a.) Physical. A hard, brittle, reddish-white metal,
crystallizing in large cubes. It is slightly volatile at high tem-
peratures. It fuses at 507°F. (264°C.), expanding at the moment of
solidification. Its admixture with other metals frequently lowers their
fusing point to a remarkable extent.
(6.) Chemical. Bismuth is only slightly affected by air at ordinary
temperatures, but it oxidizes rapidly when made red-hot.
acid dissolves it freely; boiling sulphuric acid oxidizes it, SO2 being
evolved; hydrochloric acid and dilute sulphuric acid have no action
upon it.
sulphur.
No compound of bismuth with hydrogen is known.
Uses.—For alloys. Its use in type metal depends on its property of
expanding as it solidifies, thereby increasing the sharpness of the
impression.
Nitric
It combines rapidly with chlorine, bromine, iodine, and
In solder, its use depends on its power of lowering the fusing point
of the alloy.
Compounds of Bismuth.
†-
& 4 S º
SALTS Formula Formula T. # # Bi. per
e (General) (Constitution.) | gº § 3 Cent.
:* | *ś
I e Dibismuthous di- IBi O
oxide . . tº - Bi,0, IBiC) 448-0 92.85
2. 2 | Bismuthous oxide Bi,0s Bi,0s 468-0 | 8.211 | 89-74
3.3 Dibismuthic tetrox- s - e -
g ide tº e - º, Bii",0, 480-0 86.66
Or tºl,
4. | Bismuthic oxide or 4.
anhydride .. Bi,0s 496-0 83-87
5. ſ Bismuthous chloride
o, (trichloride) BiCl, BiCl, 314° 5 || 4-56 66-13
6.3 Bismuthous oxy- e º *
‘E chloride BiClO IBiC) Cl 259-5 80° 15
7: Dibismuthous tetra-
C chloride (dichlo- EiCl
ride) . . . . . . BiCl, }; 55S-0 74-55
: Bismuthous . BiBra BiBr, 2 448-0 46'42
e oxybro-
mide ... ... ".. IBi() Br 304-0 68°42
10. Bismuthous iodide Biſs EiL 5S9:0 35-31
i. º #9 ; 351 - 0 59:25
º e y UlOT1(le l 265 - 0 78-49
13.3 ſ Dibismuthousdisul- 3 3
H. phide . . . . . . . Bi,S, "B".S", 480-0 86-66
14.5 UBismuthous sulphide BiºSs Bi,S's 512-0 81.25
CD N0,—
15. 53 nitrate BiêNO,5H,0|| NO.Bio",5H,0|| 394-0 || 2:376 52-79
NO,-]
374 HANDIBOOK OF MODERN CHEMISTRY.
CoMPOUNDS OF BISMUTH witH OxygłN AND HYDROxYL.
Dibismuthous dioxide ... e 4 º' ... BigO2; #3
Bismuthous oxide • gº e * e e ... Big03; BizOs
[Metabismuthous acid (Bi,0s, H.,0)=HBiO, or BioHo)
Bismuthic oxide or anhydride... ... Big Os; Big05
[Metabismuthic acid (Bi,0s,H.0)=HBiO, or Bio. Hol
Dibismuthic tetroxide
OT | (BidO3, Bi,0s) or Biz0, ; "Bi",0,.
Bismuthous bismuthate
(1.) Dibismuthous Dioxide (BigO2). Preparation. By reducing
bismuthous chloride with stannous chloride in the presence of an
excess of potash.
Properties.—It burns freely, forming Bi,03.
(2.) Bismuthous Oxide; Sesquioxide or Trioxide of Bismuth (Bi.O.).
Molecular weight, 468. Specific gravity, 82.
It is found native as “bismuth-ochre.”
Preparation.—(1.) By heating bismuth in air. (2.) By igniting the
nitrate or carbonate.
Properties.—A yellow, easily fusible powder, soluble in HCl, in
HNO, and in H.SO, forming bismuthous chloride (BiCl3), bismuthous
nitrate (Bi 3(NO3)), and bismuthous sulphate (Bi. 3(SO4)) respectively.
Ammonia precipitates the oxide as a hydrate from the solution of a
salt of bismuth (Biz03, H2O).
(3.) Metabismuthous Acid (Bi,0s, H.O=HBiO2=BiOHo).
Preparation.—By adding ammonia to a solution of bismuthous
nitrate in dilute nitric acid. When heated, a residue of Biz03 re-
mains. By the fusion of BioC), with sodic carbonate, a sodic meta-
bismuthite (NaBiQ.) is formed.
(4.) Bismuthic Oxide; Pento&ide or Anhydride (Bi,05).
Preparation.—(a.) When bismuthous oxide, suspended in a solu-
tion of potassic hydrate, is treated with chlorine, metabismuthic acid
(HBiO3) is formed.
4KHO + 2Cl2 + Bi,0} = 2FIBiO3 + 4.KCl + H2O.
Potassic + Chlorine + Bismuthous = Metabismuthic + Potassic -- Water.
hydrate oxide acid chloride
(6.) By heating the 2HBiO, (=Bi,0s, H.,0) to 269° F (132° C.),
the H2O is expelled and bismuthic owide remains.
Properties.—A red powder, decomposed by heat (2Biz O5=Bi.03, Bi,0s
(or 2Bi,0)--O.) into bismuthous bismuthate. When bismuthic oxide
is heated in a current of hydrogen, Bi,0s is formed. Heated with
hydrochloric acid it forms bismuthous chloride, chlorine being evolved
(Bi.024-10HCl=2|BiCl3+5H20+2Cl2). When treated with nitric
or with sulphuric acids a bismuthous nitrate or sulphate is formed
accordingly, oxygen being liberated (Biz05+6HNO3=2|BišNO3 +
3H20+ O.).
OXY8ALTS QF BISMUTEI. 375
Metabismuthic Acid (Bi,0s,H.0=HBiO, or BiO.Ho).
Preparation.—Wide (a), under bismuthic oxide. The compounds of
this acid are very unstable.
COMPOUNDS OF BISMUTH AND CHLORINE.
Bismuthous chloride & sº tº tº º & tº º ſº. BiCla.
Dibismuthous tetrachloride e is e © - - BiºCl4.
(5.) Bismuthous Chloride,-Trichloride of bismuth (BiCl3=316:5).
Molecular weight, 316:5. Specific gravity of solid, 4:56; of vapor, 11:16.
Molecular volume, TT .
Preparation.—(1.) By heating bismuth in a current of chlorine
(Big-H3Cl2=2|BiCl3).
(2.) By distilling a mixture of bismuth and mercuric chloride
(Big-H 6HgCl2=2|BiCl, +3'Hg".C.).
(3.) By distilling a solution of bismuth in nitro-hydrochloric acid.
Properties.—A fusible, volatile, deliquescent solid. It is soluble in
dilute hydrochloric acid, but is decomposed by pure water into
bismuthous oxychloride [3BiClO = (BiCls, Bi,0})], or “pearl white,”
and hydrochloric acid (BiCl3+ H2O=BiC10+2HCl). The oxychloride
is insoluble in tartaric acid, or in ammonic sulphide. -
CoMPOUNDs of BISMUTH AND SULPHUR.
Dibismuthous disulphide ... BiºS. ... "Bi".S".
Bismuthous Sulphide * - & BigSº © º ºr BigS'2.
Dibismuthous Disulphide (BiºSs) is found native, and may be
prepared by fusing together sulphur and bismuth.
(13, 14.) Bismuthous Sulphide (BiºS3=516) is found native as
“bismuth glance.” -
Preparation.—(1.) By fusing together sulphur and bismuth in
proper proportions.
(2.) By passing sulphuretted hydrogen through a bismuth solution
(2BiCl, 4-3H2S=BioS,--6HCl).
Properties.—A fusible, dark grey, heavy substance (Sp. Gr. 6:4).
It is soluble in nitric acid, but is insoluble in either dilute sulphuric,
or hydrochloric acids, or in the alkaline hydrates or sulph-hydrates.
OxYsALTs of BISMUTH.
(15.) Bismuthous Nitrate (BiêNOs, 5H2O=896+90, Sp. Gr. 2:3).
Preparation.—By dissolving the metal in nitric acid.
Properties.—When the acid solution is acted on with a quantity of
water, a precipitate is thrown down of a basic nitrate, submitrate, or
trisnitrate of bismuth (flake white; magistery of bismuth) (BiêNOs,
Bi,0s,3EI,0). -
Reactions of Bismuth, (See ANALYTICAL TABLES.)
376 HANDBOOK OF MODERN CHEMISTRY.
CADMIUM (Cd").
Atomic and molecular weight, 112. Specific gravity, 8:604, Fuses at
442°F. (228°C.), Boils at 1580° F. (860° C). Atomicity, dyad
(CdCl, ; CdC).
History.--Discovered by Stromeyer (1818).
Natural History.—Cadmium is found in zinc ores, and also as a
sulphide (Greenockite).
Preparation.—When zinc ore is distilled, the cadmium (a constant
accompaniment of zinc) passes over first, owing to its greater
volatility, its presence being indicated by a brown flame (brown
blaze). The distillate thus obtained (a mixture of cadmium and
zinc) is dissolved in dilute sulphuric acid, and H2S passed through
the solution. The yellow precipitate of CdS formed, is then
dissolved in hydrochloric acid, to which an excess of ammonic carbo-
nate is added. The precipitated carbonate of cadmium (CdCO3), on
ignition becomes CdC), from which the metal may be obtained by
distillation with charcoal.
Properties.—(a.) Physical. A white, soft, crystalline metal, mark-
ing paper like lead, and crackling when bent like tin. At common
temperatures it is both malleable and ductile, but when heated to
176°F. (80°C.) it becomes brittle. It fuses at 442°F. (228°C.) The
cadmium atom appears to occupy in the state of vapor twice the space
of the hydrogen atom.
(6.) Chemical.—At ordinary temperatures air has no action upon the
metal, but it burns with a brown flame when heated, CdC) being
formed. The metal is dissolved by the mineral acids when heated
with them, hydrogen being evolved.
|Uses.—Its presence in alloys reduces the fusing point of the alloy,
without impairing the toughness or the malleability of the compound.
CoMPOUNDs of CADMIUM witH OxYGEN, witH THE HALOIDs,
AND WITH SULPHUR. ,
Cadmic oxide gº & c. e is e CdC)
Cadmic chloride 4 tº a e - - CdCl2.
Cadmic sulphide ... tº º º CółS.
Cadmic Oxide (CdC)=128) is a brown powder, prepared either
by burning the metal in air, or by igniting the nitrate. A cadmic
hydrate (CdRI.O.) is formed by precipitating a cadmic salt with potassic
hydrate. -
Cadmic Chloride (CdCl2,2FI,0), Cadmic Iodide (a salt used in
photography), and Cadmic Sulphide (CdS=144) (Greenockite), a
bright yellow pigment of great purity and permanence, have been
prepared. The yellow cadmic sulphide may be known from the yel-
low orpiment by being non-volatile, and insoluble in ammonic sulphide.
Jºeactions of Cadmium.—(See ANALYTICAL TABLE.)
PALLADIUM. - 377
PALLADIUM (Pd"=106.5).
Atomic weight, 106.5. Specific gravity, 11.6. Fusing point, 2480° F.,
(1360° C.). Atomicity, dyad (") as in palladious compounds, (e.g.,
PdCl2); rarely tetrad (") as in palladic compounds (PdCl).
History.—Discovered by Wollaston (1803) in platinum ores
(0-5 to 1 per cent.).
Natural History.—Found associated with platinum and gold.
Extraction.—(a.) Eatraction from platinum ores. After the platinum
has been precipitated from its solution by ammonic chloride, the
filtrate is neutralised and the palladium precipitated as palladic
cyanide with mercuric cyanide. This precipitate of palladic cyanide
is collected and heated to redness, the spongy palladium thus ob-
tained being afterwards heated, hammered, and welded.
(3.) Ectraction from gold ores.—The gold ore is first fused with
silver. The fused mass is then boiled with nitric acid, whereby the
gold is separated as an insoluble precipitate. The silver in the solu-
tion is then precipitated with sodic chloride. The lead, copper, and
palladium are afterwards separated from the filtrate by placing a
piece of metallic zinc in the liquid. The mixed precipitate thus
obtained is then dissolved in nitric acid, from which the lead is pre-
cipitated by ammonia, leaving the copper and the palladium only in
solution. The palladium is then precipitated as hydrochlorate of pal-
ladamine (Pd"N.H.,2RCl) by the addition of hydrochloric acid in
excess. This precipitate, when heated, leaves the pure metal .
Properties.—( a.) Physical. A hard, white metal, malleable and
ductile, harder and lighter than platinum (Sp. Gr. 11-6). It is volatile
at a high temperature, when it evolves green vapors. At a red
heat the metal absorbs oxygen, but liberates it again on cooling.
It possesses the property of absorbing many times its volume of
hydrogen, giving it out again at high temperatures. This property
is far more marked in the hammered palladium, which will absorb 640
times its volume of hydrogen, than with the fused metal, which only
absorbs 68 times its bulk. —(“Proceedings Royal Society,” June,
1866.)
(3.) Chemical. Palladium is unaffected by air at ordinary tem-
peratures. At a low red heat it becomes oxidized; but at a higher tem-
perature the oxide formed at the lower temperature is reduced. It is
soluble in nitric acid, forming palladious nitrate (Pd(NO3)2), and also
in aqua regia. It is oxidized by fusion with the caustic alkalies, nitre,
etc. It combines with iodine, forming palladious iodide (PdL).
Hence, if an alcoholic solution of iodine be evaporated on palladium,
a stain of PdL, is produced, a reaction which serves to distinguish palla-
dium from platinum. It forms a carbide when heated in the flame of a
spirit lamp. With gold (1Pd and 4Au) it forms a perfectly white brittle
alloy; with silver (1Bd and 2Ag) it forms a white unoxidizable alloy of
378 HANDBOOK OF MODERN CHEMISTRY.
great ductility, and useful for small weights; and with tin (1Ed
and 8Sn=PdsSng) it forms an alloy of great brilliancy.
Compounds of Palladium.

P-
Formula .g lº
SALTS. §. (ºr | # rº,
º tional). º g
) 3P
1. 3 (Suboxide of palladium.. Pd,0 'Pd',0 229.0 93-01
2. E & Palladious oxide . . . . Pd() EPCl’O 122°5 86-93
3. 5 ( Palladic oxide ... .. Pd(), Pd*O, 138' 5 76-89
4. & 3 { Palladious chloride .. TºdCl, Pd"C1, 177.5 60.00
5.5:: UPalladic chloride . . . . PdCl, PdivOl, 248° 5 42.89
6. Palladious iodide. . . . PdL, Pā'ī, 360-5 |}}*.
7. Palladious cyanide .. PdCy, Pd"Cy, 158.5
8. , 3 (Subsulphide of palladium Eds 'Pd'.S 245' 0
9. Tº 3 | Palladious sulphide .. PdS PG"S 138-5
10. * = { Palladic sulphide . . . . PdS, Pdivs, 170-5 62° 46
(1.) The Suboxide of Palladium (Pd,0) is prepared by heating
hydrated palladious oxide (PdH.O.) to redness. -
(2.) Palladious Oxide (PdC) is prepared as a brown hydrate
(PdH2O2) soluble in acids and in alkalies, by adding potassic car-
bonate to a palladious salt, or in an anhydrous form, either by heat-
ing the hydrate, or by the ignition of the nitrate.
(3.) Palladic Oxide (PdC.) is prepared as a yellowish-brown
hydrate(Pd*H,04) by acting on potassic palladic-chloride(2KCl, PdCl,)
with a solution of potassic hydrate. It may be obtained in an
anhydrous form as a black powder by boiling the hydrate in water.
(4.) Palladious Chloride ; Chloride of Palladium. (Pd"Cle=1775).
Preparation.—By evaporating a solution of the metal to dryness.
Properties.—The hydrate is brown, and the anhydrous compound
black. It is decomposed by heat, the metal being reduced. It forms
double salts of a dark green color with the alkaline and with other
metallic chlorides. With ammonia it forms a series of compounds
similar to those formed by platinum, palladamine being isomeric
with platinamine, etc. (See page 406.)
(5.) Palladic Chloride (Pd"Cl) is only known in solution. It
forms double salts with the alkaline chlorides, as e.g., the red, and
somewhat insoluble salt (2KCl, PdCl4.) It is easily decomposed into
palladious chloride and free chlorine. *
(6.) Palladious Iodide (Pd"I).
Preparation.—By the action of a soluble iodide on a soluble palla-
dious salt. º
Properties.—A black substance, insoluble either in water, ammonia,
BHODIUM. 379
or in an excess of potassic iodide. It is decomposed by a heat of
662°F. (350° C).
[N.B.-In the laboratory, palladium salts are used for the estima-
tion of iodine, as they do not precipitate either chlorine or bromine.]
(7) Palladious Cyanide (Pd"Cyc).
Preparation.—By acting on neutral solutions of palladious salts
with potassic or mercuric cyanide.
Properties.—A yellow substance, soluble in ammonia, in acids, and
in an excess of potassic cyanide.
(9.) Palladious Sulphide (Pd"S) is formed by precipitating a
palladious salt with sulphuretted hydrogen. It is insoluble in ammo-
nic sulphide.
Reactions of Palladium Compounds.
1. Sulphuretted hydrogen; a black ppt. (Pd"S), insoluble in ammonic
sulphide.
2. Mercurio cyanide; a yellow ppt. (Pd"Cyg) in neutral solutions.
3. Potassic iodide; a black ppt. (Pd"I2), soluble in excess.
4. Potassic and 80aic hydrates; a red or brown ppt., soluble in
OXCOSS.
5. Potassic and sodic carbonates; a brown precipitate of Pd"H.O.,
with salts of Pd".
6. Ammonia and ammonic carbonates; a flesh-colored ppt. with Pd"Cl,
soluble in excess of ammonia.
Estimation of palladium as palladious iodide :-100 grs.-29:54 Pd.
RHODIUM (Rh=104-3).
Specific gravity, 12:1. From its analogy, regarded as a tetrad (iv)
(Rh2Cl6).
History.—Discovered by Wollaston (1803).
Natural History.—Found in platinum ores (0.5 per cent.).
Extraction.—It is obtained from the solution of the platinum ore.
The filtrate, after the extraction of the platinum (by NH,Cl) and of
the palladium (by mercuric cyanide), is acidulated with hydrochlorie
acid. Sodic chloride is then added, and the liquid evaporated to dry-
ness. On treating the residue with alcohol (Sp. Gr. 0.837) everything
is dissolved, except the double chloride of rhodium and sodium—
(Rh2Cl6,6NaCl,24H.O),
which remains as a red powder. From this compound, metallic rho-
dium may be obtained, either by placing bars of zinc in a solution of
the compound, or by heating the dry salt itself in a current of hydro-
gen, the sodic chloride being afterwards removed by Washing.
Properties.—(a.) Physical. A white hard brittle metal (Sp. Gr.
12:1). It requires a greater heat for its fusion, than even platinum.
It absorbs oxygen when melted.
380 HANDBOOK OF MODERN CHEMISTRY.
(6.) Chemical.—It is oxidised when heated in air.
It is insoluble
in acids if pure, but is soluble in nitro-hydrochloric acid, when alloyed
with platinum, lead, etc., provided these latter metals be present in
excess. It combines with sulphur by heat (RhS). It is dissolved
when fused with potassic nitrate.
By fusion with hydric potassic
sulphate, a soluble potassic rhodic sulphate (KRh2SO4) is formed.
Compounds of Rhodium.
Formula
SALTS. (General).
1. Protoxide of rhodium Rh O
2. Rhodic oxide Rh,04
Oxides. 5 y ,, hydrates of } #ho
3. Dioxide of rhodium VII" 12
4. Trioxide of rhodium Rh(),
5. Rhodic chloride Rh2Cls
º' chlorid Sodic rhodic chloride 6NaCl, Rh,0l.,24H.0
7. * | Potassic rhodic chloride 6KC1, Rh,016,6H,0
8. Ammonic rhodic chloride 6NH,Cl, Rh,0ls, 3 H.0
* ! Sulphid Protosulphide of rhodium tº Rb S
10. | *P* Sesquisulphide of rhodium .. tº e Rh,Ss
11. Rhodic sulphate . . * * tº & * * Rh,(S0),12H,0
12. Potassic rhodic sulphate tº ſº & ſº RhKa(SO4)3
Reactions of the Rhodium Compounds.
1. Sulphuretted hydrogen ; a brown ppt. (Rh2S3) in a hot solution,
insoluble in ammonic sulphide.
2. Soluble sulphites; a pale yellow ppt.
3. Potassic iodide; a yellow ppt. (RhgT6).
4. Faced alkalies; a yellow ppt. (Rh2O3,5EH2O), soluble in acids and
in excess of alkali.
5. Solutions of rhodic salts (which are usually rose-colored) are de-
composed, with precipitation of metallic rhodium, by iron or zinc.
6. The metal is reduced when heated in a current of hydrogen.
OSMIUM (Os).
Atomic weight, 199. Specific gravity, 21-4. Atomicity dyad, tetrad and
hea'ad.
History.—Discovered by Tennant, 1803 (Derivation, dopi), odor).
Natural History.—Is found in platinum ores.
Extraction.—The solution of the ore in potassic hydrate (see pre-
paration of Ruthenium) is mixed with an excess of hydrochloric acid and
metallic mercury, and digested in a closed bottle at 284°F. (140°C.).
The mercury reduces the osmium, which immediately forms an amal-
gam with the excess of mercury, from which the mercury may be
afterwards distilled, and the metallic rhodium obtained as a black
powder–OsO44-8Hg--8HCl=0s--4Hg2Cl3+4E20.
RUTHENIUM. 381
Properties.—These vary. In the state of powder rhodium is black,
and has a specific gravity of 10. It is highly combustible, and is
easily oxidised by nitric or by nitro-hydrochloric acids to OsO4. In
the compact state (i. e., after ignition) it exhibits great lustre. It has
a specific gravity of 21:4, and is not soluble in acids. It is the least
fusible of all the metals. A heat which fuses platinum, iridium and
ruthenium, will not melt, although it may volatilise, osmium.
Compounds of Osmium.

Formula Molecular
SALTS. (General.) Weight.
1. Protoxide of osmium .. & is • e º e OsO 215
2. g \ Sesquioxide of osmium ; Osmious oxide c tº Os,Os 446
3.5 K Dioxide of osmium ; osmic oxide tº º - tº OsO, 231
4-5 | Trioxide of osmium * @. tº º tº - & e OsO, 247
5. . \Tetroxide of osmium ; osmic acid º e - - OsO, 263
6.3 Protochloride of osmium ; osmious dichloride .. OsCl, 270
7.3 ) Trichloride of osmium .. • e tº º - © Os,Cls 611
8.3 Osmic chloride . . • e q is tº º tº º OsCl, 341
9.5 V Osmic hexachloride tº e tº º • e tº e OsCls 412
10. Sulphide of osmium º º tº gº º º © wº Oss, 327
(5.) Osmic Tetroxide.—(Osmic acid) (OsO4) is formed when metallic
osmium or the lower oxide of osmium is heated in air, or treated
with aqua regia. It consists of colorless crystals, which are very
volatile and intensely pungent. It is very soluble in water, the solu-
tion staining the skin black, and possesses a strong smell. It is a
powerful oxidising agent. It is soluble in alkalies, forming yellow
solutions. Sulphuretted hydrogen precipitates a black sulphide (Oss,)
from the alkaline solutions.
Reactions of Osmium Compounds.
1. They all yield a peculiar odor when heated with nitric acid.
2. Sulphuretted hydrogen, when passed through a solution of OsO,
acidulated with HCl, gives a black ppt. (Oss,), which is very slightly
soluble in ammonic sulphide.
With Osmic Acid :—
1. Potassic nitrite; produces a red salt, potassic osmite.
2. Sodic sulphite; produces a blue salt, osmium sulphite.
RUTHENIUM (Ru).
Atomic weight, 1044. Specific gravity of porous metal, 8-6, and of fused
ºnetal, 11.4.
Like the other platinum metals it is both a dyad (RuOl.) and a tetrad
(RuOla).
History.—Discovered by Claus (1846).
382 EIANDBOOK OF MODERN CHEMISTRY.
Natural History.-Found in platinum ores ; also in the mineral
“laurite,” as a sulphide, together with sulphide of osmium (Borneo).
Extraction.--When platinum ore is acted upon with aqua regia,
an insoluble white scaly residue remains, consisting of an alloy of
osmium, iridium, ruthenium, with a little rhodium. When this is
heated in a current of air, the osmium is oxidised (OsO4) and volatilises,
the vapor being condensed either in flasks or in a solution of caustic
potash. The osmic acid vapor, moreover, carries the ruthenium,
as ruthenic oxide, mechanically with it, Ru(), not being itself volatile.
This is deposited on fragments of porcelain placed in immediate
contact with the heated tube. The metallic ruthenium is prepared
from this oxide by heating in hydrogen. Ruthenium and iridium are
also found in the residue remaining in the tube. By fusing this
residue with potassic hydrate, a potassic rutheniate is produced,
which is soluble in water, from which solution RuçO3 may be pre-
cipitated by nitric acid, and the oxide reduced by ignition in hydrogen.
Properties.—(a.) Physical. A hard, brittle, and almost infusible
metal.
(3.) Chemical. It oxidises with difficulty when heated in air, but
readily when heated with potassic hydrate or with potassic nitrate,
potassic rutheniate being formed. This salt, dissolved in water,
yields a yellow-colored solution.
Compounds of Ruthenium.
Formula Molecular
SALTS. (General.) | Weight.
1. Monoxide of ruthenium (dark grey) . . is ſº RuO 120' 4
2. . ( Sesquioxide of ruthenium ; ruthenious oxide
.# (black) .. tº e tº dº tº ſº tº tº e & Rug0, 256'8
3. ‘i: ) Ruthenic oxide . . tº gº g is tº º * ºr RuO, 136'4
4. C ,, anhydride (ruthenic acid) . . tº tº RuOs 152-4
5. ,, tetroxide * 4 * * * * * tº RuO, 168-4
6. 1 g (Dichloride of ruthenium. . * * tº wº * * TuCl, 175.4
7.33 Ruthenious chloride . . . . . . . . . ººls 421.8
8.5 °F ( Ruthenic chloride ge & * * * * tº tº TuſCl, 246'4
9. , § Sesquisulphide of ruthenium .. & wº * * Ru,Sa 304'8
10.3: ) Ruthenic sulphide * , tº gº & & tº wº RuS, 168°4
g-
Oxides of Ruthenium,_The monocide (RuO) is a dark grey
powder, not affected by acids. Ruthenious oride (Ru,03) and ruthenic
ocide (RuO2) are feeble bases. Ruthenic anhydride (RuO3) is only
known in combination. It is analogous to osmic anhydride.
Reactions of Ruthenium Compounds.
Dissolve the residue formed by fusing together caustic potash and
a ruthenium compound, in water. Test the solution as follows:–
TIN. - 383
1. Nitric acid; a black ppt. (Rug03).
2. Add hydrochloric acid to the liquid having the RugO3 (formed by
test No. 1) in suspension. On applying heat, an orange yellow solu-
tion results.
3. Treat this solution with sulphuretted hydrogen; a black ppt. occurs,
the filtrate appearing of a blue color.
4. Plumbic acetate; a purple red ppt.
B.—METALs whoSE SULPHIDES ARE SOLUBLE IN THE ALKALINE
SULPHIDES.
TIN (Sn).
Atomic weight, 118. Specific gravity, 7-28. Fusing point, 442-4°F.
(228°C). Atomicity, dyad as in stannous salts (as Sn"O ; Sn"Cla);
and tetrad, as in stannic salts (Sn"O2; SnºCl4).
History.—The metal was known to the ancients.
Natural History.—Found in veins as “tin stone '' (SnO2) in the
granite and quartz (mine-tin). Also found in Small round masses in
alluvial soils (stream-tin ore). It is often found associated both
with arsenical iron pyrites, and also with manganese and iron oxides,
and with tungstic anhydride (WOs), in the mineral called “wolfram.”
Preparation,-(a.) The ore is first crushed, and afterwards washed,
to remove foreign matters (Sp. Gr. of quartz 27 ; of SnO2 6:5).
(3.) The washed ore is then roasted, by which means the arsenic
(as As2O3) and the sulphur (as SO3) are expelled. The iron present
after roasting exists as Fe2O3, and the copper chiefly as sulphate. To
effect the complete conversion of the sulphide into sulphate of copper,
the roasted ore, damped with water, is exposed to the air for some days.
(y.) The mass is now treated with water, which dissolves out the
cupric sulphate, and mechanically washes away much of the ferric
oxide, owing to the specific gravity of the ferric oxide being very
much less than that of the stannic oxide.
(6.) The residual tin ore is now reduced. This is effected by mixing
it with powdered coal and a little lime, and subjecting the mixture to
heat in a reverberatory (reducing) furnace. The coal reduces the
SnO2, CO being evolved, whilst the lime forms a fusible slag with the
earthy impurities.
(s.) The reduced metal is then refined. Crude tin contains iron,
arsenic, copper and tungsten. The purest portions of metal, being less
fusible than the alloy, melt first, thus permitting their easy separa-
tion. The purity of the tin is roughly shown by its breaking up into
irregular prismatic fragments (dropped or grain tin), when the hot
ingots are struck with a hammer.
Properties.—(a.) Physical. A white metal, soft and malleable, but
not ductile, unless heated to 212°F. (100° C.). It is very wanting
384 HANDBOOK OF MODERN CHEMISTRY.
both in tenacity and elasticity. It crackles when bent, developing
heat. Its smell when rubbed is peculiar. It may be made to crystal-
lise by slow cooling. Its crystalline character is well shown in the
moirée métallique, which is prepared by washing tin plate with dilute
nitro-hydrochloric acid. It fuses at 442°F. (227°C.), but is not
volatile. It is a good conductor of heat and electricity.
(3.) Chemical. At ordinary temperatures tin is unacted upon either
by air or by water, singly or conjointly. It burns in air at a high
temperature, with a white light, forming “putty powder” (SnO2).
When red-hot it decomposes steam, an oxide of the metal being
formed.
Action of acids.-Strong nitric acid (Sp. Gr. 1-5) has no action upon it;
dilute nitric acid (Sp. Gr. 1-3) does not dissolve it, but forms with it the
insoluble metastannic acid (H2Sn;011,4H2O), and ammonia, this latter
resulting from the decomposition of the water. When strong sulphuric
acid is boiled with it, it converts it into stannic sulphate (SnzSO,),
SO, being evolved with the separation of sulphur, the latter probably
resulting from the stanmous Sulphate becoming oxidised to stannic
sulphate, at the expense of the oxygen of the sulphurous anhydride.
Dilute sulphuric acid has no action upon it. Strong hydrochloric acid
dissolves it when heated, hydrogen being evolved. It is soluble in
aqua regia, SnCl, being formed.
The fired alkaline hydrates, when heated with the metal, dissolve it,
hydrogen being evolved, and an alkaline metastannate formed. Tin
combines readily by heat with sulphur, with phosphorus, and with
the haloids.
Impurities.—Lead, iron, copper, arsenic, antimony, bismuth, gold
and tungsten.
Uses.—Tin-foil. Tºn plate (which consists of iron coated with tin).
The iron, after being freed from adhering oxide by immersion in acids,
and by subsequent scouring and washing, is dipped into melted tin.
Sometimes the dipped plate is hammered, in order to effect the
more perfect union of the tin and iron (block tin). If the covering of
the tin be imperfect, the corrosion of the iron is rendered more rapid,
a galvanic couple being formed, which decomposes the water, the
oxygen of which rusts the iron. In tinming copper vessels, any oxide
on the copper is first removed by rubbing it over with ammonic
chloride, and heating (CuO +2NH,Cl=CuCl2 + H20+2NH3).
Pins are made from brass wire tinned by boiling in water containing
cream of tartar, alum, sodic chloride and granulated tin. An acid
solution of tin is formed, from which the tin is thrown down on the
brass by electrolysis.
Tin forms an important ingredient of many alloys, as e.g., Britannia
metal (Brass, Sn,Sb,Bi); pewter (Sn, Pb); speculum metal (Cu,Sn, a little
As); bell metal, gun metal and bronze (Cu,Sn); bronze coin (Cu,Sn,Zn);
type metal (Sn, Sb, Pb); solder, such as fine solder (2Sn 1.Pb), common
TIN AND OXYGEN.
385
solder (1Sn and 1Bb), coarse solder (1Sn and 2Pb), An amalgam of
tin and mercury is used for silvering mirrors.
Compounds of Tin.

Formula | #: | 3 &
Formula º = 5, H 5 Sn
SALTS. (Constitu- || 3: 3 :
º - - 9– t.
(General) tional). : # 3'5 per cen
1. Stannous oxide (protox-
ide of tin) .. Sn"O SnO 134 88'06
2.3 Sesquioxide of tin Sn,03 §:30
3.5 Y Stannic oxide (binoxide
of tin) * @ SnO, SnO, 150 6-95 78.66
4. Metastannic acid . . Sn,0,0,5H20 | Sn;0s Holo | 840 70-23
5. U Stannic acid . . . . . . . . . H2SnO, SnO Ho, 168
6. 3 (Stannous chloride (pro-
TE tochloride). . tº e Sn"Cl, SnCl, 189 62°43
7. § Stannic chloride (bichlo-
35 ride, tetrachloride) .. SnlyGl, SnCl, 260 || 2:234 45° 38
(Bromides and iodides
similar to chlorides.)
8. , , Stannous Sulphide (pro-
3 tosulphide) * & SnS SIn S' 150 78.66
9. # Distannic trisulphide Sn,S | Sns's,
e. (sesquisulphide of tin) } 2'-3 Sn S^
10, # lsº sulphide (disul-
hide) e e º e º e SnS, SnS", 1S2
11 Stannic sulphate . Sn?S0,
CoMPOUNDs of TIN AND OxYGEN.
Stannous oxide SnO.
Sesquioxide of tin SnoC)3.
Stannic oxide SnO2.
Metastannic acid ... 5SnO25H2O.
Stannic acid SnO2, H2O.
(1.) Stanmous Oxide,-Protoxide of tin (SnO).
Preparation.—(1.) (As a hydrate [2SnO, H2O). By adding an excess
of an alkaline carbonate to a solution of stannous chloride.
(2.) (Anhydrous). By igniting the hydrate in nitrogen or in carbonic
anhydride.
(3.) By heating stannous oxalate in closed vessels.
the open air it forms SnO2.)
Properties.—The hydrate is a white body freely absorbing oxygen
from the air. It is soluble when boiled in a strong solution of
potassic hydrate, but if the boiling be long continued, or if the
solution be kept for some time, the metal is precipitated and SnO,
remains in solution. It is soluble in acids. With sulphuric acid it
C C
(If heated in
386 HANDBOOK OF MODERN CHEMISTRY.
forms stannous sulphate (Sn"SOA). The anhydrous oxide is a black
permanent body, and burns like tinder, forming SnO2.
(2.) The Sesquioxide of Tin (Sn,03) is but little understood.
(3.) Stannic Oxide.—Binowide of tin (SnO2) is found native as
tin-stone. It is formed whenever the metal or stannous oxide is
heated in air. It is insoluble in acids, but forms soluble compounds
when boiled with the alkalies. It forms two hydrates, both of which
are acids, as follows:–
(4.) (a.) MetaStannic Acid (5SnO2,10H2O) is formed by the action
of nitric acid on tin. When this product is dried at 212° F (100° C.)
it becomes 5SnO2,5H2O, a white powder insoluble either in water or
in acids. By the further action of heat it changes to a yellow color
(probably becoming anhydrous), forming what is called “putty
powder,” a substance used as a plate polisher. The acid forms
non-crystallizable salts called “metastammates,” in which one-fifth of the
hydrogen of the acid is replaced by a metal—
ſºo! (Snoºl.
(5.) (6.) Stannic Acid (SnO2, H2O) is formed when an alkali is added
to a solution of stannic chloride. It is soluble in acids, and also in
cold solutions of potassic and sodic hydrates, forming crystallisable
salts called “stammates,” in which the whole of the hydrogen of the acid
is exchanged for the metal (e.g., SnO2,Na,0).
Sodic Stammate (SnO2, Na2O,4H2O) forms the “Tin Prepare Liquor ’’
of the calico-printer.
CoMPounds of TIN AND CHLORINE.
Stannous chloride * * * * * * * * * SnCl2.
Stannic chloride © tº a * * * w º gº SnClſ.
(6.) Stanmous Chloride.—Protochloride of tin; Tim salt (SnCl2).
Preparation.—(1.) (As a hydrate.) By dissolving tin in hydrochloric
acid, and evaporating down the solution until it crystallises (SnCl2,2IH2O;
Sp. Gr. 2:7).
(2.) (Anhydrous.) By heating the hydrate to 212°F. (100° C.).
Properties.—It has a strong attraction for chlorine, and also for
oxygen, absorbing the latter from the air, whether exposed in a solid
form or in solution, a mixture of stannic chloride and stannic oxy-
chloride being formed. Hence the use of stannous chloride as a reducing
agent;-dechlorinating chlorides;–deoxidising salts of mercury, silver
and gold;—converting ferric and cupric salts into ferrous and cuprous
salts;–depriving sulphurous acid of its oxygen, whereby a yellow pre-
cipitate of stannic sulphide is thrown down;–deoxidising indigo —
reducing combined metallic acids (such as CrO3, As2O5, etc.) to a lower
state of oxidation. When mixed with a quantity of water, stanmous
chloride is decomposed, a white. hydrated oxychloride being formed
TIN AND SULPHUR. 387
(SnCl2,SnO,2H2O). It is also decomposed by heat. It forms double
crystallisable chlorides.
Stannous chloride constitutes the “tin crystals,” or “salts of tin,”
of the dyer. It is commonly dissolved for use in a copper vessel, its
solubility being increased by the resulting voltaic action.
(7.) Stannic Chloride.—Bichloride and tetrachloride of tin ; fuming
liquor of Libavius (SnCl4).
Preparation.—(1.) (As a hydrate.) By heating tin with nitric and
hydrochloric acids. -
(2.) (Anhydrous.) By passing chlorine over metallic tin.
(3.) By distilling together powdered tin (1 part) and corrosive sub-
limate (5 parts) (2HgCl2+Sn=SnCl, + Hg2).
Properties.—A thin colorless fuming liquid, boiling at 239.5° F.
(115-3°C.); Sp. Gr. 2:234. It has a vapor density of 9-2. When
mixed with a little water, it solidifies to a soft mass called “butter of
tin” (SnCl,5EI.0). On adding an excess of water to stannic chloride,
hydrated stannic acid is thrown down. It forms numerous double
salts, as e.g., the “pink salt” of the dyer (2H1NC), SnCl). It is largely
used by dyers (nitro-muriate of tin) for the purpose of fixing and
brightening red colors.
CoMPOUNDS OF TIN AND SULPHUR.
Stannous sulphide * * * - - - * * * SnS.
Sesquisulphide of tin • * * we tº º * * * SngSA.
Stannic sulphide ... * * * tº ºr tº * tº tº SnS2.
(8.) Stanmous Sulphide.—Protosulphide of tin (SnS). Found
native as “tin pyrites.”
Preparation.—(1.) By fusing together tin and sulphur.
(2.) By passing sulphuretted hydrogen through a solution of a
Stannous salt.
Properties.—A blackish grey body, soluble in hot hydrochloric acid,
sulphuretted hydrogen being evolved.
(9.) Sesquisulphide of Tin (SngSs) is prepared by heating stannous
sulphide with one-third its weight of sulphur.
(10.) Stannic Sulphide.— Disulphide of tin ; mosaic gold; bronze
powder (SnS2).
Preparation.—(1.) By heating together, at a low red heat, tin (12
parts), mercury (6 parts), ammonic chloride (6 parts), and sulphur
(7 parts).
(2.) By passing sulphuretted hydrogen through a solution of stannic
chloride.
Properties.—A yellow-colored body, used in the arts as an imitation
of gold or bronze. It is soluble in solutions of the alkaline hydrates
388 HANDBOOK OF MODERN CHEMISTRY.
when heated, and also in aqua regia, but is insoluble in nitric or in
hydrochloric acids.
Tests for Tin.—(See ANALYTICAL TABLEs.)
ANTIMONY (SB).
Atomic weight, 122. Molecular weight, 488. Specific gravity, 5-7 to 6-7.
Fusing point, 842°F. (450° C.). Atomicity, a triad in antimonious
salts (SbCls; Sb2O3), and a pentad in antimonic salts (SbOls;
Sb2O5).
History.—Discovered by Basil Valentine.
Natural History.-It is found native, but more commonly occurs
as stibnite, or grey antimony ore (Sb2S3).
Preparation.—(1.) By melting out the antimony (owing to its
ready fusibility) from the metals with which it is alloyed (crude anti-
mony).
2. (a.) The ore (Sb2S3) is first roasted, in order to drive off some
of the sulphur and arsenic present. .
(3.) The roasted ore, which consists of a mixture of oxide (Sb.O.)
and sulphide (Sb2S3), is now fused with charcoal and sodic carbonate
(regulus of antimony). The sodic carbonate converts any sulphide
present into oxide (Sb2S3+3Na2CO3=3CO2 + 3Na2S--Sb2O3), whilst
the carbon reduces the oxide to the metallic state (Sb2O3 + 3C=
3CO+Sb.).
(3.) An amorphous form of the metal may be prepared by the elec-
trolysis of a solution of tartar emetic in antimonious chloride.
Properties.— (a.) Physical. A bluish-white, brittle metal, either
crystalline or amorphous. It fuses at 842°F. (450° C.), and vola-
tilises at a bright red heat. In solidifying it expands. Its power of
conducting heat and electricity is comparatively small.
(6.) Chemical.—At ordinary temperatures antimony is unacted upon
by the air, but when heated it burns, forming Sb2O, (antimonious
oxide). It fuses and fires when thrown into chlorine, and also
combines with bromine and iodine when brought into contact with
them, with the evolution of heat. Nitric acid oxidises it to antimonic
anhydride (Sb2O3), which is insoluble in the acid. It readily dissolves
by heat in aqua regia, and also in hydrochloric acid, hydrogen being
evolved. It is soluble in potassic sulphide.
Uses.—It is used in the preparation of several alloys, such as type
metal (2Pb, ISn, and 1Sb), a compound that expands slightly on
cooling; Britannia metal (9Sn, 18b); pewter (12Sn, 18b, and Cu), etc.
It is used in medicine.
ANTIMONY. 389
Compounds of Antimony.
3–4
Formula ; : 3 F.
Formula & #5, #: Sb
SALTS. (General.) º º #3 per cent.
$ 3P 2 c5
1. Antimoniuretted hy-
drogen (stibine) . . H.Sb SbFI, 125-0 97.60
2. ſ Antimonious oxide(ter-
oxide) . . . . Sb,03 Sb,0, 292.0 83-56
3. 3 || Antimonic oxide or
# 3 anhydride(antimonic g
& | acid) . . . . . . Sb2O, Sb,0. 324-0
4. Antimonious antimo-
niate . . . . . . Sb,0s,Sb,0s | SbO,Sbo” 308-0
3. & 3 ( Antimonious chloride SbCl, SbCl, 228-5 53-39
6.3 ± } Antimonic chloride .. SbCls SbCl, 299 - 5
7.*.* ‘Antimonious bromide SbBr, Sb.br,
8. 3 y iodide.. Sb.I., Sb.I.,
9. 3 y fluoride(?) SbF, SbF,
10...!, É ( Antimonious sulphide Sb,Sa Sb,S, 340-0 || 4-6 || 71-77
11:33 {{# sulphide .. Sb2S, Sb,S. 404-0 60-4
2-
(1) Antimoniuretted (or Antimonetted) Hydrogen; Stibine;
Antimonious hydride (H3Sb).
Preparation.—By acting either (a.) on zinc mixed with any anti-
monious salt, or (ſ3.) on an alloy of zinc and antimony with dilute
sulphuric acid (see nascent hydrogen, p. 9.).
(a.) SbCl, + 3H2 = SbH, + 3HCl.
Antimonious + Hydrogen = Stibine + Hydrochloric
chloride - acid.
(6.) Sb, Zn", + 6HC1 = 2SbFI, + 3HCl.
Zinc antimony + Hydrochloric = Stibine + Hydrochloric
alloy acid acid.
Properties.—A colorless, odorless, combustible gas forming when
burnt, if the supply of air be free, antimonious oxide and water
(2SbFIa+ 3O2=Sb2O3 + 3H2O), but if the supply of air be limited,
the metal and water, the hydrogen only being in such case oxidized
(4Sb]H3+30s–Sb, +6H2O). A piece of cold porcelain held in the
flame becomes rapidly coated with a black film of the metal. The
gas is decomposed into its elements when passed through a red hot
tube.
Passed into a solution of argentic nitrate a black precipitate of
antimonious argentide is formed.
(N.B.-HsAs precipitates metallic silver).
3AgNO3 + SbFIS = 3HNO3 + SbAgs.
Argentic nitrate + Stibine = Nitric acid + Antimonious argentide.
From this reaction its composition as Sb.Hs is inferred, the exact
determination not being possible, owing to the gas having never been
obtained free from hydrogen. SbFIs being its composition, its rela-
390 HANDIBOOK OF MOIDERN CHEMISTRY.
tionship to NH3. PHS, and AsFIs becomes obvious. Moreover com-
pounds of antimony with the alcohol-radicals, analogous to those
formed by nitrogen, phosphorus and arsenic also exist, such as for
example : trimethyl-stibine Sb (CH3)3, etc.
CoMPOUNDS OF ANTIMONY AND Oxygen.
Antimonious oxide (anhydride) ... Sb2O3
Antimonious antimonate ... ... Sb2O3, Sb2O3(=Sb2O4),
Antimonic oxide (anhydride) ... Sb2O3.
(2.) Antimonious Oxide, Triowide, Sesquioaide, or Anhydride
(Sb2O3).
Natural History.—Found native as valentinite (white antimony
ore ; Sp. Gr. 5-56) and senarmontite.
Preparation.—(1.) By the combustion of metallic antimony in air
or oxygen (2Sb2+ 3O2=2Sb2O3).
(2.) By digesting in a solution of sodic carbonate, the precipitate
formed when a solution of antimonious chloride is poured into
water.
2SbCls + 3Na2COs Sb2O, + 3CO2 + 6NaCl.
Antimonious + Sodic = Antimonious + Carbonic + Sodic
chloride carbonate oxide anhydride chloride.
Properties.—A dimorphous body, crystallising, like AS20s, both in
needles, and in octahedra (iso-dimorphous). It is yellow when
hot, and white (or buff-colored) when cold. It is fusible, volatile,
and combustible, Sb2O4 constituting one of the products of its com-
bustion.
It is soluble both in hydrochloric acid (SbCl, being formed) and in
tartaric acid. With nitric acid it forms antimonic anhydride (Sb2O5).
By the action of sulphuric acid upon it, an insoluble sulphate is pro-
duced. The basic properties of the oxide, however, are feeble. It is
soluble in solutions of the fixed alkalies, and is hence called anti-
monious acid, and its salts antimonites.
It is soluble in a boiling solution of hydric-potassic tartrate or
cream of tartar (HKCAH-106), forming the compound known as tartar
emetic (K, SbO,C, H,06), which, unlike antimony salts generally, is
both soluble in, and undecomposed by, water.
By ignition in hydrogen or with carbon, the oxide is reduced to
the metallic state.
Uses.—As a substitute for white lead.
(3.) Antimonic Oxide, Pentotide or anhydride, formerly called
Antimonic acid (Sb2O5).
Preparation.—(1.) As a hydrate; (Antimonic acid Sb2O3.H2O). By
the action of nitric acid on antimony.
(2.) By decomposing antimonic chloride (SbCl.) with water.
(3) (Anhydrous). By heating the hydrate below redness.
Properties.—Antimonic oxide is white when cold and yellow when
CEILORIDES OF ANTIMONY. 391
hot. At a strong heat it is converted into Sb2O4. It is insoluble
both in water and in acids. It is soluble in, and forms definite com-
pounds with, the alkalies.
- Hydrates (Acids) of Antimonic Oaxide.
Antimonic Acid (H2O, Sb2O5=HSbO3) is formed when antimony is
treated with nitric acid (Sb2+4HNO3=N,0s--2HSbO3+N2O2+ H2O).
It is monobasic.
It forms salts as follows : —
(a.) Normal salts, M'SbO3(M'.0, Sb2O3).”
(6.) Acid salts, M'.Sb,011(M'20,2Sb2O3).
Metantimonic acid (2H2O, Sb2O5=HASb2O7) is formed when anti-
monic chloride is treated with water. It is bibasic. It forms salts
as follows:—
(a.) Normal salts, M'Sb2O,(2M'20,Sb2O3).
(3.) Acid salts, M'SbO3(2M20,2Sb2O3).”
The Hydric-potassic metantimoniate (K2H2Sb2O7,6H2O) is used in the
laboratory as a test reagent for sodium compounds, forming with them
the insoluble (and the only insoluble sodium salt known) hydric-sodic
metantimoniate (Na2H2Sb2O7,6EI2O). It should be remembered that
the normal potassic antimoniate, into which the acid antimoniate
rapidly passes, does not precipitate sodic salts.
(4.) Antimonious Antimoniate (Miller); Diantimonic tetroacide
(Frankland); Antimonoso-antimonic oaside (Watts); (Sb20s, Sb2O3=
Sb2O, ; 'Sb".O.).
Natural History.—It is found in nature as cervantite (antimony
ochre).
Preparation.—(a.) By the ignition of antimonic oxide (Sb2O3), or
(3.) by burning antimonious oxide (Sb2Os) in air.
(a.) 2Sb2O5 = 2Sb2O1 + O.
(3.) 2Sb2O3 + O. = 2Sb2O,.
Properties.—A grey, infusible, non-volatile powder, insoluble both
in water and in acids.
Its constitution is doubtful;—
(a.) Some regard it as (Sb2O3, Sb2O5) because (1) when treated with
tartaric acid, Sb2O8 is dissolved, and Sb2O5 remains undissolved; and
(2) that when its solution in hydrochloric acid is dropped into water,
Sb2O8 is precipitated, and Sb2O3 remains dissolved.
(3.) Others regard it as Sb2O, because it is soluble in alkalies
without decomposition, forming salts called antimonites (e.g.,
R.O, Sb2O, ; K20,2Sb2O, etc.).
CHLORIDES OF ANTIMONY.
Antimonious chloride ... ... Sb'Cl(SbCl.).
Antimonic chloride tº s º ... SbCl3(SbCl3).
* N.B.-It will be noted that the acid metantimoniate is isomeric with the normal
antimoniate.
392 EIANDBOOIK OF MODERN CEIEMISTRY.
(5.) Antimonious Chloride; Terchloride of antimony; Butter of
antimony (SbCl3).
Preparation.—(1.) By distilling corrosive sublimate with antimony
(or antimonious sulphide).
Antimony + Mercuric = Antimonious + Antimony + Mercurous
chloride chloride amalgam chloride.
(2.) By the action of hydrochloric acid on antimonious sulphide.
Sb2S, + 6HCl = 3H.S + 2SbOls.
Antimonious + Hydrochloric = Sulphuretted + Antimonious
sulphide acid hydrogen chloride.
(3.) By the direct union of chlorine and the metal—
Sb2+3Cl2=2SbCls.
Properties.—A volatile, crystallizable, very deliquescent, and corro-
sive solid. It is fusible at 161-6°F. (72°C.), and volatile at higher
temperatures. It boils at 433° F (223°C.). It is soluble in hydro-
chloric acid and in a little water, but is decomposed by a large eaccess of
water, an insoluble oxychloride or powder of algaroth being formed
(3SbOls-H 3H2O=ShCl3,Sb,0s (or 3SbO10)+ 6HCl). By the long-con-
tinued action of water the oxychloride becomes antimonious oxide
[2(SbCls, Sb,0s)+3H2O=6HCI+3Sb.O.).
Uses.—For bronzing gun-barrels to prevent rust. As a caustic.
(6.) Antimonic Chloride, Pentachloride of antimony (SbCl3).
Preparation.—(1.) By acting on antimony with an excess of chlo-
rine (Sb2+5Cl2=2SbCl5).
(2.) By the action of chlorine on antimonious chloride (SbCl, +Cl,
=SbCl3).
Properties.—A colorless fuming liquid, having a suffocating odor.
Mixed with a little water it forms white crystals of antimonic oacy-tri-
chloride (SbOCl3), but when treated, with a quantity of water it forms
metantimonic acid (2SbOls--7II,0=HASb2O7--10HCl). It absorbs sul-
phuretted hydrogen, forming the solid antimonic chlorosulphide (sulpho-
trichloride of Frankland) (SbSCl3).
Use.—It is an active chlorinator, delivering up its chlorine with
great ease.
The analogy of the compounds of phosphorus and of antimony with
chlorine and oxygen may be noted here. Thus, SbCls and SbCls
correspond to PCls and PCls, whilst the chlorosulphide of antimony
(SbSC1,) corresponds to the chlorosulphide of phosphorus (PSCls).
CoMPOUNDs of ANTIMONY AND SULPHUR.
Antimonious Sulphide ... e e º © & © Sb2S3.
Antimonic sulphide e - tº s & © G s sº Sb2S3.
(10.) Antimonious Sulphide; Tersulphide or Sesquisulphide of
antimony; Sulphantimonious anhydride (Frankland), (Sb2S3=340).
ANTIMONY AND SULPHUR. 393
Natural History. —It occurs in nature as stibnite (grey antimony
ore; specific gravity 4'6).
Preparation.—(1.) By heating together (a) antimony and sulphur,
or (3) antimonious oxide and sulphur—
(a.) 2Sb2+3S2=2Sb2S3. (3.) 2Sb2O3+So=2Sb2S3+3S03.
(2.) By passing sulphuretted hydrogen through a solution of
antimonious chloride (2SbCl3+3H2S=Sb2S3+6HCl).
Properties.—The native compound is grey, brittle, crystalline (four-
sided prisms), and fusible. The sulphide as precipitated by H2S, is
orange red (antimony vermilion), but becomes grey by heat, the change
probably indicating its passage from an amorphous to a crystalline
form.
In closed vessels it may be distilled unchanged, but when heated
in open vessels it forms an oacy-sulphide (Sb2O3,2Sb2S3=Sb2S",0), (anti-
monious oxy-disulphide : Frankland), which when fused constitutes
what is called glass of antimony. “Red antimony Ore * is a native
oxy-sulphide. It is decomposed by hydrochloric acid (Sb2S3+6EICl=
3.H.S +2SbCls).
Sulphantimonites.—When antimonious Sulphide is acted on with
an alkaline sulphide, or with an alkaline hydrate, it is dissolved, a
soluble salt being formed, in which the alkaline sulphide constitutes
the base, and antimonious sulphide the acid. This is known as a sul-
phantimonite. Thus—
3K2O + 2Sb2S3 Sb2O3 + 3K2S, Sb2S3.
Potassic oxide + Antimonious = Antimonious + Potassic sulphantimonite.
sulphide. oxide.
The solution, when concentrated, deposits a red powder, consisting
of a variable mixture of sesquioxide and sesquisulphide of antimony
(Kermes mineral). If an acid be added to the solution of this com-
pound, Sb2S3 is precipitated.
The sulphantimonites are found native as lead, silver, copper, and
iron salts.
(11.) Antimonic Sulphide; Pentasulphide of antimony, Sulphanti-
monic anhydride; Sulphur auratum (Sb2S5).
Preparation.—By passing sulphuretted hydrogen through a solution
of antimonic chloride (2SbCls--5H.S=Sb2S3+ 10HCl).
Properties.—An orange yellow body, decomposed by boiling in hy-
drochloric acid (Sb2S3+6HCl=2SbCla-i-3H2S--S.).
Sulphantimonates.—When antimonic sulphide is acted on either
with the alkaline sulphides, or with the alkaline hydrates, a sulphan-
timonate is formed, the alkaline sulphide constituting the base, and
the antimonic sulphide the acid. These compounds are analogous to
the orthophosphates, as shown by their formula, viz., (3M.S, Sb,S.),
or M5SbS,. The sodic sulphantimonate (NassbS,) is known as
“Schlippe's salt.”
Tests for Antimony.—(See ANALYTICAL TABLEs.)
394 HANDBOOK OF MODERN CHEMISTRY.
ARSENICUM (A-75).
Atomic weight, 75. Molecular weight, 300. Specific gravity, 59.
Atomicily, triad in arsenious compounds (As2O3; AsCl3), and pentad
in arsenic compounds (As2S5; As2O5).
History.—Arsenic has been known from a very early date. The
metal was first prepared by Brandt, in 1733.
Natural History.-It is found native, alloyed with other metals,
as Co, Fe, Ni, etc. It sometimes occurs as a sulphide (realgar, AS.S.),
and as orpiment (As2S3), but is most often found in combination with
metals as an arsenide, as e.g., kupfermickel (NiAs) and NiAsa ; also as
tin-white cobalt (CoAs,). Frequently it is found as an arsenio-sul-
phide, as mispickel or arsenical pyrites (FeS2, FeAs2), or as cobalt
glance (CoS2,CoAs,) or nickel glance (NiS.,NiAs2). It is found in
Some mineral waters, also in coal smoke, etc.
Preparation.—By reducing arsenious anhydride with charcoal
(As2O3 + 3C= As, H-3CO).
Properties.—(a.) Physical. Arsenicum is a crystalline, brittle
metal, having a brilliantly metallic steel-grey lustre. When heated
to 356°F. (180°C.) it volatilises, without fusing. It is a conductor
of electricity. The metal is not a poison until it becomes oxidised.
(ſ3.) Chemical. When the dry metal is exposed to the air it under-
goes no change, but when wetted and powdered it slowly oxidises,
forming “fly-powder,” which is probably a mixture of As and As2O3.
Heated to 160°F. (71°C.) in air, it gives off condensible, colorless,
garlic-smelling fumes of As2O3. At a red heat it burns with a white
flame. It may be preserved unchanged in pure water. The powdered
metal fires spontaneously when thrown into chlorine, its union with
bromine, iodine, and sulphur, when heated, being also energetic.
Nitric acid converts it into arsenic acid. Hydrochloric acid has no
action upon it, unless it be mixed with potassic chlorate, when arsenic
acid is formed. It is soluble in a solution of bleaching-powder.
Some chemists regard arsenicum as a non-metal. Their arguments
in support of this view are its many analogies to phosphorus and
nitrogen. Like the former, it burns spontaneously when placed in
chlorine, and combines readily with sulphur and with the metals.
Moreover it is capable of existing in various allotropic modifications,
each possessing a different gravity. Others regard it as a metal,
because of its high metallic lustre, its power of conducting electricity,
its insolubility in common solvents, and its capability of forming
alloys, whereby the properties of the metals with which it is associated
are affected.
|Uses.—For fly-powder, and in the manufacture of lead shot, to
facilitate the lead assuming a globular form.
ARSENIC AND HYDROGEN. 395
Compounds of Arsenic.


Formula .# 3 3 *
Formula : 4--. # 5 | H = As
SALTS. (General.) (ºr 33 #. # | Percent.
ional.) : Et da C5
1. # Arsenious dihydride .. | º | *::::: 154-0 97' 40
2. E. ) Arseniuretted hydro-
fr; gen (arsine) . . . . HaAs As”H, 78-0 |2-695 96.15
3. * , Arsenious anhydride AsO
• 3 * ny As”,0. O 198:0 75-76
5: (white arsenic) 2 < 3 AsO
4. 8 ' Arsenic anhydride ... ' Aso. AS30s 65 - 22
5. § (Diarsenious disulphide
E (realgar). . * * As S, "As".S", 214-0 || 3-5 70-09
6. = { Arsenious sesquisul-
TE phide (orpiment) . . As. Sº As.S", 246-0 || 3-5 60-97
7. * \Arsenic sulphide .. As2S3 As, S's 310-0 48° 38
8. Arsenious chloride . . AsCla AsCl, 181°5 2-205
9. J 3 bromide . . As Br, As Bra 3-66
10. } 9 iodide tº e AsIa As Ia 456'0 || 4 - 39
11. Jy trifluoride. . AsF, AsF,
12. ,, pentafluoride ASF's
(not known in a free
state)
CoMPOUND OF ARSENIC AND HYDROGEN.
Arseniuretted hydrogen tº gº º tº e e AsH3.
(2.) Arseniuretted (or Arsenetted) Hydrogen.-Arsenious hy-
dride; arsine; trihydride of arsenic (HaAs).
JHistory.—Discovered by Scheele (1755).
Preparation.—By acting either (a) on a mixture of zinc and arsenious
acid or (3) on an alloy of zinc and arsenicum, with dilute sulphurie
acid (nascent hydrogen).
(a.) As2O3 + 62n + 6H2SO, = 2AsH3 + 62nSO, -- 3B.O.
(3.) As22n"3 + 3EIASO4 = 37.nSO, + 2AsH3.
Properties.—(a.) Sensible and physical. A colorless, garlic-smelling,
intensely poisonous gas (Sp. Gr. 2-695). It is slightly soluble in
Water. It becomes liquid at — 22°F. (– 30°C.), but has never been
solidified. It is decomposed by passage through a hot tube (AsH3=
Asa-i-3H2).
(3.) Chemical. Its reaction is neither acid nor alkaline. It burns
with a bluish-white flame, forming water and arsenious anhydride if
the supply of air be free (2AsH3+ 3O2=As. Os-1-3H2O), or water and
the metal if the supply be limited (4AsH3+ 3O2=As, +6H2O). The
flame deposits metallic arsenic on bodies placed within it, and arsenious
anhydride on bodies placed above it. It is decomposed by chlorine,
hydrochloric acid and the solid hydride (As,H, °) being formed.
396 FIANDBOOK OF MODERN OHEMISTRY.
The gas is absorbed by nitric acid, arsenic acid being produced;
also by cupric sulphate, an arsenide of copper being precipitated
(2AsH3+3CuSO4=3|H,SO,--As,Cu); and also by argentic nitrate, arse-
nic acid being formed, and silver precipitated (AsH3+6AgNO,4-3H.O
=6HNO3+H3AsO3+3Ag). The gas is also absorbed by a solution of
corrosive sublimate, and by oil of turpentine. Chemically, it is closely
related to ammonia and to phosphoretted hydrogen, all three gases
being inflammable, possessing a peculiar smell, being decomposed by
heat, and being formed by the action of nascent hydrogen on their
corresponding oxygen compounds (viz., N.0, ; P20, ; Cu20,).
(1.) The solid hydride (HAs. (Soubeiran) or As, H. (Wiederhold),) is
a brown solid, and is formed either when a plate of arsenicum is used
as the negative pole in the electrolysis of water, or when sodium
arsenide is decomposed with water. It burns in air.
(3.) Arsenious Anhydride; Arsenious acid; Arsenic triovide; White
arsenic ; Arsenio (As2O5). — Arsenious acid (H2AsO3=As,0s,3H2O).
(The acid is only known in solution.) -
Natural Iſistory.— Arsenic is found native as arsenite.
Preparation.—Either (1) by roasting arsenical ores in a current of
air, or (2) by heating arsenicum in air.
Properties.—(a.) Physical.—Arsenicum exists in two forms. (1.) A
vitreous form (specific gravity 3.738), which is transparent and color-
less when first prepared, but becomes opaque, yellowish-white, and
somewhat like porcelain, after exposure to air. Some doubt exists as
to the true cause of this change. (2.) A crystalline form (octahedra),
(specific gravity 2-695), which arsenic assumes when carefully sub-
limed in Small quantities, or when crystallized from a hydrochloric
acid solution.
Arsenic is very nearly, if not entirely, destitute both of taste and
Smell. The opaque variety has a lower specific gravity than the
transparent. Heat converts the opaque form into the vitreous, whilst
mere grinding in a mortar converts the vitreous into the opaque.
Heated to 380° F (193°C.), it softens and sublimes without fusing,
forming transparent octahedral Crystals on warmed surfaces. A
somewhat characteristic behaviour of arsenic is the white layer that
it forms on the surface of water when the arsenic is thrown into it in
a state of powder, the particles of arsenic repelling the water and
collecting round the air bubbles.
The solubility of arsenic in water is a question of very considerable
importance. The following are the chief circumstances that serve to
modify the dissolving action of water on the acid:—
1. The peculiar modification of acid used.
2. Its admixture or contamination with organic matter. It is said
that the presence of greasy matter, such as bacon, reduces the solu-
bility of arsenious acid to one-twentieth. If this be the fact, it affords
a partial explanation, why sometimes its action on the human body
ARSENIOUS ACID. 397
seems to be suspended.—(Dr. Blondlot, “Medical Times and Gazette,”
Feb. 11, 1860.)
3. The length of time the water has acted.
4. The temperature of the water.
5. If boiled, the length of time that the boiling has been continued.
6. The time that elapses between boiling and the examination.
We will endeavour to state a few results we have obtained, in a
tabular form :—
Solubility of Arsenious Acid.
* | * * * * Fresh
Tºrºnt º cººline
8. CICl.
1000 grains of cold distilled water, after
standing for 24 hours, dissolved tº º 1.74 grains. 1: 16 grains. 2:0 grains.
1000 grains of boiling water poured on
the acid, and allowed to stand for 24
hours, dissolved . . . . . . . . . . 10° 12
1000 grains of water boiled for one hour,
the quantity being kept uniform by
the addition of boiling water from
time to time, and filtered immediately,
dissolved . . . . . . . . . . . . 64'5
fº . K.
y 5 5*4 , , 15' 0
y 2 76.5 , , 87-0
(3.) Chemical Properties.—Arsenious acid, when in solution, has a
feebly acid reaction; but it readily combines with bases, the salts
being called arsenites. It does not neutralize the alkalies, nor does it
decompose alkaline carbonates unless heated. The arsenites generally
are easily decomposed by a stronger acid. The arsenites of the
alkalies are soluble in water, and are very poisonous. The other
arsenites are almost insoluble; hence the action of lime and magnesia
as antidotes. Most of the arsenites are decomposed by heat, whilst
all, when heated with a reducing agent, evolve the metal in a vapor-
ous form. The copper arsenite, or Scheele's green (see page 372), and
the silver arsenite are the two most important salts.
Arsenious acid is readily soluble in solutions of the fixed caustic
alkalies, but is not very soluble in ammonia. It is very slightly
soluble in sulphuric acid, but is freely soluble in hot nitric acid, the
arsenious being changed to arsenic acid. It is also readily soluble in
hydrochloric and in some vegetable acids, in alcohol (1 in 2000 of
alcohol of specific gravity 0-802), and in chloroform (1 in 200,000),
but is insoluble in absolute ether. When chlorine is passed through
a solution of the acid, arsenic acid is formed.
Uses.—In the manufacture of glass. The solutions of the arsenites
of potash and soda are used as sheep-dipping compositions. An
arsenical soap (camphor, soap, and arsenite of potash) is used as
a preservative for the skins of animals. Arsenite of soda is used as a
means of preventing the incrustation of boilers. Arsenite of copper
398 HANDBOOK OF MODERN CHEMISTRY.
(Scheele's green) is used as a pigment for paper-hangings, feathers,
muslins, etc. Arsenic and arsenite of potash (Fowler's solution) are
used in medicine.
(4.) Arsenic Anhydride (As2O5). — Arsenio Acid, HaAsO, =
As2O5,3R20.
Preparation.—By oxidizing arsenious anhydride with nitric acid
(As2O3 +2HNO3+2H2O=N20,--As,0s,3H2O).
Properties.—Physical. A white deliquescent solid, soluble in water.
When heated it is decomposed (As2O5=As40,--O.).
Chemical. As an acid it is more powerful than arsenious acid. The
Solution of the acid, when allowed to stand, deposits crystals having the
composition As2O5,3H2O, aq. At 212°F. (100° C.) the crystals melt,
and lose their water of crystallization, becoming As2O3,3H2O. Heated
to 320°F. (160° C.) it becomes As2O3,2H2O (=HAs.O., pyro-arsenic
acid). At 392° F. (200° C.), it becomes As. Og, H2O (=EIASO,
met-arsenic acid), and at 500°F. (260° C.) As2O, only is left.
Arsenic acid is tribasic (H3AsO4). It forms salts called arsenates,
which closely resemble, and are isomorphous with, the tribasic phos-
phates.
Uses.—Arsenic acid is used in the preparation of magenta by its
action on aniline. Arsenate of soda is used by the calico-printers as a
dung substitute.
COMPOUNDS OF ARSENIC AND SULPHUR.
Diarsenious Disulphide tº dº ſº & © tº ... Asgs.g.
Arsenious Sesquisulphide ... & ſº tº ... AS383.
Arsenic Sulphide ... & ſº tº & & ... Asess.
(5.) Diarsenious Disulphide; Realgar. (As4S, or "As".S") is
found native.
Preparation.—By heating together sulphur and arsenious anhydride
(2As2O3 + Sr-2As2S2+3SO2).
Properties.—A red, transparent, fusible, and volatile solid, burn-
ing with a blue flame, sulphurous and arsenious anhydrides
(SO2 and As2O3) forming the products of combustion. It is insoluble
in water and in hydrochloric acid; but is soluble in nitric acid
(forming arsenic and sulphuric acids), also in aqua regia and in
potassic disulphide. It is decomposed by the fixed alkalies, leaving,
as a precipitate, a brown arsenical subsulphide (AS1,S). It is used in
the manufacture of fireworks.
(6.) Arsenious Sesquisulphide; Tersulphide of Arsenic ; Sulph-
arsenious [acid] anhydride; orpiment (As2S3).
Natural History.—Found native.
Preparation.—(1.) By passing sulphuretted hydrogen through a so-
lution of arsenious acid acidulated with hydrochloric acid. -.
ARSENIC AND SULPHUR. -- . 399
Sulphuretted -- Arsenious = Hydrochloric + Arsenious
hydrogen chloride acid sesquisulphide.
(2.) By subliming a mixture of sulphur and arsenious anhydride.
Sulphur + Arsenious = Arsenious + Sulphurous
anhydride sesquisulphide anhydride.
Properties.—A yellow, crystalline, fusible, and volatile substance
(Specific gravity 3-5), insoluble in water and in dilute acids. It is
decomposed by nitric acid and by aqua regia. It burns in air, but
may be sublimed in closed vessels. It is a feeble sulphur acid. It
is soluble in ammonic carbonate and also in the alkalies, an alkaline
arsenite and sulpharsenite being formed.
12KHO + 2As2S3 = 3K2S, As2S3 + 3K2O, As2O3 + 6H2O.
Potassic + Arsenious = Potassic + Potassic + Water.
hydrate sesquisulphide sulph-arsenite arsenite
On adding an acid to the solution, an arsenious sulphide (As2S3) is
reprecipitated.
Uses.—It is used as a pigment (King's yellow). The aminoniacal
solution is used for dyeing, the color being deposited as the ammonia
evaporates.
(7.) Arsenic Sulphide; Diarsenic pentasulphide ; Sulpharsenic acid
(As2S3).
Preparation.—(1.) By fusing together a mixture of sulphur and
orpiment.
(2.) (a.) By passing sulphuretted hydrogen through a solution of
sodic arsenate, a solution of sulph-arsenate of sodium is formed.
(B.) When hydrochloric acid is added to this solution arsenic
sulphide is precipitated. These reactions are seen in the following
equations:—
(a.) 2Na2O, H2O, As2O3 + 7EI.S = 8H2O + 2Nass, As2S3.
Sodic + Sulphuretted = Water + Sodic
arsenate hydrogen sulpharsenate.
(3.) 2Na2S, As2S3+ 4HCl = 4NaCl + 2 H.S + As Sg.
Sodic + Hydrochloric = Sodic -i-Sulphuretted-i- Arsenic
sulpharsenate acid chloride hydrogen sulphide.
Properties.—A yellow, volatile, fusible substance, solidifying after
fusion to an orange-colored glass. It is one of the most powerful of
the sulphur acids. It forms salts analogous to the phosphates called
sulph-arsenates (M'AsSs meta-sulpharsenate; M.A.S.S. pyro-sulpharsenate;
MsAsS, ortho-sulpharsenate).
(8.) Arsenious Chloride; Terchloride of arsenic (AsCl3).
Constitution.—Half a volume of arsenic vapor + 3 volumes of Cl = 2
volumes of AsCls (specific gravity of vapor 6:3). -
Preparation.—(1.) By burning the metal in chlorine.
400 HANDBOOK OF MODERN CHEMISTRY.
(2.) By passing dry chlorine over heated arsenious anhydride.
11As2O3 + 6Cl2 = 4AsCl3 + 3(2As2O3, As2O5).
Arsenious + Chlorine = Arsenious +
anhydride chloride. |
(3.) By distilling together arsenious anhydride and mercuric chloride.
Properties.—A heavy (specific gravity 2-2), pungent, oily, volatile,
fuming liquid, boiling at 269-6°F. (132°C.), and remaining fluid at
—20:2°F. (–29°C.). It is decomposed when treated with a quantity
of water (2AsOls--3H2O=As2O3+6HCl), but with a little water,
it forms crystals of the oxychloride (ASC10).
(9.) Arsenious Bromide is prepared in a similar manner to the
chloride. It is a fusible crystalline body.
(10.) Arsenious Iodide is prepared similarly to the chloride and
bromide. It is a crystalline orange-colored body. It is not decom-
posed by water.
Reactions of Arsenicum Compounds.—See ANALYTICAL TABLES.
GOLD (Aurum) (Au).
Atomic weight, 1967. Molecular weight (probable), 393-4. Specific
gravity, 19:4. Fuses at from 2012°F. to 219.2°F. (1100° C. to 1200°
C.). Atomicity, monad (') as in aurous compounds (AuCl; AugO), and
triad ("") as in auric compounds (AuCl4; AugO3).
History.—Known to the ancients (G) Sol).
Natural History.—It is always found in the metallic state. It
occurs as cubes or octahedra in the alluvial sands of certain rivers
(gold dust), and also in masses in certain volcanic rocks (nuggets).
It is, moreover, always found alloyed with silver, frequently with
copper, and sometimes with osmium, iridium, antimony and tellu-
rium.
Extraction.— (1.) Process of washing. This consists in treating the
well-powdered ore with water, whereby the sand is mechanically
washed away from the gold, owing to the different gravities of the
sand and the metal.
(2.) Process of amalgamation. This consists in dissolving out the
gold, with mercury from the débris with which it is associated, the
quicksilver being afterwards separated from the gold by distillation.
(3.) Sometimes the gold ore is fused with a mixture of metallic lead,
lime, and oxide of iron. The lead in a state of fusion dissolves the
gold, the liquid alloy sinking to the bottom of the slag. The gold is
afterwards separated from the lead by cupellation (see page 411.)
Preparation of pure gold.—Dissolve the gold in aqua regia (1HNO3
and 4.HCl), and add ferrous sulphate. This will become oxidised to
ferric sulphate, whilst the gold will be precipitated, the precipitate
appearing brown by reflected, but purple by transmitted light
6FeSO4+2AuCl2=2(Fe23S0)+Fe2Cl6+Aug.
GOLD AND OXYGEN. - 401
This precipitate is now boiled with hydrochloric acid, whereby all
silver and iron are removed. The pure precipitated metal is then
fused with hydric potassic sulphate.
Properties.—(a.) Physical. A soft, heavy, yellow metal, possessing
great lustre (Sp. Gr. 19:4). It is the most ductile and malleable metal
known, and is also one of the most perfect conductors of heat and
electricity. It fuses at 1899°F. (1037° C.), shrinking greatly in bulk
as it solidifies. It is volatile at the heat of the oxy-hydrogen jet,
giving off a purple vapor. A very fine gold leaf is transparent to the
green rays of light.
(6.) Chemical. Gold is unaffected at any temperature either by air
or moisture. Sulphuretted hydrogen is without action upon it. It is
soluble in aqua regia, or in any mixture which, like aqua regia,
liberates chlorine; but it is insoluble either in any simple acid (except
Selenic acid), or in solutions of the alkalies. It combines readily
with phosphorus by heat, and with the haloids in the cold.
Uses.—For coinage, mixed with 8-33 per cent. of copper, to increase
its hardness. For jewellery : pure gold is regarded as of 24 carats;
English standard gold of 22 carats (that is, 22 parts of gold in every
24). An 18 carat gold contains 4; or ; its weight of gold. Gold is also
used for gilding ; for coloring glass ruby red; for gold leaf, wire, etc.
Compounds of Gold.
.s 2: . .< * :
E : B.E.2 3.5 A
. E # 3 .59 | All
SALTS. # # 5 #5 # Qi.) per cent.
à é #55 | *P*
1. Aurous oxide or suboxide Au,0 Au,0 | 409'4
2. l Oxides |º oxide or º Au..O fluo 441-4
| or auric anhydride ** || Auo -
3. ] Chlorides { Aurºus chloride . . . . AuC1 | AuCl 232.2
4. J * Auric chloride * * * * AuCls AuCl, 303-2 | 64-86
(Iodides correspond to
chlorides.)
5. | ſ Aurous sulphide . . . . Au,S Au,S" | 425-4
Sulphides AuS"
6. ) (Auric sulphide ... ... Aus. § 489°4
- AuS"
CoMPOUNDS OF GoLD AND OxYGEN.
Aurous oxide * * * & Cº - e - tº e & Cº. & © tº AugO.
Auric oxide e - © tº ºr e e - © e - © • * * Aug0s.
(1.) Aurous Oxide; Subozide of gold (AugO).
Preparation.—Precipitated on adding a dilute solution of potassic
hydrate to one of aurous chloride. -
D D
402 FIANDIBOOK OF MODERN CHEMISTRY.
Properties.—A dark powder, soluble in an excess of alkali. It rapidly
decomposes into auric oxide and the metal.
(2.) Auric Oxide; Perowide or Sesquioxide of gold; Auric anhydride |
(Aug03=441-2).
Preparation.—A solution of auric chloride is decomposed by mag-
nesia, a magnesic aurate being precipitated. This magnesic aurate is
then digested with nitric acid, when an insoluble auric oxide remains,
either as a yellow hydrate (Aug03,3H2O), or as a brown precipitate
(Aug03), the exact compound formed being dependent on the strength
of the nitric acid employed.
Properties.—By exposure to light, or by a heat of 473°F. (245° C.),
auric oxide is resolved into the metal and oxygen. With the alkalies,
the hydrated oxide forms soluble salts, called the aurates, as, e.g.,
potassic aurate (KAu02,3}{2O), a compound used by electro-gilders.
With the earths, and with other metallic oxides, it forms insoluble
compounds. With ammonia, it forms “fulminating gold '' --
(Aug0s,4NHs, H2O).
Strong nitric and sulphuric acids dissolve it, the oxide being
deposited on dilution. With HCl, HI, and HBr, it forms AuCl4,
Auls, and AuBra.
CoMPOUNDS OF GoLD AND CHILORINE.
Aurous chloride e e ſt - - - § - 4 º, º º AuCl.
Auric chloride tº a tº * - - e ſº o e - e. AuCl4.
(3.) Aurous Chloride; Protochloride of gold (AuClaž32-1).
Preparation.—By heating auric chloride to 347°F. (175°C.), until
chlorine ceases to be evolved.
Properties.—An insoluble yellow substance, decomposed at 390°F.
(200° C.). By the action of boiling water, or by mere exposure to
light, it is converted into the metal and AuCl4.
(4.) Auric Chloride; Terchloride of gold (AuCl4=303: 1).
Preparation.—(1.) By dissolving gold in aqua regia and evaporat-
ing the solution at 248° F (120° C.).
(2.) By heating gold-leaf in a current of chlorine.
Properties.—A red, deliquescent, crystalline mass. Heated to 390°
F. (199° C.), it becomes AuCl; but when heated above this tempera-
ture, it is entirely decomposed. It is soluble in water, in alcohol,
and in ether, the latter solvent being capable of removing it from its
aqueous solution. Its solution in water stains the skin and other
organic matter purple, finely divided gold being deposited. The
extreme ease with which the gold of the salt may be reduced, renders
it useful in photography. -
It forms crystallizable compounds with the alkaline chlorides, and
with the chlorides of most organic bases. With ammonia, it forms
“fulminating gold.”
PLATINUM. 403
Purple of Cassius, – When a dilute solution of stannous and
stannic chloride is added, drop by drop, to a very dilute neutral
solution of auric chloride, a purple precipitate is gradually thrown
down, the subsidence of which is aided by the presence of a soluble
salt and heat. This precipitate is called “the purple of Cassius”
(Sn"Augsn.06,4EI,0ſ?), i. e., a double stannate of gold and tin). It
may also be prepared by digesting metallic tin in a neutral solution
of auric chloride. It is soluble in ammonia, the solution being de-
composed and rendered colorless by light, metallic gold being pre-
cipitated. The precipitate, mixed with a little borax, is employed
for coloring china and porcelain a rich rose red. The color is a
mixture of metallic gold and stannic oxide.
CoMPOUNDs of GoLD AND SULPHUR.
Aurous sulphide • * s * * * • * * tº º tº AugS.
Auric sulphide * * * * * * º ºn tº AugS3.
(5.) Aurous Sulphide (AusS or Augs").
Preparation.—By passing Sulphuretted hydrogen through a boiling
solution of auric chloride.
Properties.—A black substance, soluble in the alkaline sulphides.
(6.) Auric Sulphide (Augss).
Preparation.— By passing sulphuretted hydrogen through a cold
dilute solution of auric chloride.
Properties.—A yellow substance, soluble in the alkaline sulphides.
A soluble double sulphide of gold and potassium may be prepared by
heating together gold, Sulphur, and potassic carbonate. It resists a
red heat, and is used for gilding china (Burgos lustre).
Reactions of the Compounds of Gold.
1. Heated in the open air, all gold salts are reduced.
2. Ferrous sulphate gives in acid solutions (free nitric acid being
absent) a brown ppt. of metallic gold.
3. A mixture of dilute stanmous and stannic chloride (or metallic tin),
gives in a neutral solution a ppt. of “purple of Cassius.”
4. Mercurous nitrate also gives a dark brown ppt. of reduced gold.
5. Sulphuretted hydrogen, a black ppt. (AusSs) in a boiling solution.
Estimation.—Gold is estimated as the metal, precipitated by ferrous
sulphate.
PLATINUM (Pt.)
Atomic weight, 1974. Specific gravity, 21-5. Atomicity : a dyad in
platinous salts, e.g. (Pt"Cl2), and a tetrad in platinic salts (Pt"Cl,).
History.—Discovered by Wood, of Jamaica, 1741.
Natural History.—It occurs native in the debris of the older
Volcanic rocks in small grains, alloyed with palladium, rhodium,
404 IIANDBOOK OF MODERN CHEMISTRY.
iridium, osmium and ruthenium ; and sometimes also in larger
nodules, alloyed with gold, silver, copper, iron, and lead. -
Extraction.—(1.) The ore is first dissolved in aqua regia, a solution
of platinic chloride (PIC),) being formed. Ammonic chloride is now
added to the clear filtrate, by which means the platinum is pre-
cipitated as a double chloride of platinum and ammonium
(2NH4C1, PtCl4). This precipitate is now heated, when the ammonia
and the chlorine are expelled, and the metal left in the spongy con-
dition. This spongy mass is now powdered, and the powder forcibly
compressed into a solid block. This block is then intensely heated,
and hammered whilst hot, so as to weld the metallic particles together
into a solid lump (process of Wollaston).
Deville and Debray have suggested to fuse the metal in a lime
crucible by the oxy-hydrogen blowpipe, instead of effecting the union
of the metallic particles by Welding. All impurities, except rhodium
and iridium are in this way removed, the gold and the palladium
being volatilized in the metallic state, the sulphur, phosphorus, arsenic
and osmium being volatilised as oxides, whilst the iron and copper
are first oxidised and afterwards absorbed by the lime crucible.
(2.) Another process suggested by Deville and Debray is as follows:
—The platinum ore is roasted with lead sulphide and oxide, when
the reduced lead dissolves the platinum (together with some iridium
and rhodium) an easily fusible alloy being formed, whilst an alloy
of iridium and osmium (osmide of iridium), which is insoluble in
the melted lead, sinks to the bottom of the platiniferous lead. The
alloy of lead and platinum is then ladled away from the insoluble
residue, and the lead removed by cupellation from its alloy with
the platinum. The crude platinum is afterwards refined by fusion
with the oxy-hydrogen blowpipe. It still, however, retains iridium
and rhodium. These metals are said to improve rather than to
injure the platinum for the purposes of chemical apparatus.
In preparing “platinum black,” platinous chloride (PtCl2) is dis-
solved in a solution of potassic hydrate, and heated with alcohol.
The precipitated platinum black is then collected, washed and dried.
Properties.—(a.) Physical. A white hard metal, of great tenacity.
It cannot be crystallised artificially, although native octahedra have
been met with. Its specific gravity varies from 21 to 22, according
to the process by which it is prepared. It expands very slightly
by heat; hence platinum wires may be sealed into glass. It may be
fused by the oxy-hydrogen blow-pipe, or by the galvanic battery.
Its conducting power for heat and electricity is very inferior to that
of either silver or gold.
(6.) Chemical. Platinum does not oxidise in the air at any tempe-
rature, but, like silver, it absorbs oxygen mechanically when heated,
evolving it again on cooling. It is unacted upon by any acid except
nitro-hydrochloric acid. It corrodes when heated with the caustic
PLATINUM AND OXY GEN. 405
alkalies, or with the alkaline earths. At high temperatures it is easily
attacked by carbon, phosphorus, boron, silicon, etc. It possesses in
all its forms, but more especially in the spongy condition (platinum
black), a remarkable power of inducing chemical combination be-
tween oxygen and other gases (see page 9).
Uses.—In the laboratory it is largely employed, because of its in-
fusibility, and also its power of resisting chemical reagents (e.g., oil
of vitriol stills, etc.).
Compounds of Platinum.

F-' s º
Formula .# 5 || 3 >
SALTS. §. (ºn. # |º Pt per cent.
(General). tional). 3 : 35
>
. . . (Platinous oxide.. PtC) PtC) 213-4
* 3
. 93 l Platinic oxide Pto, Pto, 229.4
# 3 (Platinous chloride PtCl, PtCl, 268-4
* .3
53 (Platinie chloride PtCl, PtCl, Pt 58-12
Potassic plati- ſ Pt 40.36
no-chloride... 2KCl, PtCl, 2KCl, PtCl, 488.3 || 3:586 UK 16:02=K,O 19-29
Sodic - platino -
chloride 2NaCl, PtCl, |2|NaCl, PtCl,
Ammonic plati- Pt 44:18
no-chloride... 2H,NCl, PtCl2NH,Cl, PtCl, 446-4 || 3:009 {#s 7.62
[Bromides and io- 3
dides analogous
- to chlorides.]
£ ſ Platinous sulphide PtS PtS’’
= 'S
*āl Platinie sulphide Pis, Pts",
' ' ', | alinic sulphate Pt(SO.),
p º: Platinic nitrate. , Pt(NO),
, C : liºus sulphite PtS0,
CoMPOUNDS OF PLATINUM AND OxygłN.
1. Platinous oxide... PtC).
2. Platinic oxide Pt().
(1.) Platinous Oxide.—Monoxide or protocide (Pt.0=213-1).
Preparation.—By decomposing platinous chloride with a solution of
potassic hydrate, and afterwards neutralising with sulphuric acid.
Properties.—A black substance, easily decomposed by heat. It acts
as a feeble base, being soluble in acids as well as in an excess of an
alkali.
(2) Platinic Oxide,-Binocide of platinum (Pt(). E229.4).
Preparation.—(As a hydrate, PtC.,2H.O.) By adding sodic carbonate
to a solution of platinic nitrate. [Only one-half of the total quantity
406 IHAN DIBOOK OF MODERN CHEMIST.T.Y.
of sodic carbonate necessary for complete precipitation should be added,
because of the tendency of Pt(), to combine with alkaline bases.]
Properties.—The hydrate is brown, and the anhydrous oxide black.
All the oxygen may be expelled from the oxide by heat. It is a weak
base, the salts being yellowish-red. Occasionally it acts as an acid
(platinic acid), as, for example, in platinate of soda (Na2O,312tC2,6H2O).
CoMPOUNDs of PLATINUM AND CHLORINE.
1. Platinous chloride sº sº & gº sº e is ſº º PtCl2:
2. Platinic chloride s & tº gº tº e e ‘º e PtCl2:
(3.) Platinous Chloride.— Protochloride of platinum (PtCl2=268°4).
Preparation.—(1.) By evaporating a solution of platinum in aqua
regia to dryness, and heating the residue at 455° F (235°C.), until
chlºrine ceases to be evolved.
Properties.—An olive-green powder, soluble in potassic hydrate,
in hot hydrochloric acid (the solution being red), and in platinic
chloride (the solution being brown); insoluble in water, or in nitric or
sulphuric acids. Heat decomposes it. With the alkaline chlorides
it forms double salts called chloro-platinites, or platinoso-chlorides.
(4.) Platinic Chloride,-Tetrachloride, perchloride or bichloride of
platinum (PtCl4=339:4). - -
Preparation,-By dissolving platinum in aqua regia, and evaporat-
ing to dryness.
Properties.—A red-brown, crystalline, deliquescent salt, soluble in
alcohol, in ether, and in water, the aqueous solution being of a deep
orange color. Heated to 455°F. (235°C.) it becomes PtCl2, but when
heated beyond this it is entirely reduced. Sulphurous acid reduces it
to PtCl2. With metallic chlorides it forms double salts called chloro-
platinates, or platino-chlorides. The potassic and ammonic platino-
chlorides (2KCl, PtCl, and 20WH,Cl), PtCl) are only slightly soluble
in water, and quite insoluble in alcohol. They constitute, therefore,
a means of estimating the ammonium or the potassium present in a
solution. Both the potassic and ammonic platino-chlorides consist of
yellow octahedral crystals. The ammonium salt is easily decomposed
by heat, but the potassium salt is decomposed with difficulty. The
sodium compound is, on the contrary, of a red color, and very soluble
both in water and in alcohol. Platinic chloride also forms double
salts with the chlorides of some of the organic bases.
BASEs PRODUCED BY THE ACTION OF AMMONIA ON THE CHLORIDES
of PLATINUM.
These bases are to be regarded as ammonias, in which a part of
the hydrogen of two or more ammonia molecules has been displaced
either by platinosum (Pt") or by platinicum (Pt").
PLATINUM. - 407
(1) Diplatosamine (hydrated), Reiset's first base; [Pt"HºH20,
#,
Or H4 ... N,2H2O).
Płºń,
On adding an excess of ammonia to a boiling hydrochloric acid
solution of platinous chloride, a green precipitate is deposited (green
salt of Magnus; Pt"Cl2(NH3)2 or Nº Cl2). Of this salt there are
Pt.”
also yellow and red isomers.
The hydrochlorate of diplatosamine (Pt"HoN,2HCl, H2O) is formed
on heating “the green salt of Magnus” with an excess of ammonia.
The sulphate of diplatosamine (Pt"HoN.H.S.O.) is formed when
argentic sulphate is added to a solution of the hydrochlorate.
The hydrated base diplatosamine (Pt"Huona,2H2O) is formed by
acting on a solution of the sulphate with baric hydrate.
This base is a strong, caustic, deliquescent alkali, and like the
alkaline hydrates, both absorbs carbonic acid from the air, and expels
ammonia when added to its salts.
[Nitrous acid gives with the salts of diplatosamine a blue or green
precipitate or coloration.]
(2.) Platosamine (hydrated), Reiset's second base [Pt"H.N.,H.0 or
Hg |
H. J. N.B.0].
Pt" |
This is prepared by heating the hydrate of diplatosamine to 230°F.
(110° C.) so long as it gives off water and ammonia. It acts as a
base, forming insoluble but easily decomposed salts with acids.
The hydrochlorate of platosamine may be produced by heating the
hydrochlorate of diplatosamine until it ceases to give off water and
ammonia. Thus—
Pt"H.N.,2HCl, EI.O + heat = Pt"H.N.,2HCl + H20 + 2NH3.
Hydrochlorato of = Hydrochlorate of + Water + Ammonia.
diplatosamine platosamine.
(3) Platinamine (hydrated), Gerhardt's base (Pt"H2N2,4II.0 or
H.
Ptiv } N2, 4 H2O).
The hydrochlorate of platinamine (Pt"H.N.,4HCl) is formed by
passing chlorine through hydrochlorate of platosamine suspended in
boiling water.
The nitrate of platinamine (Ptºli.N.,4HNOs) is formed by boiling
the hydrochlorate of platinamine with argentic nitrate. -
The hydrated base platinamine (Pt"H.N.,4H.0) is formed on adding
ammonia to a boiling solution of the nitrate. It has the same com-
position as that assigned to fulminating platinum.
Other platinum compounds derived from ammonia, such as the salts
of Gros and Raewsky, are known. They are believed to be com-
408. HANDBOOK OF MODERN CHEMISTRY.
pounds of the base diplatinamine (Pt"HaN,2H2O), although the
base itself has not, as yet, been isolated. -
CoMPOUNDS OF PLATINUM AND SULPHUR.
(1.) Platinous sulphide... dº ſº e ... Pt.S.
(2.) Platinic sulphide ... e e gº ... Pt.S2.
(8, 9.) These sulphides are formed by the action of sulphuretted
hydrogen on platinous and platinic chlorides respectively. Platinic
sulphide is soluble in the alkaline sulphides and hydrates, forming
the sulpho-platinates.
Reactions of Platinum Compounds.
Platinic Salts.
1. Sulphuretted hydrogen; a black ppt., soluble in excess of ammonie
sulphide. -
2. Ammonia; a yellow ppt. (2NH4C1, PtCl4), decomposed by heat.
3. Potassic hydrate; a yellow ppt. (2KCl, PtCl4).
4. Stamnous chloride; a deep brown in acid solutions.
5. Potassic iodide; a brown ppt. of Pt.Tº.
Estimation of Platinum.—(1.) As a metal.
(2.) As a potassic or ammonic platinic chloride—
100 (2KCl, PtCl4) = 40-36 Pt.
100 (2NH,Cl,PtCl) = 44-18 Pt.
MOLYBDENUM (Mo),
Atomic weight, 96, Atomicity; dyad in molybdous compounds (as MoCl2,
Moſ)), and tetrad in molybdic compounds (MoC), MoCl).
Natural History.—It occurs chiefly as a disulphide (called molyb-
dena (uox{{33atva) from its resemblance to black-lead), and also as a
plumbic molybdate (Pb)\ſo0,).
Preparation.—The sulphide is first roasted, whereby MoC),
(molybdic anhydride) is formed. This is reduced by heating with
charcoal.
Properties.—A white brittle metal, fusible with difficulty. It is
oxidized by boiling with nitric acid. By heat it combines with
chlorine (MoCl), forming red vapors, which condense to black scales.
It forms three oxides, viz., Mo"O, Mo'"O2, and MoviC)3. MoQs,
which is known as molybdic anhydride, is prepared by roasting the
sulphide and acting on the residue with ammonia, whereby molybdate
of ammonia is formed, a salt largely used in the laboratory as a test
reagent for the presence of phosphates, forming with phosphoric acid a
phospho-molybdate of ammonia. At a red heat, molybdic anhydride
fuses to a yellow glass, and sublimes. No definite hydrate is known.
MOLYBDENUM. - 409
Molybdenum forms three sulphides, viz., MoS2, MoSs (sulpho-
molybdic acid), and MoS, (persulphomolybdic acid).
It forms three chlorides, viz., molybdous chloride (MoCl2), a Ses-
quichloride (MozCl6), and a molybdic chloride (MoCl4).
Compounds of Molybdenum.
*
& 4–3
Formula Formula T; ;
SALTS. (General). (Constitutional). § *aš
#P-
g; (Molybdous oxide (protoxide) . . . . Moſ) IMIO’’O 112
5 (Molybdic oxide (dioxide) . . . . . MoQ, MovO, 128
& ,, anhydride (trioxide) . . MoQ. Movio, 144
... ( Molybdous chloride.. e e º & MoCl, Mo"Cl, 167
# Sesquichloride of molybdenum .. Mo,Cls % 405
# (Molybdic chloride (tetrachloride) .. MoCl, Monci." | 238
& Molybdic disulphide * * * * * * MoS, Moi'S, 160
3 ,, . trisulphide (sulpho-molyb-
# dic acid * * * * * * * * * * MoS, Movis, 192
E. Molybdic tetrasulphide (persulpho-
£ molybdic acid) . . . . . . . . MoS, MoS,
Tests for Molybdenum Compounds.
(A.) Tests for molybdous salts (corresponding to Mo"O); color, black
and opaque.
(B.) Tests for molybdic salts (corresponding to Moi"O.); color, red-
dish brown.
(1.) Sulphuretted hydrogen; a brown ppt., soluble in ammonic sul-
phide. t
(2) Sodic and potassic hydrates and their carbonates; a brown ppt.,
soluble in ammonic carbonates.
(C.) Tests for molybdates.
(1.) A piece of zinc in a dilute acid solution of a molybdate, turns
the liquid first blue, then green, then black.
(2.) Stannous chloride; a blue ppt. (MoC),4MoQ.).
(3.) Acids; a ppt. of MoQs, soluble in excess.
All molybdenum compounds color a borax bead dark brown in the
inner flame, and yellow in the outer flame. The color of the bead
disappears on cooling.
410 HANDBOOK OF MODERN CHEMISTRY.
CHAPTER XVII.
THE METALS OF GROUP I.
LEAD and its Compounds—SILVER and its Compounds—MERCURY and its Com-
pounds—THALLIUM and its Compounds—TUNGSTEN and its Compounds.
LEAD (Pb-207).
Atomic weight, 207. Specific gravity, 11:445. Fuses, 617°F. (325°C.).
Atomicity; dyad (PbCl2), and tetrad (PbO2; Ph(C2H5)4). Some-
times a pseudo-triad. |
History.—The metal was known to the ancients (h-scythe of
Saturn).
Natural History.—It is not found native, but occurs almost en-
tirely as a sulphide, “galena ’’ (PbS). In small quantities it is found
as a carbonate “white lead ore ” (PbCO3), and as a sulphate, “An-
glosite ” (PbSO,).
Preparation.—From Galena—1. (a.) The ore is first of all mixed
with a little lime, and then roasted with free access of air, in a rever-
beratory furnace. The following changes take place : —A part of the
PbS becomes oxidized to PbSO4; a second part loses its S (as SO2),
whereby PbO is left, whilst a third part remains undecomposed.
Thus a mixture results of PbSO4, PbS and PbO.
(6.) After the mixture of PbSO,PbO and PbS has been well
incorporated, air is excluded, and the heat of the furnace raised. The
following changes occur : —The sulphate and the oxide respectively
decompose the lead sulphide, the metal being reduced, and SO.
set free. Thus—
(a.) PbSO, 4- PbS = 2Pb + 2SO.
Lead sulphate + Lead sulphide = Lead -- Sulphurous anhydride.
(6.) 2PbO + PbS = 3Pb + SO.
Lead oxide + Lead sulphide = Lead -- Sulphurous anhydride.
2. Preparation of pure lead.—The pure nitrate is ignited, and the
oxide formed reduced with black flux.
Impurities.—Antimony (forming “hard lead'), manganese, silver,
tin, iron, copper.
Purification (“Refining. Improving ”).-The lead is first melted.
The tin and antimony present (which render the lead hard) oxidize
more rapidly than the lead. The oxides of these metals are removed
from the surface of the melted metal as-fast as they are formed,
leaving the lead in a pure state.
Extraction of Silver.—(1.) Concentration of the silver alloy by Pattin-
son's process.-This process depends on the circumstance that the alloy
LEAD. 41 1
of silver and lead is more fusible than pure lead. The lead con-
taining the silver is melted, and then well stirred as it cools. A
portion of lead, almost entirely free from silver, first solidifies and
sinks to the bottom of the vessel in the form of crystalline grains.
The silver remains dissolved in the liquid metal, which is then
poured off from the solid portion.
(2.) The silver is now obtained from this concentrated argentifer-
ous alloy by “cupellation,” as follows:–The alloy is exposed to a
high temperature in a free current of air, whereby litharge (PbO) is
formed. This PbO, which fuses at a low temperature, is then separ-
ated from the silver, by merely allowing the melted litharge to run off,
thereby leaving the silver in a state of comparative purity.
Properties.—(a.) Physical. Lead is a bluish-white metal, very soft
when pure. Its softness is more or less destroyed by the presence of
plumbic oxide, a small quantity of which is soluble in the melted
metal. It is not very malleable or ductile. By slow cooling it may
be obtained in cubes and octahedra. At a heat of 617°F. (325°C.)
it fuses, and at a white heat boils and volatilizes. It contracts
considerably at the moment of solidification. It is inferior to most
metals as a conductor of heat and electricity.
(ſ3.) Chemical. Action of air.—A perfectly dry air is without action
on lead at ordinary temperatures, but it rapidly tarnishes in moist air,
a film of oxide forming on the surface of the lead, which prevents
any further action. At high temperatures, the metal rapidly absorbs
oxygen, emitting white fumes of lead oxide, and at the same time
volatilizing slightly.
Action of water.—Pure un-aerated water has no action on lead.
Action of air and water.—Lead rapidly oxidizes from the combined
influence of air and water, the water dissolving the lead oxide formed
by the action of the air, leaving a clean surface of lead for the
further action of the air. This solution of the oxide absorbs carbonic
anhydride from the air, whereby a basic lead carbonate is precipitated
(PbCO3, PbH.O.). The water is then capable of dissolving fresh oxide
as soon as it is formed on the surface of the lead. Thus the almost
complete corrosion of metallic lead (as in e.g., in old leaden coffins)
is effected, with the conversion of the metal into a basic carbonate.
The circumstances influencing this combined action of air and water on
lead are important, viz.:-
1. The presence of chlorides, nitrates, nitrites, and ammonia in the
water promote corrosion.
2. The presence of sulphates, phosphates and carbonates, especially
of calcic carbonate in water containing CO2, hinder corrosion. The
presence of a limited quantity of carbonic acid in water interferes
with corrosion, by fixing on the lead a film of insoluble plumbie
carbonate; whilst an excess of CO2 may increase corrosion, plumbie
carbonate being soluble in water highly charged with the gas. On
412 HANDIBOOK OF MODERN CHEMISTRY.
boiling, the soluble lead carbonate subsides as the gas escapes.
The presence of vegetable matter in water also hinders corrosion, by
coating the metal with a compound of lead oxide and organic matter.
In contact with air and sea-water an oxide and a chloride of lead are
formed. Calcic sulphate, in the presence of moisture, rapidly cor-
rodes lead. . This is seen when lead pipes are placed in contact with
plaster.
Action of Acids.-Sulphuric acid and hydrochloric acid do not act
on lead at ordinary temperatures, and only slightly even when
boiling. Nitric acid (especially if dilute) dissolves it, nitric oxide
being liberated. Acetic acid dissolves it rapidly, changing it, in the
presence of carbonic acid, to white lead. Hence green oak wood
(which contains acetic acid) should never be placed near lead fittings
in buildings, nor should metallic lead ever be allowed to be in contact
with acid liquids that are used as food.
Salts of Lead.
3. e :
SALT Formula Formula ; : ## PbO or Pb
o (Common). (Constitutional). #º 3, § per cent.
#P | #5
1. Plumbous oxide; sub- - Pb
oxide of lead ... Pb,0 { Pł0
2. 2 | Plumbic oxide—
.# (Litharge) . . . . PbO IPbO 223 9.4 Pb-92.8
3. ‘ā \ Plumbic dioxide or
C peroxide (Plattnerite) PbO, PbO, 239 9.4 Pb-86-61
PbO,PbO, Pb()Pbo”
4. Minium or red leads. . . . 2PbO, PbO, PbPbo",
\ | 3PbO,PbO, PbPbO"(Pb",0)”
5. Plumbic chloride PbCl, PbCl, 278 5-8 Pb-74°46
- (Matlockite | IPbCl
(Pattinson's PbO,PbCl, O
white oxy- | PbCl
º chloride).
3 PbCl
6 # Oxy- O
º É chlorides \ Mendipite ... |} 2PbO,PbCl, Fº
O PbCl
Patent or
Turner's | 7PbO, PbCl, Pb,0,0),
yelllow .
7. Plumbic bromide .. PbPr. PbPr, 367 6:63
8. Plumbic iodide . . . . Pbſ, Pbl, 461 | 6’ 38
9. Plumbic fluoride .. PbP, Pb F,
10. śſ Plumbous sulphide ... Pb,S { {}s
11. 5. Plumbic sulphide -
#\ (galena) . . . . . PbS PbS" 239 || 7-59 || Pb-86-61
12. ‘’’ \ Plumbic persulphide.. PbS, (?)
13. Plumbic selenide .. PbSe 8:0
14. Plumbic sulphate . . PbS0, SO,Pbo” 303 || 6’ 3 PbO-73-6
15. Plumbic nitrate. . . . Pb2NO, 331 4'4 || PbO-67:37.
16. Plumbic carbonate
(lead spar) . . . . PbCO, COPbo” 6'46
LEAD. 413
Alkalies have no special action on lead.
Chlorine acts on lead until a sufficient protective covering of lead
chloride has been formed.
Uses—For such alloys as type-metal (Pb and Sb), shot, solder,
etc. The metal is largely used in building operations, as, e.g., for
cisterns, roofing, etc., and also in the construction of sulphuric acid
chambers. .
CoMPOUNDs of LEAD AND OXYGEN.
Plumbous oxide tº º º g tº tº e tº tº ... Pb2O.
Plumbic oxide i. e. e. g is tº tº ſº & ... PbO.
Plumbic peroxide ... tº $ tº ... PbO2.
Ted leads tº e de & & ſº Pb,0s; Pb,0, ; Pb,05.
(1.) Plumbous Oxide.—Suboride of lead (Pb2O).
Preparation.—(1.) By heating plumbic oxide to redness.
(2.) By heating lead oxalate to 608°F. (320°C.).
Properties.—A grey substance. Plumbic oxide and the metal are
formed when plumbous oxide is acted upon by acids.
(2.) Plumbic Oxide,-Lead protozide or monocide; litharge; massicot
(PbO).
Atomic weight, 223. Specific gravity, 9-5.
Preparation.—(1.) (As a hydrate, 2PbO, H.O; 3Bb0, H2O). By pre-
cipitating lead solutions with alkalies.
(2.) (Anhydrous). By heating lead in air.
(3.) By igniting the carbonate.
Properties.—(a.) Physical. Lead oxide is found of various colors.
It is yellow, if the heat used in its preparation be below that neces-
sary to fuse the oxide (massicot); whilst it is red (due to Pb2O3) if
the heat used be great (litharge). Litharge, when heated, turns
brown, the brown color disappearing as the oxide cools. It fuses at
a bright red heat, at which temperature it combines with silica and
clay (such as clay crucibles) to form a fusible silicate of lead. It is
easily reduced when heated with organic matter.
(6.) Chemical.—Litharge is slightly soluble in water, solution
being favored by the presence of organic matter, and hindered by the
presence of saline matters in the water. The solution is alkaline. It
absorbs CO2 from the air with great rapidity, a lead carbonate being
precipitated. It is a powerful base, and exhibits a great tendency to
form basic salts.
It is soluble in alkaline solutions, forming, with the alkalies, com-
pounds that are easily decomposed.
Uses.—As a glaze for earthenware. Also in the manufacture of
glass, on account of the ease with which it combines with silica at a
high temperature. As a flux. For “dhil mastic” (a mixture of lead
oxide and brickdust, made into a paste with linseed oil), a compound
which sets very hard, and is used for repairing stone. As a hair dye
414 HANDBOOK OF MODERN CHEMISTRY.
(a solution of the oxide in lime-water), the sulphur of the hair forming
the black PbS with the lead. -
(3.) Plumbic Peroxide or Dioſcide.—Puce, or brown lead oride
(PbO2) [Mol. Wt. 239; Sp. Gr. 9:4]. This compound is found native
(heavy lead ore).
Preparation.—(1.) By digesting red lead in boiling dilute nitric
acid.
(2.) By fusing together litharge, potassic chlorate and nitre.
Properties.—A brown substance, insoluble in water and in acids.
It is decomposed at a red heat (2PbO2=2PbO + O.). It acts as a
powerful oxidising agent ; hence its use in the manufacture of lucifer
matches, for the purpose of igniting the sulphur, and in the laboratory
as an absorbent of sulphurous anhydride (PbO2+SO2=PbSO,). It
forms, with hydrochloric acid, lead chloride, and with sulphuric acid,
lead sulphate, chlorine being evolved in the former case, and oxygen
in the latter. Its properties are acid rather than basic ; hence it has
been called plumbic acid. Thus it combines with the alkalies, as in
the salt potassic plumbate (K2O, PbO2,3H2O).
(4.) Red Leads.-Minium. A substance usually represented by the
formula Pb2O4, and less frequently as Pb2O3 and Pb,05.
Preparation.—By exposing plumbic oxide which has not been fused
(massicot), to a faint red heat of 608°F. (320°C.), for some hours in
the presence of air.
Properties.—A heavy red powder (Sp. Gr. 9:08), evolving oxygen
when heated (2Pb,01–612b0+ O.). Most acids decompose it, forming
plumbic salts and plumbic peroxide.
Uses.—In the manufacture of flint glass. For this purpose it must
be very pure, for if other oxides be present, the glass will be colored.
(5.) Plumbic Chloride (PbCl2) [Mol. Wt. 278; Sp. Gr. 5-8] is
found native as “horn-lead.”
Preparation.—By precipitating plumbic nitrate with hydrochloric
acid.
Properties.—A white substance, almost insoluble in cold water, but
soluble in boiling water (1 in 33), from which solution it is deposited
in white needle-crystals on cooling. It fuses by heat into a horny
substance, which at a higher temperature volatilizes.
(6.) There are several Oxychlorides of lead ; e.g., (1.) Pattinson's
white oxychloride (PbO, PbCl.), a compound used as a substitute for
white lead. It is prepared by adding lime-water to a solution of PbCl,
in hot water (2PbC), --CaO=PbO, PbCl.--CaCl2). (2) Mendipite
(2PbO, PbCl.). (3) Turner's yellow (Paris, patent or mineral yellow)
(7PbO, PbCl.), prepared by heating together litharge and ammonic
chloride.
A red Chlorosulphide of Lead (3SbS,2PbCl.) may be formed by
precipitating an acid solution of plumbic chloride with H2S, avoiding
an excess of the gas.
LEAD OXYSALT S. 415
(8.) Plumbic Iodide (PbT.) [Mol. Wt. 461 ; Sp. Gr. 6:38].
Preparation.—By mixing together solutions of plumbic acetate and
potassic iodide. h
Properties.—A bright yellow powder, soluble in hot water, the solu-
tion on cooling depositing golden scales.
A blue compound of an oxy-iodide with a lead carbonate is known
(Pb.OI,4BbCO3).
CoMPOUNDs of LEAD AND SULPHUR.
1. Plumbous sulphide tº dº $. º a º tº º tº Pb.S.
2. Plumbic sulphide - e - * * * & © tº PbS.
3. Plumbic persulphide ... e - tº PbS, (?).
(10.) Plumbous Sulphide.—Subsulphide of lead (Pb2S). This body
is produced during the process of smelting galena. It may be pre
pared by heating PbS in close vessels, part of the sulphur being
expelled. -
(11.) Plumbic Sulphide.—Protosulphide of lead; galena (PbS)
[lſol. Wt. 239; Sp. Gr. 7:59]. Found native as galena.
Preparation.—(1.) (As a hydrate.) By the action of H.S on a salt of
lead.
(2.) (Anhydrous.) By fusing together sulphur and lead.
Properties.—When heated in air, a mixture of plumbic oxide and
plumbic sulphate is formed, a part of the sulphur being expelled.
Nitric acid converts it into a sulphate : boiling hydrochloric acid de-
composes it, with the evolution of H2S.
Lead Oxy-salts.
(15.) Plumbic Nitrate (Pb2NO3). (Mol. Wt., 331; Sp. Gr., 4:4).
Preparation.—By dissolving the metal, or the oxide, or the carbon-
ate of the metal, in dilute nitric acid.
Properties.—A white, opaque, crystalline (octahedral) substance,
soluble in water (1 in 8 at 60°F.), and decomposed by heat into PbO,
O, and N2O4. -
Several basic plumbie nitrates, such as (Pb2NOs, PbH.O.), etc., and
also several plumbic nitrites, are known.
Lead combines with the various modifications of phosphoric acid, to
form insoluble plumbie phosphates (see page 137).
Plumbie chromate (PbCrO4) is a pigment known as chrome yellow.
(14.) Plumbic Sulphate (PbSOA), (Mol. Wt, 303: Sp. Gr., 6-8),
is found native as “Anglesite,” or “lead vitriol,” and also mixed with
lead carbonate as “Lanarkite.”
Preparation.—(1.) By adding sulphuric acid, or a soluble sulphate,
to a salt of lead in solution. -
(2) It occurs as a secondary product in the manufacture of alumi-
nic acetate.
Properties.—A white powder, soluble in ammonic acetate and in
4 || 6 EIANDBOOK OF MODERN CHEMISTRY.
concentrated sulphuric acid, slightly soluble in nitric and in hydro-
chloric acids, insoluble in water. -
A plumbic sulphite (PbSOs) is known.
(16.) Carbonate of Lead (PbCO3), (Sp. Gr. 6:46), is found native
as “cerusite.” White lead, or ceruse, is a basic carbonate (either
8PbCOs, PbH.O. or 2PbCO, PbH.O.).
Preparation of White lead.—The principal reactions involved in its
preparation are as follows:— -
(1.) The formation of acetate of lead, Pb(C.H.O.), by the action of
acetic acid on oxide of lead.
(2.) Tribasic acetate of lead is then formed [Pb(C.H.O.).,2PbO], by
combining the acetate of lead with two molecules of PbO.
(3.) By acting on this tribasic lead acetate with CO2, the lead oxide
is converted into carbonate, whilst the acetate of lead that remains is
again capable of combining with more oxide. Thus—
Pb(C.H.O.)2,2PbO + 2CO, 2PbCO3 + Pb(C.H.O.).
Basic acetate of lead -- Carbonic = Plumbic -}. Plumbic acetate.
anhydride carbonate
Processes adopted in the Preparation of White Lead:—
(A.) Dutch Process. –A piece of lead is placed in an earthen pot
containing crude vinegar. A large number of these pots, built up in
heaps, are imbedded in spent tan, an arrangement being made by
gratings for the supply of air. After some weeks, the lead becomes
almost entirely converted into carbonate, the lead acetate combining
with fresh plumbic oxide, as soon as that with which it is already
combined is converted into carbonate. The vinegar supplies the acetic
acid, and the putrifying organic matter (the tan) the carbonic anhy-
dride. The carbonate is then ground and levigated, an operation
which acts very deleteriously on the work-people.
(B.) Thénard's Process.—This consists in boiling together litharge
and acetic acid, and decomposing the tribasic acetate formed, with a
current of carbonic anhydride. The product is said to be inferior as
a pigment to that prepared by the former process.
Properties.—Lead carbonate is insoluble in water, unless the water
be charged with carbonic acid. Heat decomposes it into CO2 and
PbO. Acids dissolve it, with effervescence.
In common with all lead salts, lead carbonate is blackened by a
mere trace of sulphuretted hydrogen. The blackening, however, dis-
appears on prolonged exposure to light and air, the black plumbic
sulphide becoming converted into the white plumbic sulphate.
Reactions of Lead Compounds.—(See ANALYTICAL TABLES.)
SILVER (Argentum) (Ag'=108).
Atomic weight, 108. Molecular weight (probable), 216. Specific gravity,
10.5. Fuses at 1681°F. (91.6°C.). Atomicity monad. (AgCl; AgaO.)
History.—Silver was known to the ancients ( D = Luna).
SILVER . 417
Natural History.—Silver is found in a free state. It also occurs
as a sulphide, “silver glance; ” as a chloride, “horn silver;” and as a
carbonate; also as a compound of bromide and chloride, “embolite”
(2AgBr,3AgCl); and as a sulphantimonite, “dark-red silver ore.” It
is present in small quantities (2 or 3 ozs. per ton) in galena (PbS).
Extraction.—(1.) Liquation Process of Pattinson.—From argentifer-
ous lead (see page 410).
(2.) Amalgamation Process.—The powdered ore is first roasted with
sodic chloride, whereby a silver chloride is formed. The mass is then
agitated in water, with mercury and scraps of iron. The iron re-
duces the silver to the metallic state, whilst the mercury dissolves the
reduced silver. The amalgam is then heated, by which means the
separation of the mercury from the silver is effected.
Preparation of pure Silver.—Dissolve the impure metal in nitric acid;
precipitate the silver as AgCl, with hydrochloric acid; collect, wash,
dry, and fuse the precipitated chloride with anhydrous sodic car-
bonate in an earthen crucible.
Properties.—(a.) Physical. A white metal, with high lustre, very
malleable and ductile, and the best conductor of heat and electricity
known. It may be crystallized. Specific gravity, 10:5. It is harder
than gold, but not so hard as copper. Very thin leaves are said to
transmit a bluish-green light.
It is slightly volatile by heat. It fuses at 1681°F. (91.6°C.), ex-
panding greatly at the moment of its solidification.
(6.) Chemical. Silver is unaltered at any temperature either by
moisture or by air (Ozone probably oxidizes it). When melted, how-
ever, in air, it mechanically absorbs more than 22 times its bulk of
oxygen, disengaging it again as it solidifies. (This accounts for what
is known as the spitting of the globule.) This absorption of oxygen
may be prevented by the addition of 1 or 2 per cent. of copper to the
silver.
Action of Acids.-Hot sulphuric and dilute nitric acids dissolve it.
With the former, Ag,SO, is formed, and SO, evolved; and with the
latter, AgNO3 is formed, and nitric oxide (N2O3) evolved. Hydro-
chloric acid is decomposed by the red hot metal, hydrogen and
argentic chloride being formed.
Silver is unaffected by the alkalies. It combines with the haloids.
If NaCl be fused, or even kept for a time in a silver dish, AgCl and
NaHO will be formed. It unites when fused with phosphorus. Its
attraction for sulphur is great; hence, when exposed to the air it
rapidly blackens, Aggs being formed by the action upon it of the H.S
present in the atmosphere.
Uses.—For coinage and plate (925Ag and 75Cu = 1000 English
standard silver). “Frosted silver’’ is produced by heating the silver
in air and immersing it when hot in dilute sulphuric acid. Oridized
silver is produced by dipping the metal in a solution obtained by
E E
4.18
HANDBOOK OF MOI).ERN CHEMISTRY.
boiling together sulphur and potash, whereby the silver becomes
covered with a minute film of sulphide.
Electro-plating is performed
by depositing silver on some baser metal by electrical agency.
Compounds of Silver.


* .
F l Formula | ## 3 º
SALTS. * (d. 3 # #5 Ag of Ag:0
(Common). tional) + 3 | *, 3 per cent.
3: (a 5
r;
l. 3 (Argentous oxide . Ag,0 (?) OAg, (?)
2. 5: ) Argentic oxide Ag,0 OAg, 232.0 7-2 Ag=93-1
|-4
3. C. ,, peroxide Ag30, {3\; 248.0 5-47
4.é à {º chloride Ag,Cl (?) Ag,Cl (?)
5.5%: Argentic chloride.. AgCl AgCl 143’5 5:55 | Ag=75.26
6. , bromide. . AgBr AgBr | 1880 6:35 | Ag-57:45
7. ,, iodide AgI AgI 235-0 5-5 | Ag-45-96
8. ,, fluoride . . Ag|F Ag|F 127.0
9. ,, sulphide. . Ag.,S Ag;S 248.0 7-2 Ag=87-1
I 0. ,, Sulphate Ag,S0, SO, Ago, 312-0 5:32 | Ag,0=74.36
11. , nitrate . . AgNO, N(),Ago 170-0 || 4:33 Ag,0=68-24
12. ,, carbonate Ag.,CO, COAgo,
13. Triargentic phosphate . . Ag, PO, POAgo, 419-0 || 7-32
14. Argentic pyrophosphate | Ag, P,0, P20, Ago, 5:30
15. ,, metaphosphate | AgP0, PO, Ago
16. ,, hyposulphate. . . Ag.,S,0s(?)
17. , thiosulphate . . . Ag.,S,0, SS”0Ago"
CoMPOUNDs of SILVER AND OxYGEN.
Argentous oxide Aga().
Argentic oxide AgaO.
Argentic peroxide ... p º º º Ag30s.
(1.) Argentous Oxide; Suboatide of Silver (AgaO).
Preparation.—By heating argentic citrate to 212°F. (100°C.) in a
stream of hydrogen. The residue, which contains argentous citrate,
is then dissolved in water, and the argentous oxide precipitated from
the solution by potassic hydrate.
Properties.—A black powder, easily decomposed by heat and by
chemical reagents. It is soluble in ammonia.
(2.) Argentic Oxide; Protoxide of silver (Ag30). [At. Wt., 232;
Sp. Gr., 7.2].
Preparation.—By the action of a heat of 140°F. (60° C.) on the
brown hydrated oxide, produced when potassic hydrate is added to a
solution of a soluble silver salt. -
Properties.—(a.) Physical. A brown substance, decomposed at a
red heat (Ag,0=Aga--0), and also partially by the action of sun-
light.
(6.) Chemical.—Argentic oxide is a powerful base, completely
neutralizing acids, the salts formed being isomorphous with the
SILVER AND CHILORINE. 419
alkaline salts. Its solution in water (in which it is slightly soluble)
is feebly alkaline. It is insoluble in solutions of sodic or of potassic
hydrates, but dissolves readily in ammonia, the solution slowly
depositing the explosive argentic nitride, or “ fulminating silver’’
(Ag,N ?). It forms a yellow glass with the fusible silicates.
(3.) Argentic Peroxide (AgaO2) is deposited in small grey crystals
on the positive pole of the battery, when a voltaic current is passed
through a solution of argentic nitrate. With nitric and sulphuric
acids, oxygen is liberated, and argentic salts formed. From hydro-
chloric acid it liberates chlorine. It both decomposes and is decom-
posed by ammonia, nitrogen being evolved.
CoMPOUNDs of SILVER AND CHLORINE.
Argentous Chloride * a º * * * ... Ag.,Cl.
Argentic Chloride ... & a tº * * * ... AgCl.
(4.) Argentous Chloride, Subchloride of silver (AgeCl).
Preparation.—Either by precipitating a solution of argentous citrate
with sodic chloride, or by the action of ferric chloride on metallic
silver (2Aga--Fe2Cl6=2AgaCl-H2Fe(Cl2).
Properties.—A black substance insoluble in nitric acid. By the
action of heat or of an ammonia solution, it is converted into silver
and argentic chloride.
(5.) Argentic Chloride (AgCl)-LMol. Wi. 143’5; Sp. Gr. 5-5].
Silver chloride is found native both in cubical crystals, and also as a
compact semi-transparent mass called “horn silver.” It is found
associated with argentic bromide in “embolite.”
Preparation.—By adding hydrochloric acid, or a soluble chloride, to
a soluble silver salt.
Properties.—A white substance becoming violet on exposure to
light, AgeCl and free chlorine being formed. The decomposition is
less rapid if the chloride be very pure, and more rapid if organic
matter be present. It melts at 500°F. (260° C.) becoming a horny
mass as it cools. It is slightly volatile, but does not decompose at a
high temperature. It is insoluble in nitric acid, but is soluble in
boiling concentrated hydrochloric acid (1 in 200) from which solution
it may be precipitated by dilution with water. It is also soluble in
solutions of the alkaline and earthy chlorides, forming with them
double salts. Ammonia dissolves it freely, depositing crystals of the
chloride on evaporation. Cold solutions of potassic or sodic hydrates
do not act upon it, but when concentrated alkaline solutions are boiled
With argentic chloride, an alkaline chloride is formed, and argentic oxide
precipitated. The oxide is reduced when heated with glucose. The
chloride absorbs ammonia gas freely, but gives it up when heated.
It is soluble in solutions of the hyposulphites (thiosulphates), also in
the soluble sulphites and in potassic cyanide. When digested in
420 HANDBOOK OF MODERN CHEMISTRY.
solutions of potassic bromide or iodide, argentic bromide and iodide
are formed, potassic chloride remaining in solution. It is not reduced
when heated with carbon; but it is reduced either:—(1.) When
heated in a current of hydrogen (2AgCl-i-H2=Age +2HCl); or, (2.)
When ignited with the alkaline carbonates (4AgCl-H2Na2CO3=
4NaCl-i-2CO3 + O., +2Agg); or, (3) When brought into contact with
the easily oxidisable metals (e.g., Zn, Fe, &c.). The chloride is largely
used in photography. -
(6 and 7.) Argentic Bromide (AgBr=188) and Argentic Iodide
(AgI=235).
Preparation.—By adding potassic bromide or potassic iodide, to a
solution of argentic nitrate.
Properties.—Both salts have a yellow colour. They are insoluble
in acids, not very soluble in ammonia, but freely soluble in a solution
of sodic hyposulphite (thiosulphate).
Argentic iodide is soluble in a boiling solution of argentic nitrate,
crystals being deposited on cooling, having the formula (AgI, AgNO3).
These crystals are more sensitive to light even than the iodide.
CoMPOUNDs of SILVER AND SULPHUR.
(9.) Argentic Sulphide (Ag,S). [Mol. Wt. 248; Sp. Gr. 7:2.]
Natural History.—It is found native, both massive and in crystals,
as “silver glance.” It also occurs combined with the sulphides of
antimony and arsenic as “dark " and “light-red silver ores.”
Preparation.—(1.) By passing sulphuretted hydrogen through a
solution of a salt of silver.
(2.) By heating the metal with sulphur in a covered crucible.
Properties.—(a.) Physical. It is a soft, dark-coloured, fusible body,
conducting electricity when hot, but not when cold. It fuses when
heated, if air be excluded, but is decomposed when roasted in the
open air.
Boiling sulphuric acid forms with it argentic sulphate and SO2:
Boiling hydrochloric acid forms argentic chloride and H.S. Nitric
acid forms with it a yellow body, having the formula (AgaS, AgNO3),
The alkalies decompose it, when heated with it. It is not soluble
in the alkaline sulphides. It is decomposed by cupric chloride,
argentic chloride being formed, and also by ignition with many of
the metals, such as Cu, Pb, Fe, etc.
0xy-Salts of Silver.
(10.) Argentic Sulphate (AgeSO.). [Mol. Wt. 312; Sp. Gr. 5:32.]
Preparation.—By boiling together silver and sulphuric acid, from
which solution the salt may be precipitated on the addition of water.
Properties.—A crystalline body, somewhat insoluble in water (1 in
200 aq, at 60° F.; 1 in 88 aq. at 212°F.).
MERCURY—QUICKSILVER. 421
An acid sulphate (AgBSO.) has also been prepared.
(11.) Argentic Nitrate.—Nitrate of silver ; lunar caustic (AgNO3).
[Mol. Wt., 170; Sp. Gr., 4:33; fuses at 426°F. (219°C.)]
Preparation.—By dissolving the metal in nitric acid, and crystallis-
ing or evaporating the solution to dryness.
Properties.—A colorless crystalline salt, unacted upon by light if
perfectly pure, but blackened in the presence of a trace of organic
matter. It is soluble in water (1 in 1 at 60° F.; 2 in 1 at
212° F.), and also in boiling alcohol (1 in 4), but is insoluble in
nitric acid. It fuses at 426°F. (219°C.), and, when cast into sticks,
forms what is called “lunar caustic.” At a higher temperature it
decomposes.
It is used in surgery as an escharotic. This action depends on the
readiness with which it parts with its oxygen, the oxygen combining
with the organic matter and the silver being precipitated. It is used
in photography, also in hair-dyes, and for marking inks. In the case
of marking inks, either the fabric is first mordanted with sodic carbon-
ate, and then written upon with an argentic nitrate solution, whereby
an argentic carbonate is precipitated—a salt easily blackened; or else
the fabric is written upon without preparation with a solution of
argentic nitrate, containing an excess of ammonia, which combines
with the nitric acid of the silver-salt.
MERCURY. Quicksilver (Hg=200).
Atomic and molecular weight, 200. Molecular and atomic volume, [T].
Specific gravity at 60°F. (15.5°C.) 13:56; of vapor, 6.97°. Fuses
at 37.9° F (38.8° C.). Boils at 675° F (35.7° C.). Atomicity, dyad
in mercuric compounds (HgCl2); also a pseudo-monad, as in mercu-
rous compounds (Hg2Cl2).
History.— Known to the ancients.
Natural History.-It occurs native, but is found chiefly as a sul-
phide, “Cinnabar ’’(HgS). It is also found as a chloride (Hg,Cl),
and as an iodide.
Extraction.—(1.) Process at Almaden. The ore (HgS) is roasted,
and the mercury condensed as it distils over. The sulphurous acid is
allowed to escape.
(2.) Process in the Palatinate.—The ore (Hgs) is distilled with lime.
The mercury passes over and is collected, whilst the sulphur remains
in the retort as calcic sulphide and sulphate (4HgS+4CaO==3CaS+
CaSO4+2Hg2). (Scraps of iron may be used instead of lime, when
ferrous sulphide remains in the retort.)
Impurities.-Chiefly tin and lead.
Properties.—(a.) Physical. Mercury is a silvery-white, lustrous,
liquid metal. It is the only liquid metal known. It becomes solid at
422 HANDBOOK OF MODERN CHEMISTRY.
— 37.9°F. (– 38.8°C.), contracting greatly as it solidifies. The solid
mercury has a specific gravity of 14.0. It crystallizes in octahedra,
and is very malleable. Above 41°F. (5° C.) mercury is slightly vola-
tile. The vapor (Sp. Gr., 6-97) is transparent, and neither conducts
heat nor electricity. At 675° F (357°C.) the metal boils.
[NOTE.-The vapor density of mercury compared to air is 6-7, and
to hydrogen 100;-that is, its vapor density is one-half its atomic
weight; hence the mercury atom (like the cadmium atom) occupies as
a gas, twice the volume occupied by the hydrogen atom.]
(6.) Chemical. It is not tarnished (if pure) either by air or water
at Ordinary temperatures, although it appears that, when reduced to
a minute state of subdivision, as, e.g., by trituration with various sub-
stances chemically inert upon it, as in the preparation of the Hyd. c.
Cret., and pil. hydrargyri, etc., of the Pharmacopoeia, it undergoes a
partial oxidation (Hg2O), to which the active properties of these me-
dicines are probably due. It rapidly absorbs oxygen when heated to
800°F. (426°C.), becoming the red oxide of mercury (HgC). At a
dull red heat this oxide is decomposed into mercury and oxygen. It
combines at common temperatures with sulphur, with the haloids,
and also with many of the metals, forming with them definite
compounds. Iron and platinum are the only metals not corroded by
mercury.
Neither hot nor cold hydrochloric acid, nor cold sulphuric acid have
any action upon it. With hot sulphuric acid, mercury forms a sul-
phate, SO, being evolved. With strong nitric acid, a mercuric
nitrate is formed, nitric oxide being evolved, whilst by the action of
dilute nitric acid a mercurous nitrate results.
Uses.—In medicine, as blue pill, grey powder, etc. Its action on
the body is intense. Workmen exposed to the action of mercury
vapor, become affected with mercurial palsy. It is also used as an
amalgam with tin, for silvering looking-glasses. Also for amal-
gamating zinc plates, and for the extraction of gold and silver
from their ores, depending on the readiness with which it forms
an amalgam with them.
CoMPOUNDs of MERCURY AND OXYGEN.
Mercurous oxide tº e ſº tº e º e e e Hg20.
Mercuric oxide & Hg.0.
(1.) Mercurous Oxide.--Subowide, or black, or grey owide of mercury
(Hg.0). [Molecular weight, 416. Specific gravity, 10-68.]
Preparation. — By decomposing calomel with potassic hydrate
(Hg2C1,4-K.0=Hg.0+2KCl).
Properties.—A powerful base. It is decomposed by the slightest
heat, or even by mere exposure to light (2Hg2O=2|Hg0+ Hg2).
The efficacy of blue pill, grey powder, etc., is believed to be due to
the presence of this oxide. -
MERCURY.
423
Compounds of Mercury.
H -
Formula Formula # | 3.5 EI
SALTS. (General). (Constitutional). £: '# = | per £nt.
3= | #3
1. 2 (Mercurous oxide (black
º | oxide) * * * * Hg,0 'Hg',0 416 || 10-68 Hg=96.15
2, 3 |Mºº oxide (red
© oxide) . . . . . . Hg.0 Hg.0 216 || 11:29 Hg=92-59
3. 3 (Mercurous chloride
ſ: | (calomel) s e FIg,Cl, ‘Hg',01, 471 || 7-14 | Hg=84.92
4. 2 ) Mercuric chloride (cor-
35 | rosive sublimate) . . HgCl, HgCl, 271 5:42 Hg=73-80
[Bromides analogous
to chlorides].
5. Mercur-ammonic chlo-
ride (white preci-
pitate) • * * * NH.Hg"Cl NH, Hg"Cl
6. Mercurous iodide
(green) . . . . . . Hg, Ia ‘Hg", I, 654
7. Sesqui-iodide of mer-
cury (yellow) Hg. Is
8. . Mercuric iodide (red). . HgI2 HgI, 454 || 6-25 | Hg=44-05
9. 3 ( Mercurous sulphide
3 (Ethiop's mineral).. Hg,S (Hg',S”
0, E, ) Mercuric sulphide
à (vermilion) . . . . HgS” HgS 232 8-2 Hg=86-21
1. Mercurous sulphate . . Hg,S0, SO,(Hg',0.)”
2. Mercuric sulphate HgS0, S0,Hgo” 296 || 6’46
3. Triumercuric suphate
(Turpeth mineral).. HgSO4,2Hg0 SHgo", 8:319
4. Mercurous nitrate or
Tetrahydric mercu-
- rous dinitrate . (Hg)"2N0,2H,0|N.0, Ho,(Hg',0.)”
5. Mercuric nitrate 2 Hg''2NO3, H2O
(2.) Mercuric Oxide,-Nitric oxide, or Red owide of mercury; Red
precipitate (HgC). [Molecular weight, 216. Specific gravity, 11:29.]
Preparation.—(1.) By heating mercury to 800°F. (426°C.) in air.
(2.) By gently calcining mercuric nitrate. Hence the name nitric-
owide of mercury. (These two varieties are red and crystalline.)
(3) By mixing together solutions of sodic hydrate, and either mer-
curic chloride or mercuric nitrate. (This variety is amorphous, and
of a yellow colour.) -
Properties.—(a.) Physical. The oxide is black when hot, and either
red and crystalline, or yellow and amorphous when cold. The yellow
variety has the most marked chemical affinities. The oxide is decom-
posed at a dull red heat (HgC)=Hg-i,0). It is slightly soluble in
Water, the solution having an alkaline reaction and a metallic taste.
(6.) Chemical. The red and yellow forms appear to be allotropic
modifications of the same salt:—
424 ELANDBOOK OF MODERN CHEMISTRY.
(1.) The yellow variety is converted, by a cold solution of oxalic
acid, into an oxalate. It is rapidly changed into an oxychloride when
boiled with a solution of mercuric chloride, and, when boiled with
potassic bichromate, yields a basic mercuric chromate (HgCrO4,2Hg.0).
(2.) The red variety, is not acted upon by oxalic acid. It is very
slowly acted upon by a mercuric chloride solution, and when boiled
with potassic bichromate, forms the compound HgCrO4,3HgO.
It is soluble in fused potassic or sodic hydrate, from which solution
a crystalline body may be obtained (K2O, Hg.0).
By the action of ammonia upon mercuric oxide, the ammoniated oacide
of mercury is formed (4Hg.0,2NH3,2H2O=LIg, H3NO2). This com-
pound is a yellowish substance, easily decomposed by friction, or even
by exposure to light. Chemically, it possesses strong basic properties.
When dried “in vacuo’’ over sulphuric acid, it loses 2H2O, and forms
the compound 4EIgC),2NH4. When this body is heated to 260°F.
(126.1°C.), it becomes mercuramine (Hg,O′N.H., or Hº: | O2, H20, or
H., *
H2 }sº a dark brown substance, insoluble in water or in
EI //
†. It acts as a powerful base. It will be seen by the formulas
given, that different views are entertained as to its constitution.
Most chemists regard it as a compound of mercuric oxide and two
ammonia molecules, where two atoms of hydrogen have been dis-
placed by one of dyad mercury.
By passing ammonia gas over the yellow oxide, and then cautiously
heating the residue to 260° F (126:1°C.), a brown explosive nitride of
mercury (N.Hg") is formed. By the action of acids this body yields
salts of mercury and ammonium. It may be regarded as a double
ammonia molecule, where six atoms of hydrogen are displaced by
three atoms of divalent mercury.
CoMPOUNDs of MERCURY AND CHLORINE.
Mercurous chloride ... e e º tº ºn 4 Hg2Cl2.
Mercuric chloride tº sº tº - © tº e tº e HgCl2.
Mercur-ammonic chloride ... e is © NH.Hg"Cl.
(3.) Mercurous Chloride.--Subchloride or Protochloride of mercury;
Calomel (Hg2Cl2).
[Molecular weight, 471. Specific gravity, solid, 7:14; of vapor, 8:14.
Molecular volume, anomalous, . Relative weight, 1192.]
Preparation.—(1.) By precipitating a solution of mercurous nitrate
with hydrochloric acid, or with sodic chloride.
(2.) By subliming a mixture of corrosive sublimate (17 parts) and
mercury (13 parts) (HgCl2+Hg=Hg2Cl2).
(3.) By well triturating together mercuric sulphate (2 parts), mer-
MERCURY AND CHILORINE. 4.25
cury (4 parts), sodic chloride (3 parts), and subsequently subliming
the mixture (HgSO,--Hg-i-2NaCl=Hg2Cl2 + NagsO4).
(4.) By passing sulphurous anhydride through a saturated solu-
tion of crystalline mercuric chloride, heated to 122° F. (50° C.)
(2HgCl, + 2 H2O+SO.-Hg2Cl2+2FIC!-- HaSO.).
Impurity.—Corrosive sublimate may be present, derived partly from
the sublimation of undecomposed mercuric chloride, and partly from
the decomposition of the calomel into mercury and mercuric chlºride
(dissociation). Its presence may be detected by heating a little of
the calomel moistened with alcohol on a clean knife-blade, when a
black spot will be formed if corrosive sublimate be present. The
calomel may be purified by thorough washing with water.
Properties.—(a.) Physical. A white, heavy, tasteless, insoluble
compound. It may exist both in an amorphous and crystalline (four-
sided prisms) condition. It sublimes before fusing.
The experimental vapor density of calomel (hydrogen being 1) is
1192. If we allow Hg2Cl2 to be the molecule of calomel, occupying
2 vols. as a gas, its theoretical density is nearly double its experimental
density (i.e., wellºr 7 [. *}=235.5). If we regard the molecule
to be HgCl, then the actual and observed densities almost correspond.
Why then do we not adopt HgCl as the formula for calomel? For
two reasons:—(1.) Because it interferes with the theory that a dyad
element (like Hg") can unite with an uneven number of monad
elements (like C1') (see page 39); and (2.) That when mercurous
salts are decomposed, they invariably form mercuric salts, free mer-
cury being produced, thus favoring the notion that the molecule of the
mercurous salt contains 2 atoms of mercury rather than 1 atom.
Can we then explain this anomalous vapor density of calonel 2 It is be-
lieved that at high temperatures the salt undergoes dissociation (see
pages 13 and 47), the 2 volumes of mercurous chloride splitting up
into 2 volumes of mercuric chloride and 2 volumes of mercury,
making in all 4 volumes instead of 2 volumes. The vapor density of
mercurous bromide is also similarly anomalous.
(3.) Chemical. Solutions of sodic and potassic hydrates or lime-
water decompose it, forming mercurous oxide (Hg.,0), or black
oxide of mercury (Hg2Cl2 + CaO=Hg2O+CaCl) (a mixture known
as “black wash.”) With ammonia it forms the black compound
Hg.H.NC1; (Hg2Cl3+2HAN=Hg.H.NC1-i-H.NCl). Sulphuric acid
has no action upon it. Boiling nitric acid dissolves it, forming mer-
curic nitrate and chloride. Boiling hydrochloric acid, and solutions
of sodic or ammonic chlorides also dissolve it, forming mercuric chlo-
ride, and precipitating the metal.
(4.) Mercuric Chloride; Chloride, Bichloride or Perchloride of mer-
cury; Corrosive Sublimate (HgCl2).
Molecular weight, 271. Relative weight, 135'5. Specific Gravity of
solid, 5:42; of vapor, 9.8.
426 LIANDBOOK OF MODERN CHEMISTRY.
Preparation. (1.) By heating together mercury and chlorine.
(2.) By subliming a mixture of mercuric sulphate and common salt
(HgSO,--2NaCl-Na.SO44-HgCl).
Properties.—(a.) Physical. A white heavy crystalline (octahedral)
substance, having an acrid metallic taste. It sublimes at a low tem-
perature, fuses at 509°F. (265° C.), and boils at 563° F (295°C.),
the vapours evolved being condensible and very poisonous. It is
freely soluble in water (1 in 16 at 60°F., 1 in 3 at 212°F.); in alcohol
(1 in 3 at 60°F., 1 in 1 at 212°F); in ether (1 in 3); and in solutions
of the alkaline chlorides. Ether dissolves it from its aqueous solu-
tion. It is intensely poisonous. It is a powerful antiseptic.
(3.) Chemical. The aqueous solution is acid to litmus, and is decom-
posed by light with the precipitation of calomel. Alkalies decompose
it. With ammonic chloride it forms a double salt called “sal
alembroth’’ (HgCl2,6NH,Cl, H2O).
Mercuric 0xy-chlorides.—These are formed by the combination of
mercuric chloride with mercuric oxide. Three of them (and indeed
more) have been described, all being formed by the action of potassic
carbonate on mercuric chloride, viz.:-
(1) 2Hg0, HgCl2. (2.) 3EſgO, HgCl2. (3.) 4HgO, HgCl2.
No. 1 (2Hg.0, HgCl2) is formed by adding a cold saturated solution
of potassic hydric carbonate to eight or ten times its bulk of a cold
saturated solution of mercuric chloride (red oxychloride).
No. 2 (3Hg0, HgCl2) is formed by mixing together equal volumes
of the solutions (yellow oxychloride).
No. 3 (4Hg0, HgCl2) is formed by adding a mercuric chloride solu-
tion to a large excess of a hydric potassic carbonate solution.
We may here remark that if a mercuric chloride solution be added
to normal sodic or potassic carbonate, a yellow mercuric oxide is pre-
cipitated; but that if it be added to hydric sodic or hydric potassic
carbonate (bicarbonate), a red oaychloride is formed.
(5.) Mercur-ammonic Chloride, White precipitate, (Mercurius
precipitatus albus) (NH2Hg"Cl).
Preparation.—By adding a solution of corrosive sublimate to an ex-
cess of a solution of ammonia (HgCl2+2H3N=NH2Hg"Cl-i-NH,Cl).
Constitution.—The importance of this compound depends on the fact
of its having been the first recorded case where the mobility of hydro-
gen was recognised. White precipitate (that is the precipitate formed
where the ammonia is in excess) is regarded as ammonic chloride where
the dyad Hg" has replaced two atoms of the monad hydrogen. Thus—
NH,Cl=ammonic chloride, and NH2EIg"Cl=white precipitate.
If the mercuric chloride be in eaccess, the body N.E., EIg,Cl6 is formed.
This compound is regarded as a double molecule of ammonic chloride,
in which 4 of the monad group (HgCl)' has replaced 4 atoms of
hydrogen. Thus—
N.HaCl. = 2 of ammonic chloride; N.H., (EIgCl)',0]. - the precipitate.
MERCURY AND IOIDINE. 427
Properties.—When white precipitate is boiled with water a yellow
powder is produced (Hg,N-Clº,2H2O). Thus—
4Hg"H.NC1 + 2 H2O = Hg,N-Cl2,2H2O + 2HNOl.
White precipitate + Water = Yellow precipitate + Ammonic chloride.
Boiled with potassic hydrate, white precipitate forms NH3 and
HgC). Thus—
Hg"H.NC1 + KHO = NH, 4- Hg0 + KCl.
White precipitate + Potassic = Ammonia + Mercuric + Potassic
hydrate oxide chloride.
Heated to 608°F. (320°C.) a red crystalline powder is formed
(2HgCl2, Hg,N.). Thus—
6Hg"H.NC1 = 3NH3 + H2N, HgCl2 + 2 HgCl2, Hg2N2.
White precipitate = Ammonia + –H Red powder.
Boiled with a solution of ammonic chloride “fusible white pre-
cipitate ’’ is formed (Hg"H5N2Cl2). Thus—
Hg"H.NC1 + NH,Cl - Hg"HGN.Cl2.
White precipitate + Ammonic chloride = Fusible white precipitate.
White precipitate is used as a poison for destroying vermin.
CoMPOUNDs of MERCURY AND TODINE.
Mercurous iodide ... G - ſº Hg. Iz.
Sesqui-iodide of mercury ... (HgI, HgI2)=FIgºſs.
Mercuric iodide tº $ tº * † tº HgI2.
(6.) Mercurous Iodide (HgI2).
Preparation.—By triturating 5 parts of iodine with 8 parts of mer-
cury, the mixture being moistened with a little alcohol.
Properties.—A green insoluble powder, decomposed both by light
and heat into mercuric iodide and metallic mercury.
(8.) Mercuric Iodide,-Biniodide of mercury (HgI2).
[Molecular weight, 454. Relative weight, 227. Specific gravity of solid,
62-5; of vapor, 15-708.] -
Preparation.—(1.) By triturating together 5 parts of iodine and
4 of mercury, and subliming the mixture.
(2.) By precipitating a solution of mercuric chloride with one of
potassic iodide.
[The mercuric iodide is soluble in excess of either salt.]
Properties.—(a.) Physical. Mercuric iodide is dimorphous. If the
crystals be octahedral, the color of the salt is red; if they be rhom-
boidal, it is yellow. It is soluble in hot alcohol, but is insoluble in
water. It fuses at 392°F. (200° C.). The vapor has a remarkably
high specific gravity (15708).
(3.) Chemical. It is soluble in the alkaline chlorides, in neutral
ammonic salts, and in hydrochloric and hydriodic acids. With the
more basic, or electro-positive soluble metallic iodides, it forms double
salts. Thus potassic-mercuric iodide (2(KI,Eig12),3H2O) crystallizes
428 HANDBOOK OF MODERN CHEMISTRY.
on cooling from a hot solution of mercuric iodide in potassic iodide. It
forms double salts with mercuric oxide, sulphide, and chloride, as e.g.
(HgI2. HgCl2) and (HgI2,2HgCl2).
The solution of mercuric iodide in a solution of potassic iodide contain-
ing potassic hydrate, constitutes the “Nessler test” for ammonia. This
solution forms, with ammonia, a brown precipitate (Hg".NI, H.O).
Iteaction of the Nessler test with ammonia—
2EIgle+3RHO--NHa=Hg".NI, H20+3KI+2H.O.
COMPOUNDS OF MERCURY AND SULPHUR.
Mercurous sulphide ... e - e. ge º 'º Hg2S.
Mercuric sulphide º HgS.
(9.) Mercurous Sulphide. — Subsulphide of mercury; Ethiop's
mineral (Hg2S). - -
Preparation.—By passing sulphuretted hydrogen through a solution
of mercurous nitrate. -
Properties.—A black substance, easily decomposed by heat (Hg2S
= Hg-i-HgS).
(10.) Mercuric Sulphide.—Cinnabar (that is, the native HgS);
Vermilion (that is, the finely-powdered Hgs) (HgS).
[Molecular weight, 232. Relative weight, anomalous, 77°3, i.e., 2 volumes
of mercury vapor + 1 volume of sulphur vapor forms (not 2 volumes but)
3 volumes of mercuric sulphide vapor; that is, they unite without con-
densation. Molecular volume, T. Specific gravity of solid, 82; of
vapor, 5'5.]
Natural History.—It is found native both in crystals (hexahedra)
and in masses. It constitutes the principal ore of mercury.
Preparation.—(1.) By adding a solution of mercuric chloride, either
to a solution of sulphuretted hydrogen, or to one of a soluble
sulphide (black variety of Hgs). -
(2.) By agitating together 6 parts of mercury and 1 of sulphur
(black variety of Hgs). --
(3.) The red form of sulphide is prepared from the black, either by
subliming the black variety in vessels from which air is excluded, or
by the prolonged action of an alkaline sulphide containing an excess
of sulphur.
(4.) By triturating 300 parts of mercury with 114 of sulphur, and
digesting the product with a solution of potassic hydrate at 120° F.
(48.9°C.) (red variety of HgS.)
[N.B.-On passing H2S through a solution of a mercuric salt, a
white precipitate is first formed. This results from a small quantity
of the mercuric sulphide first produced forming a double salt with the
mercuric salt in solution.]
Properties.—(a.) Physical. There are two varieties of this body,
viz., black and red. The black is converted into the red variety
without chemical change.
MERCURY oxy-SALTs. 429
The red salt, when heated, air being eaccluded, sublimes without
fusing, the sublimate being black but becoming red on cooling;
whilst, when heated in the presence of air, the sulphur burns off
(as SO2), and the metal is set free.
(3) Chemical.–Mercurous sulphide is unaffected either by acids
(except by nitro-hydrochloric acid), or by alkalies unless ignited in con-
tact with them, when the mercury sublimes, and an alkaline sulphide
and sulphate are formed—
4HgS+8KHO=4Hg-H K.S.O., +3K.S +4EI2O.
It forms compounds with metallic sulphides, and also with other
mercuric salts. It is a very permanent body; hence its value as a
paint.
Oxy-SALTs.
(11.) Mercurous Sulphate (Hg2SO.) is a white, crystalline powder,
formed on adding dilute sulphuric acid to mercurous nitrate, or by
gently heating together mercury and sulphuric acid.
(12.) Mercuric Sulphate (HgSO4) is a white powder, formed by
heating together mercury and sulphuric acid at high temperatures
(Hg-H2H.SO,-HgSO,--SO2+2H2O).
Properties.—It is decomposed by pure water, the insoluble yellow
basic salt, trimercuric sulphate, or turpeth (turbith) mineral being formed
(HgSO4,2Hg.0), together with a soluble acid sulphate.
(14.) Mercurous Nitrate, or Protonitrate of mercury;
(Hg.)"2NO3,2H.O.
Preparation.—By digesting mercury in an excess of dilute nitric
acid. If the mercury be in excess, a basic nitrate is formed, having
the formula (3(Hg2)"2NO3, Hg"20, H2O). This basic nitrate may be
known from the neutral salt by its becoming black when triturated
in a mortar with sodic chloride, calomel being formed, and mercurous
oxide separated. Thus—
(a.) (Hg)"2NO,2H,0 + 2NaCl = Hg,Cl, + 2NaNO3 + 2H,0.
Normal mercurous + Sodic Calomel + Sodic + Water.
nitrate chloride nitrate
(3.) 3(Hg.)"2NO, Hg",0, H.0 + 6NaCl = 3Hg,Cl, + 6NaNO,-- Hg,0 + H.0.
Basic mercurous + Sodic = Calomel + Sodic -i-Mercurous–H Water.
nitrate chloride nitrate oxide
(15.) Mercuric Nitrate (2Hg"2NO3, H2O).
Preparation.—By dissolving mercuric oxide (or metallic mercury)
in an excess of nitric acid.
A yellow basic nitrate (Hg2NO3,2'Hg'O,Hg"O) is precipitated by the
action of water upon mercuric nitrate, from which salt, by the con-
tinuous action of hot water, all the nitric acid may be removed, mer-
curic oxide only remaining.
Beactions of Mercury compounds.-(See ANALYTICAL TABLEs.)
430 HANDBOOK OF MOIDERN CHEMISTRY.
THALLIUM (T1=204).
Atomic weight, 204. Molecular weight (probable), 408. Specific gravity,
11.8 to 11-91. Fusing point, 561° F (294° C.). Atomicity, monad
as in thallous compounds (') (TICl ; OTl2), and triad as in thallic
compounds ("") (Tl"Cls).
History.—Discovered by Crookes (1861), by means of its peculiar
spectrum. This spectrum was first noticed in a deposit taken from a
flue at a sulphuric acid manufactory, where thalliferous pyrites had
been used in the manufacture of the acid. (Thallium is derived
from 6a)\\óc, “green,” so named from its pecular spectrum.)
Natural History.—It occurs sparingly, but widely in some speci-
mens of Spanish and Belgian pyrites, also in certain mineral waters,
and in some specimens of mica and lepidolite.
Extraction.—By treating the deposit contained in the flues of
sulphuric acid chambers with water, and precipitating the thallous
chloride from the clear solution with hydrochloric acid. By the action
of sulphuric acid, the thallous chloride may be converted into thallous
sulphate, from which solution the metal may be precipitated by the
action of metallic zinc or of the galvanic battery.
Properties.-(a.) Physical. A heavy crystalline body, exhibit-
ing, when freshly cut, a brilliantly metallic surface. It is softer
than lead, leaving a bluish line when rubbed on paper. This line may
be known from a lead line, by its turning yellow (oxidising) after a
short time. The metal crackles like tin when bent. It is diamagnetic.
Its specific gravity varies from 11-8 to 11-91. Its specific heat
is 0.0325. It is volatile at a red heat, and boils below a white heat.
Its spectrum consists of one intensely green line. The salts of thal-
lium are active poisons.
(B.) Chemical. Thallium rapidly tarnishes in air at common tempe-
ratures. When melted it rapidly oxidises, but it may be distilled in
a current of hydrogen. It burns in oxygen, emitting a green light,
and producing thallic oxide (Tl2O3). It combines energetically with
the haloids, and also with sulphur and phosphorus. The action of
both nitric and sulphuric acids upon it is energetic, whilst that of
hydrochloric acid is very slight.
In chemical position, thallium is more closely allied to the mona-
tomic metal silver, than to the alkaline metals. With the alkali metals
it agrees in its atomicity, as well as in the solubility and alkaline reac-
tions of its oxide (Tl20) and of its carbonate (Tl2CO3); but it disagrees,
in that the metal may be preserved unaltered in water, and may be
precipitated from its salts by zinc. With silver it agrees in the sparing
solubility of its chloride, and in the insolubility of its sulphide,
whilst it must also be remembered that silver oxide, like thallous
THALLIUM.
431
oxide is slightly soluble in water, and that its solution is alka-
line.
Compounds of Thallium.
Formula Formula
SALTS. (General) (Consti-
€ In de tutional).
1. Thallous oxide .. Tl,0 OTL.
TIO
2. Thallic oxide Tl,0, O
TIO
3. Thallous chloride T1Cl T1Cl
4. Thallic chloride TIC1, T1C1,
5. Sesquichloride of thallium - tºtic
6. Dichloride of thallium | - ſºci
7. Bromides analogous to chlorides
8. Thallous iodide. . tº - - TII
9. Thallic iodide . . TII,
10. Thallous sulphide Tl,S
11. Thallic sulphide Tl,S,
12. Thallous carbonate . . Tl,CO, COTlo,
13. Thallous nitrate TINO, NO.Tlo
14. Thallous sulphate Tl,S0, SO, Tlo,
15. Thallic sulphate • & e s e Ti”,(SO.),TH,0 *
| H.TIPO,
( Orthophosphates HT), PO,
16. Thallous phosphates Hºo
Dy c -, * r # 2, 2’ 7
yrophosphates l Tl,P,0,
Metaphosphate TIPO,
(1, 2.)—The Oxides of Thallium. Both Thallous Oxide (Tl2O)
and Thallic Qa’ide (Tl2O3), are basic oxides, and form soluble crystalline
salts. The thallous oxide is formed whenever a freely-cut surface
of the metal is exposed to the air, but on placing the tarnished metal
in water the oxide layer is instantly removed. The solution is alkaline,
and rapidly absorbs carbonic acid from the air. When electrolysed, it
yields metallic thallium. t
Thallic oxide (Tl2O3) is a dark red powder, and is formed when
thallium is burnt in oxygen. It may be prepared as a hydrate
(Tl"HO2 or Tl2O3, H2O), by adding potassic hydrate to a solution of
a thallic salt.
A suboa;ide of thallium is supposed to exist.
(3-6.) The Chlorides of Thallium.–There are four thallium chlo-
rides. Thallous chloride (TICl) is formed either by burning the metal in
chlorine, or as a white curdy precipitate on adding a soluble chloride
to a solution of a thallous salt. It dissolves (like PbCl2) in boiling
water. With platinic chloride it forms the double salt 2TiCl, PtCl,
and with ferric chloride, the compound 6T1Cl,Fe2Cl6. -
432 HANDBOOK OF MODERN CHEMISTRY.
(10.) Sulphide of Thallium (Tl2S) is formed either by adding
hydric ammonic sulphide to a solution of a thallous salt, or by the
action of sulphuretted hydrogen on a solution of the oxalate, acetate,
carbonate, nitrate or sulphate of thallium.
(14.) Thallous Sulphate combines with aluminic sulphate to form
an octahedral alum (Al..."Tl2(SO4)4,24H2O).
Reactions of the Thallium Compounds.
1. They all impart a green color to flame, and produce the spectrum
peculiar to the metal (vide supra).
2. The metal is reduced whenever a thallous salt is ignited with
a mixture of charcoal and sodic carbonate.
3. The metal is precipitated when a piece of zinc is placed in a
solution of a thallous salt.
(A.) THALLOUS SALTs.—1. Soluble chlorides or bromides; a white
ppt. of thallous chloride (TICI), or of thallous bromide (TIBr).
2. Soluble iodides; a yellow ppt. of thallous iodide (TII).
3. Potassic chromate ; a yellow ppt. of thallous chromate.
4. Platinic chloride; a yellow ppt. of 2T1Cl, PtCl4.
5. Alkaline hydrates and carbonates; no ppt. (see Reaction with
thallic salts).
6. Ammonic sulphide; a brownish-black ppt. (Tl2S), insoluble in
0XC6SS.
(B.) THALLIC SALTs.—1. Soluble chlorides or bromides; no ppt.
2. Alkaline hydrates and carbonates; a brown gelatinous ppt. (TIHO.).
3. Oxalic acid ; a white ppt.
TUNGSTEN (w (wolfranium)=184).
Atomic weight, 184. Specific gravity, 17-4. Atomicity tetrad ("), as in
Tungstous compounds (WO2), and hea'ad ("), as in Tungstic com-
pounds (WOs).
Natural History.—It occurs as Scheelite (CaWOA) as Wolfram
(Mn WO4,3FeWOA), and as a tungstate of lead and of copper.
Preparation.—By reducing tungstic anhydride (WOS) with char-
coal at a white heat.
Properties.—A white, hard, brittle, infusible metal. Its alloy
with steel is intensely hard, and permanently magnetic in a high
degree. When finely powdered it burns in air. Tungstic acid is
formed by the action upon the metal either of nitric acid or of aqua
regia, or else by heating it with nitre, or by boiling it in an alkaline
solution. It combines with chlorine when heated with it.
Oxides of Tungsten.—Tungsten forms three oxides, WO2, (which
does not form salts with acids), WOs, and W303 (or WO2, WOs).
Tungstous 0xide (W.O.).-This is prepared by heating WOs in
- TUNGSTEN. 433
a stream of hydrogen. It is a brown powder, and burns in air, form-
ing WOs. It is an indifferent oxide. s
Tungstic Oxide—Tungstic anhydride (WO). (Called tungstic
acid).
*—w igniting the residue left after treating calcic
tungstate (Scheelite) with hydrochloric acid.
Properties.—A yellow powder, insoluble in water and in most acids,
but soluble in alkalies. When a hot alkaline solution is neutralized
with an acid, a yellow precipitate of tungstic acid (H2WO4) occurs,
but when a cold dilute solution is similarly treated, a white precipi-
tate of hydrated tungstic acid (HAWO4, H2O) is formed. Tungstic
acid reddens litmus, and is soluble in alkalies.
The Tungstates.—Tungstic acid, it will be seen, exists in two
modifications:—
(a.) Common tungstic acid is of a yellow color, and insoluble in
water. This variety forms both normal salts (M.W.O.) and acid salts
(3M20,7WO3). Tungstate of soda (Na2VO4) is employed as a mor-
dant in dyeing, and is also used for the purpose of rendering muslim
uninflammable.
(3.) Metatungstic acid is a white body, soluble in water. The
metatungstates are formed by the action of hydrated tungstic acid
on the tungstates.
The oxide W2O5 is of a blue color, and is formed whenever an acid
solution of tungstic acid is brought into contact with a bar of tin or
Zll 10.
Several chlorides are known, viz., WCl2, WCl4, WCls, WCl6.
Reactions of the Tungstates.
1. Sulphuretted hydrogen and ammonic sulphide ; no ppt.
2. A boraa bead in the reducing flame with compounds of tungsten
becomes yellow, changing to red as it cools.
3. If to acidulated solutions a piece of zinc be added, the blue
W.05 is formed.
434 EIANDBOOK OF MODERN CHEMISTRY.
SUPPLEMENT TO THE METALS.
GALLIUM (Ga).
[Omitted from page 347.]
Atomic weight, P Fuses at 86-27°F. (30:15° C.). Specific gravity
5'935.
History.— Discovered by M. Lecoq de Boisbaudran (1875). Termed
gallium from Gallia (France).
Occurrence.—It occurs associated with zinc in the zinc blende of
Bensberg; also in the yellow transparent blende of Asturias, and in
the brown blende of Pierrefitte. In smaller quantities it is found in
cadmies from Corphalie. Zinc dross, and the Swedish brown blende,
contain sensible traces of gallium. -
Preparation.—By the electrolysis of a solution of the oxide in
potassic hydrate.
Properties.—By the above process gallium may be obtained in a
fused state. It has a silvery white color. It continues in this super-
fused state for several days when allowed to remain at rest and
carefully protected; but if any part of its surface comes into contact
with a trace of solid gallium, a spot is seen to form, which rapidly
spreads. On crystallising it assumes a bluish tint, and its lustre
diminishes. Gallium may be liquefied by the heat of the hand. The
solid metal may be cut with a knife, and is both flexible and malleable.
Heated to bright redness in the presence of air, gallium does not
volatilise, and merely oxidises superficially. When cold, the metal has
only to be rubbed with a rod to restore it to its original brightness.
Gallium Chloride (GazCl6) is a deliquescent substance, very soluble
in water. -
Gallium Sulphate is a non-deliquescent substance, and also very
soluble in water.
Gallium Alum is colorless and limpid.
[Wide “Chemical News,” April 20, 1877, et seq.]
IRIDIUM. 435
IRIDIUM (Ir.)
[Omitted from page 409.]
Atomic weight, 198. Specific gravity, 21:15. Atomicity, dyad (IrO);
tetrad (IrCl3), and hea'ad; also a pseudo-triad.
History.—Discovered by Smithson Tennant.
Derivation.—Iris the rainbow, from the varied tints of its
compounds.
Natural History.—Found native in platinum ores. It also
occurs as an alloy with osmium.
Preparation.—(1) (a.) Chlorine is first passed over a heated
mixture of the iridium alloy and sodic chloride, double chlorides of
iridium and sodium (2NaCl, IrCl3), and of osmium and sodium being
formed.
(3.) The mass is now treated with boiling water, whereby thesa
double chlorides are dissolved away from the insoluble portion.
(y.) The concentrated solution is then distilled with nitric acid,
which decomposes the double osmium salt, liberating the volatile
osmic anhydride (OsO4).
(8.) The residual solution in the retort (which contains the iridium)
is then treated with ammonic chloride, and the resulting dark red-
brown precipitate of ammonic iridic chloride (2NH,Cl,IrCl3) ignited.
In this way iridium is obtained in a spongy form. (Wöhler.)
(2.) Frémy prepares the metal from the potassic iridic chloride
(2KCl, IrCl3), formed by the action of potassic chloride on a solution
of the metal in aqua regia (IrCl3), by igniting it in a current of
hydrogen.
Properties.—(a.) Physical. A hard, white and brittle metal. It
crystallizes in cubes and also in six-sided prisms (dimorphous). The
metal may be obtained in a finely divided state as a black powder,
having properties similar to platinum black, by precipitating it with
alcohol from a solution of the sulphate. It fuses when heated in the
voltaic arc or in the oxyhydrogen jet.
The fused metal has a specific gravity of 21:15.
Its alloy with osmium has a specific gravity of 22:6.
(6.) Chemical.—The pure metal when in mass is unacted upon
either by air, by heat, or by any acid. On the contrary, its alloy
with platinum is soluble in aqua regia, whilst the finely divided
metal when heated in air absorbs oxygen, forming IreOs, a black
powder used for imparting an intense black to porcelain. The
finely powdered metal is oxidized (but not dissolved as in the case of
rhodium) by fusion with hydric potassic sulphate. It is also oxi-
dised by fusion with sodic nitrate and sodic hydrate, the compound
resulting being soluble in aqua regia, forming a deep black liquid
436 HANDIBOOK OF MODERN CHEMISTRY.
containing the double sodic iridic chloride (2NaCl,IrCl). Iridium,
like palladium, combines with carbon when heated in the flame of a
spirit lamp.
Compounds of Iridium.
- Molecular
Compounds. Formula. Weight.
Iridious oxide . . © & e - e tº Ir’’O 214
§ \ Iridic oxide º e tº ºr & Cº. * - 'Ir”,0, 444
: { Iridic dioxide . . e G tº e tº e Irivo, 230
& | Iridic hydrate . . . tº o O e tº º Irly Ho, 266
Iridic anhydride . . . . . . . . Irvio, 246
3 g (Iridious chloride.. gº º to e tº 2 Trºof 269
3.3 |# chloride . . . . . . . . 'frºël, 609
O ‘g ( Iridic tetrachloride º º tº e e ºf Irivol, 340
... . . (The iodides similar to the chlorides).
r: 3 | Iridious sulphide.. * - e e Ir”S 230
&# (Iridic sulphide .. tº tº e G tº º 'Ir”.S., 492
Q4
Reactions.
(1.) Sulphuretted hydrogen first decolorizes a solution of
2NaCl, IrCl3, precipitating sulphur, and afterwards precipitates the
brown IraS3. -
(2.) Ammonic sulphide, reaction as above, the precipitated IreS,
being soluble in excess.
(3.) Sodic or potassic hydrate, a brownish black precipitate, the
solution turning green, and when heated blue.
(4.) Potassic chloride, a dark brown precipitate (2KCl, IrCl3).
#,

437
CHAPTER XVIII. Y-
NOTES FOR PRACTICAL ANALYSIS.
I.—INTRODUCTORY.
(1). The solution being a liquid, note its reaction to test paper.
An acid reaction indicates, An alkaline reaction indi- A neutral reaction indi-
Cates, cates,
A free acid. Afree alkali or alkaline earth Water.
An acid salt. A salt with an alkaline re- A normal (neutral) salt.
A normal salt having an acid action.
reaction. An alkaline sulphide or
cyanide.
(2.) Evaporate a portion of the solution to dryness:–
(a.) If it leaves no residue, it may be simply water.
(3.) If it leaves a residue, proceed to examine the solid constitu-
ents as follows:—
FXAMINATION OF SUBSTANCES BY DRY METEIODS.
A.—HEAT THE DRY SOLID IN A GLASS TUBE.
RESULTs. INDICATIONs.
1. No action . . . . . . . . . Absence of organic matter, of fusible and volatile substances,
of hydrates, and of salts containing water of crystallisa-
tion.
2. Change of color . . . Charring indicates organic matter. If acetates be present,
acetone is evolved, and a carbonate remains which may
be known by its effervescing on the addition of HCl.
If the body be yellow when hot, and white when cold=ZnO.
If it be brown when hot, and yellow when cold=SnO2.
If it be reddish brown when hot, and yellow when cold=PbO.
If it be orange red when hot, and yellow when cold=Bi,0s.
3. Substance sublimes | Yellow drops (sulphur, sulphides or hyposulphites).
Yellow crystals (HgI2; As,Ss).
White octahedral crystals (As,0s).
White crystalline sublimate (oxalic acid).
Black sublimate (HgS; or, if with a violet vapor, iodine).
White sublimate, yielding NHs when heated with potash
ammonium salts).
Melts, and yields a white crystalline sublimate (HgCl).
Sublimes without melting (Hg,Cl).
Sublimate treated ) (a.) Metallic globules, and a metallic mirror (mercury com-
with Na,C0 ounds).
and charcoal | (3.) No globules, but a black shiny mirror (arsenicum com-
yields . . . . . . pounds).
438 HANDBOOK OF MODERN CHEMISTRY.
RESULTs. - INDICATIONs.
4. Gases are evolved NHa; (ammonium compounds).
having peculiar odor Frankincense odor (benzoic acid).
or other characteris- Irritating fumes (succinic acid).
tics. White fumes and crystalline sublimate (oxalic acid).
H.S ; (sulphides, sulphites, hyposulphites). [Tests.-(a.)
Smell. (3.) Lead paper.]
CS, ; (sulphocyanates). [Test.—Odor].
CN; (cyanogen compounds). [Test.—(a.) Odor. (6.) Burns
with a red flame.]
CO, ; (carbonates). [Test.—Whitens lime water].
cº ; (oxalates and formates). [Test.—Burns with a blue
8.II 16 |,
N,0s; (nitrates of the heavy metals). [Tests.-Color; red-
dish brown].
SO; ; (sulphites and hyposulphites.) [Tests.-(a.) Odor.
(3.) Acid reaction].
O ; (peroxides; nitrates; chlorates). [Tests.--Supports com-
bustion].
Cl; (chlorides of certain metals; chlorates; hypochlorites.
[Tests.-(a.) Odor. (3.) Bleaches indigo. (y.) KI and
starch].
B.—HEAT THE SUBSTANCE WITH THE BLoWPIPE ON A PIECE OF
CHARCOAL.
RESULT. INDICATION of PRESENCE of
Decrepitates. Numerous salts, such as NaCl, etc.
Deflagrates. Nitrates, chlorates.
Fuses and is then ab- || Alkaline salts. \
sorbed by the char-
coal.
(a.) If a white RESIDUE remains after heating with the blowpipe,
moisten it with a drop of cobaltous nitrate and again heat.
RESULT. INDICATION of PRESENCE OF
Blue . . tº e tº º Al,0s.
Pink . . tº e e g MgO.
Green . . * * tº e ZnO.
(3.) If a coloFED RESIDUE remains, heat a small portion in a clear
borax bead.
IN INNER (REDUCING) IN ouTER (oxiIIZING) INDICATION OF PRESENCE
FILAME. FLAME. OF.
Blue . . . . . . . . Blue. Co0.
Red . . . . . . . . Blue. CuO.
Sherry red . . . . . . . . NiO.
Colorless . . . . . . Amethyst. Mn().
Green . . . . . . Reddish. Fe,04.
Green . . . . . . Green. Cr,0s.
(y.) If a METALLIG RESIDUE remains when heated in the inner
flame, note the characteristics of the bead as follows:—
[It may be necessary in this case, in order to effect perfect reduction, to heat the
metal with KCy.] -
(1.) A metallic non-volatile residue, without incrustation.
CHARACTERS OF BEAD. INDICATION of PRESENCE OF.
Brilliant white; malleable .. tº e * - Ag.
Yellow tº ſº tº º * * tº º tº e Au.
Red scales or globules * - tº e Cu.
Magnetic globules .. • * tº gº * s Fe, Co, Ni.
FRACTICAL ANALYSIS.
439
(2.) A metallic residue, with incrustation. (This incrustation is due
to the volatility of the metal.)
CHARACTERS OF BEAD.
Malleable and marks paper º ºg
Bright; malleable tº º
Brittle .. tº ſº tº ſº • *
Brittle .. tº º tº º
The metal reduced but instantly
volatilized
Do. do. do.
Do. do. do.
INCRUSTATION.
Reddish brown when hot, yellow
when cold tº gº tº ſº ſº tº
Yellow when hot; white when
cold .. * * s & tº s
Dark orange when hot; yellow
when cold gº tº sº tº
White fumes and white incrus-
tation (Sb2O3).. s &
White incrustation. Garlic odor
Yellow when hot; white when
cold .. tº 4 © ºl tº º
Reddish brown ..
INDICATION of
PRESENCE OF
Pb.
Sn.
Bi,
Sb.
As.
Zn.
Col.
C.—HEAT A PORTION OF THE RESIDUE MOISTENED witH HOl ON A
CLEAN PLATINUM WIRE IN THE INNER BLoWPIPE FLAME,
CoLoR of FLAME.
Yellow
Violet
Green tº º
Crimson
Red . § it
Bluish green..
INDICATION OF PRESENCE of
Na.
K.
Ba.
Sr or Li.
& ſº tº º e & Ca.
tº º tº º e is Cu—B,0s.
Lithium (Li-T).
Brilliant crimson.
II.—ExAMINATION FOR BASES.
TABLE I.
Reactions of the Salts of the Alkaline Metals.
Sodium” (Na=23).
Potassium (K=39:1).
Ammonium (NHA) (?).
(A.) WET REACTIONs:—
1. Sodic or potassic hydrate and heat
2. Tartaric acid (C,E,0)
3. Platinic chloride (PtCl) and HCl
4. Carbazotic acid (CºHA(NO),0) , .
5. Nessler's reagent; potassic solu-)
tion of potassic mercuric iodide
(2KI, HgI.) © tº tº º º
6. Hydrºfluojicic acid (2.ÉF,SIF)
7. Potassic metantimonate (KSbO3).
(B.) DRY REACTIONs:—
1. Application of heat tº º
2. Color imparted to flame ..
White crystalline ppt.
(NasbO) in neutral
or slightly alkaline
solutions.
Fixed.
Yellow ; Spectrum,
yellow line at D.
insol. in alcohol, Sol. in hot water.
Yellow crystalline ppt.—
(C6H2K (NO2)3O).
ºse
A white gelatinous ppt. (2KF,SiF.).
Fixed.
Violet; Spectrum, one line in red
and one in violet.
White crystalline ppt. (KHC, H,0)
Yellow crystalline ppt. (2KCl, PtCl,)
insol. in alcohol, slightly sol. in
water. On ignition, Pt-HKCl is left.
Alkaline vapors of NHa: (a) Ammonia
smell. (b.) Turns turmeric paper
brown, the color disappearing when
the paper is warmed or left. (c.)
White fumes with HCl of NH,Cl.
White ppt. (NH, HC, H,0s) in a con-
centrated solution of an ammonium
salt on standing, Sol. in excess of
water and in ammonia.
Yellow crystalline ppt. (2NH,Cl, PtCl,),
insol. in alcohol. On ignition, Pt
only is left, the NH,Cl being volatile.
Yellow crystalline ppt.
A brown precipitate, or coloration only
if the quantity present be small
(NHg,I, H.,0). . . .
Volatile.
* All the sodium salts except the metantimonate are soluble in water.
TABLE II.
A Solution may contain a Salt of Potassium, Sodium, Ammonium, and Lithium.
(A.) DETERMINE PRESENCE OF AMMONIUM.–Boil a small quantity of the solution with KHO or NaHO in a test-tube, and note
(a.) the odor, (3) the reaction on turmeric, and (y.) the action with HCl of the fumes (NH3) evolved.
(B.) If an ammonium compound be present, evaporate the Solution to dryness and ignite, until ammoniacal fumes cease to be
evolved. Allow the residue to cool; dissolve in water; filter if necessary. -
[N.B.-The evaporation to dryness and ignition is not required in the absence of ammonium salts, but is rendered necessary
if ammonium compounds be present, inasmuch as the ammonium reactions interfere with those of potassium.] -
Test the solution on a clean platinum wire in the Add to the solution in a watch glass HCl
blow-pipe or Bunsen flame. and PtCl4:
A yellow color - Stir: a yellow precipitate
indicates indicates
S O D I TOſ M . P O T A S S I U M .
(C.) For LITHIUM the ignited residue, previous to dissolving it in water, is to be digested in a mixture of ether and absolute
alcohol. The flame produced when the filtrate is fired will be of a brilliant crimson color.
Reactions of the Salts of Barium, Strontium,
TABI,E III.
Calcium, and Magnesium.
Barium (Ba'-137).
Strontium (Sr’’=875).
Calcium (Ca”=40).
Magnesium (Mg"=24).
(A.) WET REACTIONs:—
1. Ammonia and ammonic
carbonate. (NH,Cl to
be added to prevent
º: precipitation of
8) . . . .
2. Calcic sulphate
3. Dilute sulphuric acid. .
4. Ammonia and ammonic
oxalate . . . . . .
5. Hydro-fluo-silicic acid
6. Ammonia . .
7. Ammonia and hydric
sodic phosphate
(Na,HP0.) tº tº
8. Potassic chromate
(K.CrO.) . . . . . .
(B.) DRY REACTIONs:—
1. In blow pipe flame, or
in Bunsen burner,
the flame is colored
White ppt. (BaCO). Sol. in
acids
Immediate white ppt. (Baš0,).
Immediate white ppt. (Baš0.)
in strong and in dilute solu-
tions, insoluble in HNOa.
(Precipitation interfered
with by the presence of an
alkaline citrate.)
White ppt. (Ba”C,0) soluble
in HCl and HNOa.
White crystalline ppt. (Bar',
SiF!). Insol. in alcohol.
No ppt.
A white ppt. (BaFIPO.). Soi.
in acetic acid.
Yellow ppt. (Ba''CrO.) in di-
lute solutions. Soluble in
HNOa.
Green.
White ppt. (SrC0.).
acids.
Sol. in
White ppt. (SrS0,) after stand-
2% (7.
wift ppt. (SrS0). In very
dilute solutions, ppt. not im-
mediate. Insol. in alcohol
or in a concentrated solution
of (NH4)2SO, even when
boiled.
White ppt (Sr"C.O.).
No ppt.
º-
A white ppt. (SrBPO.). Sol.
in acetic acid.
No ppt.
Red.
White ppt (CaCO). Sol. in
acids; somewhat soluble in
NH,Cl when boiled.
No ppt.
White ppt (CaSO) in concen-
trated solutions. Soluble
in a boiling solution of am-
monic sulphate.
White ppt (Ca"C.O.) in very
dilute solutions. Sol. in
HCl and HNO, ; insol. in
acetic and Oxalic acids.
No ppt.
A white ppt. (CaaP,0s).
in acetic acid.
Sol.
No ppt.
Orange red.
No ppt. A soluble double chloride
2NH4C1, MgCl, being formed.
No ppt.
No ppt.
No ppt. in the presence of NH,Cl.
No ppt.
White ppt. (MgH,02). Soluble in
NH,Cl. (See above.)
White crystalline ppt. (Mg(NH,)PO,).
Insol. in ammonia, ammonic car-
bonate or chloride, Soluble in
dilute acids. - --
No ppt.
No special color imparted to the flame.
lf the ignited residue be moistened
with nitrate of cobalt and heated in
the blow pipe flame, a pink-colored
mass is obtained. -

TABLE IV.
A solution contains a salt of Barium, Strontium, Calcium, and Magnesium.
Add to the solution NH,Cl (NoTE 1), NH, HO and ammonic carbonate, until no further ppt. is formed; heat gently (NotE 2); filter.
Precipitate=BaCOa, SrCOa, CaCO,5–
Filtrate contains
magnesium.
Dissolve the ppt. in HCl, and evaporate to dryness;–
Dissolve a small portion of the residue in H20, and add to it a
solution of CaSO4.
If a ppt. occurs with CaSO4, drench the remainder of the
residue with methylated spirit; heat the mixture and filter.
INSOLUBLE
=BaCl2.
Test its power
of imparting a
green color to
the B unsen
flame.
This indicates
IBARIUMI.
indicates the presence of
strontium, but calcium
may also be present.
The absence of barium
is also indicated.
We thus prove the
absence of barium and
the presence of
PRECIPITATE AFTER
10 MINUTES
STRONTIUMI.
PRECIPITATE
IMMEDIATE
indicates the pre-
sence of barium,
but strontium and
calcium may also
be present.
We thus prove
the presence of
IBARIUM.
No PRECIPITATE
indicates the absence of
barium and strontium, but
calcium may be present.
If no precipitate occurs
with CaSO4, dissolve the
remainder of the residue
in water, and add to the
solution ammonia and am-
monic oxalate.
A white ppt. indicates
CALCIUMI.
SoLUBLE Portion contains
SrC1, and CaCl2:
Add dilute H.S0, until no further ppt. is
formed ; filter and wash; boil the ppt. with a
concentrated Solution of ammonic sulphate ;
filter and wash the residue ;-
INSOLUBLE Portion
=SrS0,
Heat the residue, moist-
ened with HCl, on a pla-
tinum wire in the Bunsen
flame, when a crimson
color indicates the pre-
Sence of
STRONTIUMI.
Solubſ. B Portion
=CaSO,.
Add NH, H0 and
ammonic oxalate.
A white ppt. indi-
cates
CALCIUMI.
Prove the com-
plete precipitation
of Ca, Sr, and Ba,
by adding a drop of
a solution of am-
monic carbonate.
Add
NH,Cl, ammonia,
and sodic hydric
phosphate.
A white crystalline
ppt, indicates
MAGNESIUMI.
NoTEs. 1.-The ammonic chloride is added to prevent the precipitation of the magnesia by the ammonia which is subsequently added.
2.—The mixture is not to be boiled, otherwise the ammonic chloride will dissolve a part of the ppt., especially if it be CaCO3.
TABLE W.
A Solution contains a Salt of Potassium, Sodium, Lithium, and Magnesium.
Divide the solution into two parts, one part consisting of about two-thirds of the whole.
Smaller portion.
Larger portion.
Add NH,Cl, NH.HO and Na2HPO,.
A white ppt. indicates
IM A G IN E S I U M .
Evaporate to dryness and ignite.
1. Test a portion of the residue in the flame. A yellow color indicates
S O DI U M .
2. Digest the residue with a mixture of absolute alcohol and ether, and filter. The
filtrate, when fired, burning with a crimson flame indicates
L I T H I U IMI.
3. Dissolve the residue from (2) in water, and add HCl and platinic chloride. A yellow
ppt. indicates
IP O T A S S I Uſ M .
TABLE WI.
A Solution may contain a Salt of Barium, Strontium, Calcium, and Magnesium,
AND
A Salt of Sodium, Potassium, and Ammonium. -
(A.) Test for an ammonium salt by heating with KHO. Note.—(a) smell, (3) action on turmeric, (y) action with HCl on
glass rod.
(B.) Add NH4C1, ammonia and ammonic carbonate until no further ppt. is thrown down. Heat gently and filter.
Filtrate contains a
Compound of magnesium, sodium, and potassium.
Divide into two parts (1 and 2.)
Precipitate is either
BaCO3—SrCO3—CaCO3.
Wash thoroughly and proceed as
in Table IV. 1. 2.
Add ammonic chloride, ammonia and
hydric sodic phosphate. Evaporate to dryness and ignite, in order to get
A white crystalline ppt. rid of all compounds of ammonium.
indicates
M A G N E S I U. M. 1. 2.
Test a small portion of Test a solution of the
the residue in a remainder of the residue
Bunsen flame or on a with HCl and PtCl4
platinum wire. A yellow crystalline ppt.
A yellow color indicates indicates
S O DI U. M. IP O T A S S I U. M.
Reactions of the Salts of Aluminium, Chromium, and Iron (Ferrous and Fer ic.)
Iron (Fe=56)
as Fe" (ferrous salts).
White ppt. of ferrous hydrate (FeH2O2),
changing to green and then to red
(Fe2 HaOs).
Whitish green ppt. (FeCOs), becoming
red by exposure to air, forming a
basic carbonate.
Green ppt. becoming red on exposure
to air ; insoluble in excess.
Black ppt. (FeS) soluble in HCl, H2S
being evolved. -
Light blue ppt. (Ka Fe"FeCya), becoming
dark Prussian blue (3 FeCya,” Fe2Cys),
insoluble in acids; decomposed §§
alkalies.
Blue ppt. (Fe"a ..",0s.) (Turnbull’s
blue) insol. in EICl.
No action.
TABLE VII.
Aluminium (Al = 27°5)
Al" and Aliv.
Chromium (Cr-52 5).
Cr", Criv and Crvi.
Iron (Fe=56)
as Feiv (ferric salts).
6. Potassic
7. Potassic
(A.) WET REACTIONs:
1. Ammonia (with or with-
out NH,Cl) . . . .
2. Ammonic carbonate tº #
3. Potassic or sodic hydrate
4. Ammonic sulphide tº º
5. Sodic hydric phosphate ..
ferrocyanide
(KAFeCys) & tº &
ferricyanide
(KalPeCys) * * sº tº
8. Potassic sulphocyanat
(KCNS) . . tº º © tº
(B.) DRY REACTIONs:
1. Heat on charcoal .. tº º
2. Heat on platinum foil with
KNOa and Na,COs ..
3. Borax bead..
White ppt. of aluminic hydrate
(Al2.HsOe); slightly sol, in ex-
cess ; insol. if much NH,Cl be
present.
White ppt. of a basic carbonate,
White ppt. (Al... He Os), soluble in
excess, Al2.He Os being repre-
cipitated by NHaCl.
White gelatinous ppt. (Al2.HsOs)
(HaS is evolved).
A white ppt. (A12 P20s) insol. in
NH,Cl; sol, in KHO.
Blue colored mass (Cobaltous Alu.
mi oote) when moistelled with
cobaltous nitrate.
Green ppt. of chromic hydrate
(Cra HsOs); Sol, in excess, solu-
tion becoming pink.
Green ppt. of a basic carbonate,
Green ppt. (Cr2|He 0s) soluble in
excess, solution becoming grº on,
reprecipitated on boiling, or on
adding NH3Cl.
Bluish green ppt. (Cra HsOs)
when added in excess and the
mixture heated ; insol. in ex-
C688.
A yellow mass (K2CrO2) formed,
sol. in water; solution precipi-
tated as PbCrO, with lead ace—
tate.
Yellow in the inner and emerald
green in the outer flame.
Red ppt. of ferric hydrate (Fe2HsOs);
insol. in excess.
Red ppt. (Fe2H6Os) with evolution of
CO2.
Red ppt. (Fe2HsOe); insoluble in ex-
CeSS,
Black ppt. (FeS); sol. in dil. HCl,
HaS being evolved and white S left.
(Note 5.)
A yellowish white ppt. (Fez P20s). Am-
monic acetate renders precipitation
complete.
Blue ppt. (3FeCya,2Fe2Cys); Sol. in
oxalic acid ; decomposed by KHO.
No ppt., but solution turns reddish
brown.
Blood red color, Fe(CNS), ; color de-
stroyed by HgCl2, tartaric acid, etc.
Minute magnetic spiculae; sol. in HCl :
solution giving a blue ppt. With
Ka FeCys,
$ºmsºmºre
Yellowish brown in the outer flame
and bottle green in the inner flame.
Similar to ferric salts.
NoTES.–1. Ammonic carbonate precipitates this group as well as Ba, Sr, and Ca compounds.
:
. Sullyhuretted hydrogen produces with a
. Potassic ferrocyanide serves to distinguish the presence of iron as a proto or ferrous salt.
. To convert a ferrons into a ferric salt, boil the solution of the ferrous sat with a little nitric acid, or with HCl and a few crystals of KCIOs.
. A Doty, onia, in addition to the above, ralso º the phosphates of iron, cleromium and aluminium, and the phosphates of the alkaline Gai thu.
er, ic salt a ppt. of sulphur, tho ferric being reduced to a ferrous salt (Fe, Cle +
HaS = 2 FeCla + 2 HCl + S).
TABLE VIII.
A Solution contains a Salt of Aluminium, Chromium and Iron (Ferric and Ferrous Salts).
1. Determine the absence of phosphates by heating with ammonic molybdate. The absence of a ppt. indicates the absence of
phosphoric acid.
2. Test for a ferrous salt with potassic ferrocyanide, and for a ferric salt with potassic sulphocyanide.
3. If a ferrous salt be present convert it into a ferric salt by adding a little HCl and a few crystals of KClO3; heat gently until
any chlorous odor ceases to be evolved. --- -
Add ammonic chloride and ammonia : heat gently.
The precipitate may contain—
Ala EIGO6 (white) Crg H606 (green) —Fe2H606 (red).
Filter immediately and wash the precipitate thoroughly. Wash the precipitate into an evaporating dish, and add an excess of
EHO ; boil for some time ; and filter. d
Precipitate consists of Fe. Hø06 (red), and CrºH606 (green.) Filtrate contains Al2.H606.
Fuse one portion of the ppt. on platinum Dissolve in HCl and add potassic Add HCl in slight excess and then N.H., HO
foil with potassic nitrate and sodic car- ferrocyanide ; a blue ppt. in slight excess. A white gelatinous
bonate. Act on the fused mass with (Prussian blue) indicates precipitate indicates
boiling water and test the yellow solu- º
tion with plumbic acetate; a yellow ppt. I R, O N. A L U M I N I TO Mſ.
(PbCrO.) indicates e
[Confirmatory test.—Heat on charcoal with
C H R O M I U. M. cobaltous nitrate.]
phosphoric acid.
TABLE IX.
A Solution contains a Salt of Aluminium, Chromium and Iron (Ferric and Ferrous Salts), and also Phosphates of the Metals of the
Alkaline Earths.
1. Determine the presence or not of ferrous salts. If present convert them into ferric salts, by boiling with hydrochloric acid and potassic chlorate.
2. Determine the presence of phosphates in a fresh portion with ammonic molybdate and heat.
Add ammonia and ammonic chloride ; heat gently; filter and wash thoroughly.
The precipitate may contain—
Al,B,0s and Al,P,0s; Cr. Hø0s; Fe,H,0s and Fe,P,0s; and also phosphates of baryta, strontia, lime and magnesia.
Dissolve in a little HCl and add KHO in excess; filter.
Precipitate consists of iron (Fe, HSOs) and the phosphates of the alkaline earths.
Digest with acetic acid; boil, and filter whilst hot.
A yellow ppt. of ammonic phospho-molybdate indicates
Filtrate contains Al,H30s and Al,P,0s; and Cr, H30s.
Boil for some time and filter.
Residue = Fe,P,0s
indicates
I IR, O IN
(as a phosphate).
Filtrate contains Fe,H30s (that is, iron other than as phos-
phate) and the phosphates of the alkaline earths.
Precipitate Cr, EI,0s
(green.)
Piltrate contains Al, HsOs and Al2P,0s.
Add citric acid and excess of ammonia; filter.
Precipitate=phosphates of the
alkaline earths.
Dissolve in HC1 ; add potassic
acetate and Fe,Cls until the
liquid remains red. Boil for
Some time, filter and test the
filtrate for the
ALKALINE EARTHS.
TABLE IV.
Filtrate contains
iron.
Test with HCl and
potassic ferrocyan-
ide. A blue ppt.
indicates
I F. O IN
(not as a phosphate).
Fuse with Na,CO,
and KNO3 on pla-
tinum foil. A yellow
soluble mass indi-
cates
CEIROMIUMI.
[Confirmatory test.—
Acetic acid
and
Lead acetate.]
Add a slight excess of acetic acid; boil, and filter
whilst hot.
Precipitate Al...P,0s.
Filtrate Al,H,0s.
Indicates the presence of
PEIOSPEIATE OF
ALUMINA.
Neutralise with am-
monia. A white
ppt. indicates
ALUMINA.
zęeactions of the Salts of Aſanganese, 2&nc,
Wickel,
a rºcł Cobalt.
Manganese (Mn=55).
”, iy and vi.
Zinc (Zn’’=65).
Nickel (Ni–58-8).
” and iv.
Cobalt (Co-58-8).
’’ and iv.
(A.) WET REACTIONs:—
1. Amnionic sulphide
2. Sulphuretted hydrogen
3
. Ammonia
4. Ammonia and Ammonic
chloride . . . . . .
5. Sodic or potassic hy-
drate . . # * * *
6. Ammonic carbonate
7. Potassic cyanide . .
8. Potassic ferro-cyanide..
(B.) DRY REACTIONs:–
1. Borax bead . .
2. Fused with sodic carbon-
ate and potassic nitrate
3. Heated on charcoal with
sodic carbonate in the
inner blow-pipe flame
Flesh colored ppt. (MnS);
soluble in acetic and
other acids.
Precipitation imperfect.
Whiteppt., turning brown by
exposure to air (MnH,02).
The brown ppt. is insolu-
ble in NH3Cl.
No ppt. (2NEI,Cl,MnO1,
formed which is soluble.)
Whiteppt. (MnH,02); insol.
in excess. Darkens by ex-
posure from absorbing 0.
White ppt. (MnOOA) be-
coming brown.
White ppt. (MnCy); solu-
ble in excess.
White ppt.
Outer flame, amethyst;
inner flame, colorless.
Green sodic and potassic
mangānāte. -
*
White ppt. (ZnS); insoluble in acetic
acid or in KHO ; soluble in mineral
acids.
Precipitates ZnS from a solution of an
acetate, or of a zinc salt containing an
alkaline acetate, even if free acetic
acid be present, and also if the solu-
tion of the zinc salt be neutral.
White ppt. (ZnH2O2); soluble in
€XCéSS.
No ppt.
White ppt. (ZnH,0.); soluble in ex-
cess, and in (NH4)HO and NH3Cl.
White ppt. Soluble in excess.
White ppt. (ZnCy.); soluble in ex-
C98S,
Yellowish white ppt.
-
Becomes yellow when hot, white when
cold. Turns green when moistened
with cobaltous nitrate and heated.
Plaek ppt. (NiS); insoluble in acetic
acid; soluble in excess of yellow
ammonic sulphide.
Precipitates NiS from a solution of an
acetate or of a nickelous salt mixed
with an alkaline acetate. No pre-
cipitate occurs in an acid solution,
Light green ppt. (NiII,02) soluble in
excess (solution blue); reprecipi-
tated by KHO.
No ppt.
Light green ppt. (NiH,0); insoluble
in excess.
Green ppt. Soluble in excess, forming
a greenish blue Solution.
Yellowish green ppt. (NiCy); solu-
ble in excess, forming a brownish
yellow solution (2KCy,NiCy). The
NiCy, may be reprecipitated by a
dilute acid. The double salt is
decomposed by NaC10, Ni,H.0,
being precipitated.
Greenish white ppt.
Outer flame, sherry red; inner flame,
grey (from reduced Ni).
*
A grey metallic powder, attracted by
the magnet, producing a green solu-
tion when dissolved in HNO,
Black ppt. (CoS); insolublein’s
acetic acid & in dilute HCl; .
soluble in aqua regia. * :
A black ppt. (CoS) as above.
Blue ppt. (basic salt); soluble
in excess (solution reddish
brown). *
No ppt.
Blueppt. (basic salt); insolu-
ble in excess. On boiling be-
comes Co B,0s.
Rose-red ppt. of basic car-,
bonate; soluble in excess,
forming a red solution.
Red brown ppt. of CoCy, ; ,
soluble in excess forming
2KCy,CoCya. This on boil-
ing, becomes K.Co.,Cyra,
which is neither reprecipi-
tated by HCl, nor decom.
posed by NaClO.
Dark green ppt.
A blue glass either in the
Outer or inner flame.
*mºmºsº
A grey or white metallie pow-
der, attracted by the magnet;
soluble in HNOs producing
a reddish-colored solution.
--
TABLE XI,
A Solution contains a Salt of Zinc, Manganese, Nickel, and Cobalt,
Filter rapidly (to prevent the oxidation of the sulphides) and wash the ppt. With water
containing (NHA).S. The ppt. may contain *
ZnS (white)—MnS (flesh colored)—NiS (black)
Boil the precipitate in acetic acid and filter.
Add ammonic sulphide in excess.
CoS (black).
Filtrate contains manganese acetate. Precipitate contains ZnS (white) and NiS and CoS (black).
Add NH,Cl, ammonia and am- Dissolve in the least possible quantity of nitric acid, and add NaIIO in excess and filter.
monic sulphide; a flesh colored
ppt. indicates
Filtrate contains Zinc (ZnH2O3). Precipitate consists of NiH,0, and CoH,02.
MANGANIESE.
- Pass H.S through the solution. A white ppt. Dissolve in HCl and add a few crystals of KC10, ; heat until
Confirm the presence of manganese (ZnS) indicates all chlorous odor disappears. Neutralise the solution with
by fusion with potassic nitrate Na,CO, Add KCy until the precipitate first formed is re.
and sodic carbonate on platinum Z I N C. dissolved. Boil, and when cold add a strong solution of
foil. - sodic hypochlorite. After standing for some time, filter.
} A black ppt. (Ni, HsO4) Filtrate contains Cobalt, as *
indicates KGCo.,CyI2.
NICKEL.
Confir 3 Cºl J º – W. a Evaporate to dryness and test by
(Confirm by bead expt) borax bead; a blue color indi-
CateS - - .
COBAI.T.

- TABILE XII.
Reactions of the Salts of Copper, Bismuth, and Cadmium.
Copper (Cu-63-5). As cupric salts, Cu”.
Bismuth (Bi-208).
Cadmium (Cd=112).
*
/
(A.) WET REACTIONs:–
1. Sulphuretted hydrogen (group
reagent) . . . . . . . .
. Ammonic sulphide is g º 0.
. Sodic and potassic hydrates
;
4. Ammonic hydrate. ,
Or
5. Ammonic carbonate
6. Sodic carbonate . . . . . .
7. Potassic cyanide . . . . . .
8. Potassic ferrocyanide .
9. Potassic chromate (K.Cr,0.)
10.
11.
Sulphuric acid
Potassic iodide
(B.) DRY REACTIONs:–
I. Heated on charcoal with sodic
carbonate s & 4 s
2. Borax bead . . . . . . . . .
Brownish black ppt. (CuS); sol. with de-
composition, in nitric acid and in potassic
cyanide; insol. in ammonic sulphide.
Brownish black ppt. (CuS).
Light blue ppt. (CuII,02); insol. in excess,
turns black on boiling (30 u0, H.,0). In
presence of grape sugar, etc., the ppt.
dissolves, forming a blue solution, which
on boiling precipitates cuprous oxide
(Cu,0).
Greenish blue ppt. (basic salt); soluble in
excess to form a deep blue solution
(cupr-ammonic hydrate).
A greenish-blue ppt., becoming black
(3Cu0, H.,0) on boiling; soluble in am-
monic hydrate.
Greenish-yellow ppt. (CuCy); Sol, in ex-
cess. (No ppt. occurs when this Solu-
tion is treated with H.S). -
Reddish-brown ppt. (Cu,FeCyg); insol.
in dilute acids; decomposed by alkaline
hydrates, 3Cu0, H20 being separated.
Brick-red ppt. ; Sol. in NH4H0, forming
a green solution.
No ppt.
Grey ppt.
Red bead; sol. in HNO3, giving a red-
dish-brown ppt. with K FeCyg.
Blue glass. A trace of tin turns the bead
a red color, owing to formation of Cu,0.
Brownish black ppt. (Bi,S); sol. in
strong HNOs ; insol. in ammonic sul-
phide.
Ditto.
White ppt. (BiH,03); insol. in excess,
becoming yellow on boiling (Bi,0a).
White ppt. of BiH,0, with NH,EIO,
and of a basic
carbonate with
(NH4)2CO3; insol. in excess. .
White ppt., as with (NHA),CO3,
White ppt. ; insol. in excess.
Light yellow ppt.
Yellow ppt. of basic chromate; sol, in
dil. HNO3; insol. in KHO. (Distin-
guish from lead,
No ppt. (Distinguish from lead.)
A brown ppt. (Biſs).
A brittle bead, with a dark orange in-
crustation when hot, becoming yellow
when cold.
Yellow when the bead is hot, and color-
less when cold.
Yellow ppt. (CdS); sol, in hot dilute
HNOs, and in cold dilute H,SO, ;
insol. in ammonic sulphide and in "
potassic cyanide.
Ditto.
A white ppt. (CdII,03); insol. in ex-
CéSS,
White ppt. of CdII,0, with NH HO,
and of CdCO, with (NH3)2COs; in-
Sol. in excess. -
Same ppt. as with (N H9.00,
White ppt. (CdCys); sol. in excess.
(A. ppt. occurs when this solution *:
is treated with H.S.)
White ppt.
Slightly yellow ppt. ; sol. in NH.H.O.
No ppt.
A white ppt.
Forms a reddish-brown incrustation.
Yellow when the bead is hot, colorless
when cold.
º ~. * * , y
Reactions of the Salts of Tin (Sn"
TABLE XIII.
& Sn"), Antimony (Sb" & Sb'), and Arsenic (As” & ASV).
Tin (Sn"=118).
As Stannous salts (1) (3).
Tin (Sniv-118).
As stannic salts (2) (3).
Antimony (Sby = 122).
Antimony (Sb"— 122).
As antimonic salts (6).
As antimonious salts (6).
Arsenic (Asv = 75).
Arsenic (As”=75).
As arsenic salts (8) (9) (10).
As arsenious salts (8) (9).
(A.) WET REACTIONs.
. Sulphuretted
hydrogen
l
. Ammonic Sul-
phide . . . .
. Sodic and potas-
sic hydrates. .
.
4. Ammonic
hy-
drate * -
5
. Ammonic car-
bonate . . .
Airk brown ppt. (SnS);
insol. in NH, H0; insol. in
the normal, but Sol. in the
yellow ammonic sulphide,
and repptd. as SnS., on
adding HCl ; sol. in KHO
and NaHO.
A dark brown ppt. (SnS);
Sol. in excess.
White ppt. (2SnO, H2O);
Sol. in excess (K2SnO2).
White ppt (2SnO, H2O); in-
sol. in excess ; soi. in KHO
or NaHO. -
White ppt. (2SnO, H2O);
insol. in excess; Sol. in
KHO
A yellow ppt. (SnS,); sol. in
N.H., HO, in alkaline sul-
phides, in KHO, and in
HC1.
Yellow ppt. (SnS2); sol. in
CXCèSS.
White ppt. (SnO2, H2O); sol.
in excess and in HCl (4).
White ppt. (SnO2, H2O) ;
sparingly sol. in excess
(precipitation prevented by
tartaric acid); so). in KHO.
White ppt (SnO2, H20); Sol,
in KHO or Na HO.
Orange ppt. (Sb2S3, mixed
with S and Sb2S3); sol. in
all-aline sulphides and hy-
drates; sol. in boiling HCl,
with evolution of H2S and
precipitation of S.
Orange red ppt., Sb2S3; so).
in (NH4)2S, and in KHO ;
reppd. by HCl ; very slight-
ly sol. in NEI, HO, and
in Sol. in ammonic carbo-
nate ; Sol. in boiling HCl,
forming SbCla (5).
Orange ppt. (Sb2S2, S, and
Orange red ppt. (Sb2S3);
- Sb2S3) ; Sol, in excess.
sol. in excess.
White ppt. (Sbaſ) a) (12);
sol. in excess, potassic an-
timonite being formed.
White ppt. (Sb.02) (12),
insol. in excess ; Sol, in
IKHO,
White ppt. (Sb2O3).
A yellow ppt. (As2S3 +S),
sol. in (NH i),S, NH, HO
and in ammonic carbonate.
A yellow ppt. (As2S3); sol.
in alkaline hydrates, car-
bonates (= alkaline arsen-
ite) and sulphides (= al-
kaline sulpharsenites) re-
pptd. by HCl, or by HNOa;
nearly insol. in boiling
HCl ; sol. in boiling HNOa.
Yellow ppt. (As2S3); sol. Yellow ppt., soluble in
in excess. €XCCSS.
No ppt. No ppt.
No ppt. No ppt.
No ppt. NO ppt.
. Marsh's Test—
By setting free
hydrogen in
the presence
of the metal.
{}
7. Reinsch’s Test—
By boiling a
solution of the
=mº
SbH, is evolved, when H is set free, by the action of Zn on
HaSO4, but not by the action of Zn on KHO
Tests for SbFia—(a.) Passed through a solution of AgNOa,
precipitates a compound of Ag and Sb (3AgNO3 + SbH a
=3|HNO a-i-AgaSb), (1 l).
(8.) Flame bluish green.
(y.) Mirrors of metallic Sb are formed either on a cold piece
of porcelain held in the SbH a flame, or in the glass tube
through which the Sb IIa is passing, very near the spot at
which the flame of a spirit lamp is applied. These deposits
are insoluble in a solution of bleaching-powder, or of
sodic hypochlorite.
Metal precipitated on the copper.
AsH3 is evolved when H is set free either by the action of
Zn on H2SO4, or of Zu on KHO.
Tests for AsH3.—(a.) Passed through solution of AgNO3,
precipitates metallic silver, the solution containing As2O3.
(6AgNO3 + AsH3+3H2O=6HNO3 + 3 Aga + ASPI30s).
(8.) Flame bluish-white ; white fumes being apparent
above the flame of As2Os.
(y.) Mirrors of metallic As formed either when a cold
piece of porcelain is held in the ASPIs flame, or on the
glass tube through which the ASH's is passing, at
some distance from the point at which flame is ap-
plied These metallic mirrors are soluble in a solution of
bleaching-p wiler or of sodic hypochlorite.
Grey film of As, Cuz thrown || Grey film thrown down on
down on the copper in di- the copper in concentrated
lute HCl solutions. HCl solutions, but not in
Confirm presence of metal | dilute HCl solutions. -

-Prº-
9. Amnonio ar-
gentic nitrate
... 10. Ammonio cu-
pric sulphate
A.
11. Auric chloride
AuCl2) º
(B.) DRY REACTIONS.
Fused on charcoal
with sodic carbon-
ate and potassic
cyanide.
With an excess of SnCl2, a
black ppt. of metallic Hg.
With SnCl2 a purple ppt.
(purple of Cassius),
White malleable bead; sol. in HNO3, the solution giving a
white ppt. with HgCl2.
The bead has a yellow incrustation of SnO2, which, when
heated with cobaltous nitrate, becomes bluish green.
Brittle metallic bead ; when heated in air gives off dense
white fumes of Sb,0a, which incrust the globule.
Tho bead is soluble in aqua regia (=SbCls)-; insol. in
HCl, converted by HNOa into a mixture of Sb2Oa and
Sb20s, which is insol. in HNO3, but Sol. in a solution of
tartaric acid,
rº -Fºr Hºrrºwº
A yellow ppt. (Ag3AsOs);
sol. in NH. (10, NHaCl and
HNOa.
A yellowish green ppt. (CuPI
AsOa), Sol. in
NH,Cl and HNOa.
Hall0,
º crystallins nºt. of
Mg N H . AsO.A., in the pre-
sence of NH AHO and
NH,Cl.
A reddish-brown ppt. of
triargentic arseniate (Aga
AsO4); Sol. in NFL, HO
and HNOa. -
A greenish-blue ppt. of hy-
dric cupric arsenate (CuH
AsO4) soluble in NHAHO
and HNOa.
Ppt. of metallic gold from
acid solutions.
[Heat the arsenical compound with C and Na2COs in a
reduction tube J . A steel-grey mirror forms in the upper
part of the tube, insoluble in HCl and oxidised by HNOa.
Heated in air forms Asa Os. The metal is capable of com-
plete volatilization (garlic odor). º,
T. Wash with hot water, and boil in a srong solution of tarfaric acid.
Filter ; acidulate the filtrate with HC], and pass H2S through the solution.
An Orange precipitate (Sb2S3) indicates antimony,
12. This precipitate does not occur with tartar emetic,
ution be placed in a platinum dish, and a rod of zinc immersed in the soluti
The metal is in soluble in cold IIC], but soluble in warm HNO3.
8, Arsenious compounds act under certain circumstances as powerful reducing agents.
Thus:-(a) If HgCl, be mixed with SnCl2, a white piecipitate is first formed of Hg2Cla, and when the mixture is heated, metallic mercury
NoTEs.-1. Stannous salts readily become stannic salts.
is precipitated, and SnCl4 is formed.
(8.) CuCl2 forms with SnCl2, C12Cl2, and SnCl4.
(y.) Fe2Cld forms with SnCl2, FeCl2, and SnCl2. g
Stannotis chloride, in a solution containing HCl, becomes, exposed to the air, stannic chloride and stannous oxychloride (Smø0Cl2).
2. Stannic is reduced to stanilous chloride by the action of metallic tin or copper (SnCl4 +Sn=2SnCl2). &
3. A piece of zinc (but not Fe) precipitates metallic tin as a grey spongy mass upon the zinc from acid solutions of stannous and Stannic Salts.
4. Neutral salts (as Nags Oa) precipitate metastannic acid (Sn.0,0,5H2O) from solutions of stannic salts, when heated. g
5. Water decomposes SbOla, a white insoluble antimonous oxychloride or powder of algarnth (SbOCl), soluble in tartaric acid being formed. d
[NOTE.-The precipitate of BiOC1 produced by the action of water on BiCla, is insoluble in tartaric acid.]
6. Antimony is preci ſº from its solutions as a black powder by metallic zinc, iron, copper, lead, etc.
7. If an antimony so
into contact With it.
(a.) 2012+ As2O3+5H2O= A8204,31120+4HCl.
(6.) 4AuCla-i-3Asg02 +15EL20=3(As203,3H2O)+Au, +12HICl. * tº
Also note that arsenious and arsenic compounds may act as oxidising agents, becoming themselves either reduced to a lower oxide, or to the metallic state.
9. For the distinctions between arsenious and arsenic compounds, see Reactions of Reinsch's Test, and magnesic sulphate.
10. Arsenic acid is reduced to arsenious acid by SO2
11. Filter the solution of the silver and proceed as
Precipitale. "
Thus—
ollows with the precipitate and filtrate :-
on, metallic antimony will be deposited on the platinum, at the spot where the zinc comes
Filtrate. ~~
Neutralize with NH, H0. -
(a.) If A5 be present, a yellow ppt. of arsenite of silver occurs (Aga AsO2), -,
(3.) If Sb only be present, no ppt, is formed.
*
TABLE XIV.
4 Solution may contain a Salt of Lead, Mercury, Copper, Bismuth, and Cadmium ; and also a Salt of Tin, Antimony and Arsenic.
Acidulate the solution with HCl and pass H2S for some time through it.
The precipitate will consist of -
PbS, HgS, CuS, BioS3. CdS, and SnS, SnS, Sb,San As, S3.
Black; black; black ; black; yellow ; brown ; yellow ; orange red; yellow.
Wash the precipitate and boil with ammonic sulphide; filter.
Heat gently.
Residue contains lead, mercury, copper, bismuth, and cadmium. Filtrate contains tin, antimony and arsenic.
Dissolve in a little boiling nitric acid ; dilute with water; add dilute H.S0, until a ppt. 1. Add HCl, when the metals are reprecipitated as SnS, Sb,S, and
ceases to be formed ; when cold add to the solution an equal bulk of methylated alco- As,S, ; filter and wash. -
hol; filter. 2. Digest the ppt. at a gentle heat with ammonic carbonate; filter.
–––– — --T
Solution contains
Residue contains lead and mercury. Filtrate contains bismuth, copper and cadmium. Residue contains SnS, and Sb2S3
arsenic.
Add tartaric acid and excess of Distil off the spirit from the solution; add excess Dissolve in boiling HC1. Mix the acid solu- Add HCl. A yellow
ammonia. Boil; filter. of NH, H0 ; boil and filter. tion with zinc in a Marsh's apparatus, in ppt. of As,Ss indi-
! order to generate antimoniuretted hydrogen, CateS
Residue HgS Filtrate contains | Precipitate BiH,0, Filtrate contains Cu and Cd. º
esldue figb. PbSO,. indicates A metallic mirror | If there is any metallic ARSENIC.
EISMIUTEI If copper be preseut the solu- formed When a ppt. On the zinc, detach
Reduce with | Add potassic chro- & tion is blue. Add HCl in cold piece of it, and dissolve it in heating i
Na,CO. mate. A yellow (Confirm by dissolv- slight excess, and pass II,S porcelain is held HCl, Dilute with H.O. (nº º ‘...."
A metallic mirror | Ept. of plumbic ing in a little HCl through the solution. Filter in the ignited Add HgCl, ; a grey .." * C ãº. --
indicates chrºmate—. and adding a quan- and wash the ppt. with Hºs gas indicates ppt. of Hg or a white º ) sodic carbon-
IMIERCTURY {PbCrO.)indicates| tity of water to the Water. Boil the ppt, with ANTIMONY. ppt. of Hg,C), indicates ge
- LEAID dried residue. dilute H.S0, and filter. TIN.
(as a mercuric salt) !, f
Black Resi- p.
due CuS. Filtrate Có.
indicates | Add NII, HO
and H2S ; a
COPPER. yellow ppt. of
CdS indicates
CADIVIITUIVI.
Reactions of Salts of Zead,
TAIBLE XV.
Lead (Pb- 107).
” and iv
Silver (Ag+ 108).
Silver and Mercury (as Mercurous and Mercuric Salts).
Mercury ('Hg'=200).
As mercurous Salts. (NotE 1.)
|
White ppt. (PbC12); soluble in boil-
ing water, or in an excess of cold
water. The boiling solution deposits
crystals on cooling ; insoluble in
am monia.
Black ppt. (PbS) from acid solutions.
White ppt. (PbSO.); insol in water
and in dilute acids, Sol. in boiling
HCl, in Na HQ, and in an ammoni-
acal solution of tartaric acid.
White ppt. (Pb) [20,); Sol. in excess,
especially when heated.
White ppt. (basic salt); insol. in
€ XCGSS,
A white ppt. (basic carbonate); insol.
in H., () and KCy.
Yellow ppt. (Pb. 2); sol. in excess of
KI, and in boiling H20 ; golden
scales are pptd. as the water cools.
A white ppt. (PbCyg); insol. in ex-
cess, Sol. in dilute HNO3.
Yellow ppt. (PbCrO4); sol. in KHO,
insol. in acetic acid.
A malleable motallic bead with yollow
incrustation of PbO when hot. The
bead is 8ol. in Il NO, the solution
giving a white ppt. With II 2 SO4,
White ppt. (AgCl); insol. in boiling
water, sol. in ammonia, the AgCl
being repptd. on adding an excess
of HNOa. Turns violet on exposure
to light.
Black ppt. (Ag.,S) from acid solu-
tions; sol. in dilute boiling HINOa.
No ppt.
Brown ppt. (Ag30). When heated,
Ag,0 evolves O.
Brown ppt. (Ag30); Sol, in excess.
White ppt. ; insol. in excess.
Yellow ppt. (AgI); insol. in dilute
HNO3, almost in sol. in NH, HO
(AgCl is sol. in NPſ, HO).
White ppt. (AgCy); Sol. in excess
and in N.H., H 0, and in sodic hypo-
sulphite; insol. in dilute HNOa.
*º-
Dark red ppt. (Aga CrO4).
A bright malleable bead, without in-
crustation ; Sol. in NHO, the solu-
tion giving a white ppt. with HCl.
White ppt. ('Hg/2012 calomel);
insol. in hot water; insol. in,
but blackened by, ammonia
(NH2 Hg2Cl).
Black ppt. ('Hg2S); insol, in di-
lute acids.
No ppt., or a white ppt. if the
mercury Salt be in great excess.
Black ppt. ('Big',0); insol. in
eX CéSS.
Black ppt. of basic dimercurous
ammonio nitrate ; insol, in ex-
COS8,
White ppt , , becoming brown;
insol, in excess.
Green ppt.
A grey ppt. of metallic mercury.
Brick red ppt.
Instantly reduced and volatized.
Wide NOTE 2.
Mercury (Hg"=200).
As Mercuric Salts. (NoTE l.)
---
No ppt.
A white ppt. (HgS, Hg NOA), chang-
ing to yellow, then to brown (HgS
and HgCla), becoming ultimately
black (Hgs); insol. in (NH4)2S,
HCl, or HNOa.
No ppt.
Yellow ppt. (HgC); insoluble in
OX CeSS.
A white ppt. of a mercuric salt and
mercuranide, called “white pre-
cipitate" (N.H., Hg"Cl).
Reddish-brown ppt. ; insol. in ex-
CöSS.
Bright red ppt. (HgI2); soluble in
excess of RI or mercuric salt. .
A white ppt. with mercuric mitrate
(not with HgCla) of Hg ya ; sol.
in excess.
White ppt. (Hg a C12) calomel; re-
duced to metallic state when
boiled in excess of the reagent.
Reddish-yellow ppt. with KaCrOa,
but no ppt. with K2Cr,07.
Instantly reduced and volatized.
be a fixed acid (as CrO2; P20s, etc.), a fixed residue (as Cr20a) rernains.
Heat one part of a perfectly dry mercury salt with twelve parts of ignºted sodic carbonate in a glass tube. The metal is reduced and sublimes.
(A.) WET REACTIONs: —
1. HYDRoch LORIC ACID (group re-
agent) .. * * - * e tº
2. Sulphuretted hydrogen
3. Sulphuric acid
4. Sodic or potassic by drates
5. Ammonia. . .
6. Sodic or potassic carbonate
7. Potassic iodide (KI)
8. Potagsic cyanide . .
9. Stannous chloride (SnCl2)
10. Potaš8ic chrºe (K2CrO4) . .
3, Iyſ.
Potassic bichromate (K2Cr, Oz)
(B.) Duty REACTIONS:-
Reduce on charcoal with Na2CO2
NOTE3.—".
Mercurous and mercuric salts are oxidizing agents.
When mercuric 8alts are employed for this purpose, mercurous salts are first forme
2. A slip of copper, placed in a solution of a salt of mercury, becomes rapidly coated with a grey stain of the metal. This st
by heat. Mercury salts, heated alone in a tube, either sublime without decomposition (HgCl2 ; Hg. Cla; HgS; IIgia), or are decomposed.
grey coating, the particles combining, when slightly shaken, to form a globule. Dissolve this globule in nitric acid, and tast the solution for mercury.
- id, and finally the metal.
ain bocomes bright when rubbed, and may be volatilized
If the acid with which they are combined
The sublimate appears like a
TABLE XVI.
A Solution contains a Salt of Lead, Silver and Mercury (as a Mercurous Salt).
Add hydrochloric acid (in excess) and heat very gently. The precipitate contains
PbCl, AgCl
'Hg/2012.
Filter : Boil the precipitate in a quantity of water, and filter whilst hot.
The residue contains AgCl and 'Hg. Cl2. Filtrate contains PbCl2.
Add CA Yº ſº. - - }]”. e
-------- - - - - ----- - ----- an excess of ammonia and filter A white ppt. (PbS0,) with sulphuric
: A - Al
- .* 4- A. - acid indicates
Residue (black) contains mercury. Filtrate contains AgCl.
LIEAD,
A metallic mirror and globules are formed Add nitric acid in excess; a white ppt.
when the black residue (NH2/Hg,'Cl) (AgCl) indicates
is heated with sodic carbonate in a
glass tube. This indicates the pre-
sence of
SILVER.
IVIERCURY
(as a mercurous salt).
*"T"-------------------------------------- --_-_
COMPLETE EXAMINATION For BASEs.
(A.)—The Substance being a Solid, and neither a Free Metal nor an Amalgam ;
. Examine the body by the dry methods already described (page 437).
. Dissolve it, or as Inuch of it as will dissolve, in water. (Note the reaction of the solution to litmus).
. Treat the insoluble residue first with dilute HCl and boil; and afterwards with conc. HCl and boil.
:
[The solutions 2 and 3 may be mixed and examined together.]
Treat the residue insoluble in HCl, with HNO3, and boil.
Treat any residue insoluble in HNO3 with aqua regia.
Any residue insoluble in water and in acids is to be dried, mixed with four times its weight of a mixture of equal parts of
K2CO3 and Na2CO3, and the mixture fused in a crucible. The fused mass is then to be boiled in water, and filtered.
JProceed as follows:–
:
Residue. Filtrate.
Contains the bases as carbonates.
tº … e. tº gº & Examine for acids.
Dissolve this in HCl and examine in the ordinary way.
NoTE.—The insoluble residue may consist of BaSO, SrSO, CaSO4, and PbSO, ; also of AgCl and PbCl, ; also of ignited
SiO2, Al2O3, Cr,03, Fe2O3, SnO2, and Sb2O,.]
(B)—The Substance being a Metal;
I.—Dissolve in nitric acid diluted with water.
(a.) Metals soluble with evolution of red fumes (Ag, Hg, Pb, Bi, Cu, Cd, As, Fe, Zn).
(ſ3.) Metals evolving red fumes but leaving a white insoluble residue (Sb, Sn).
II.-If the metal is insoluble in HNO3, boil in HCl.
III.-Any residue insoluble in HCl, dissolve in aqua regia and test the Solution for gold and platinum.
TABLE XVII.
General Analysis.
1.—Test for ammonia in original material.
2.—The rare metals, as gold, platinum, etc., must be searched for separately.
No. 1.
Group reagent,
HYDROCIIIloric AcID.
Add an excess of acid
and filter.
SULPH
No. 2.
Group reagent,
URETTED HYDROGEN.
Previous to passing the H.S
through the solution, dilute
No. 3.
Group reagent,
AMMONIA.
Evaporate filtrate from No. 2 to
dryness after adding a little
No. 4.
Group reagent,
AMMONIC SULPHIDE.
To filtrate add (NHA),S
or pass H.S through
No. 5.
Group reagent,
AMMONIC CARBONATE.
Add to the filtrate
after boiling am-
No. 6.
No Group reagent.
Notes 1, 2 and 4. with water. Pass the H.S HNO, Dissolve the residue in the filtrate contain- monic chloride and
through to Saturation, and HC1. Add a little water and ing ammonia from ammonic carbon-
heat gently. filter off any undissolved SiO2. No. 3. ate.
Add ammonic chloride and then
the ammonia. Notes 5 and 6. ---.
Precipitate. Precipitate. Precipitate. Precipitate. Precipitate. Filtrate contains
AgCl white PbS black do $2 a. Al,H,0s white NiS black BaCO, white salts of
PbCl, white FIgS black TE := 3 Fe, H.O., red CoS black SrC0, white Mg”0
Hg,Cl, white CuS black ### Cr, H,0s green ZnS white CaCO, white Li,0
= Group 1. Bi,S, black # = 3 Al,P,0, white MnS flesh colored = Group 5. K., O
Examine by CdS yellow J - a 7 Phosphates of hit = Group 4. Examine by Na,0
Table XVI, S alkaline earths } Whlte Examine by Table IV. = Group 6.
nS brown P. as tº = Group 3 Table XI Examine b
SnS, yellow | ‘... = 3 . . Fºroup. 3. . &l O10 All. xamine by
sis 3 : : Examine by Table IX. if phos- Table W.
sh's. | Orange \ = 3 G. phates be present, or by Table
Ass, well 3 * : VIII. if no phosphates be
S, Sa yellow A resent.
= Group 2. p
Examine by Table XIV.
NoTES.–1. If the solution be a hydrochloric acid solution, pass on to No. 2.
o
:
is complete.
. Silicic, boric, benzoic and uric acids are also precipitated by HCl.
The presence of gold and platinum must be determined in the original solution.
. Any precipitate occurring of oxychlorides may be disregarded, as these will be converted by II,S into sulphides.
. If organic matter is present, the residue must be ignited.
. The original solution should be tested for iron as a ferrous salt.
Citric, tartaric, and other organic acids prevent the precipitation of the group.
If present, care must be taken that its conversion at this stage into a ferric salt
459
be insoluble.
III.-ExAMINATION FOR ACIDs.
1. Test the substance as to its solubility in water.
If the base be known, and the substance be found to be soluble,
certain acids will be excluded, because the compounds are known to
Thus, knowing baryta to be present, and finding the
salt to be soluble, we know it cannot be sulphate of baryta, because
that is insoluble.
Or, conversely, knowing the base to be magnesia,
and finding the salt to be insoluble, we know it cannot be a sulphate
of magnesia, because that is soluble.
2. Heat a portion of the finely-powdered substance in a test tube.
Source.
Gas
evolved. Tests.
Oxygen. Supports combustion.
SO, Odor. Blues starch and iodic acid.
N20, Reddish brown vapor. .
CO, Renders lime-water turbid.
CO Blue flame.
CN Odor. Burns with a rose flame.
CS, Odor; gas combustible.
II,S Odor; blackens lead paper.
Peroxides; nitrates; chlorates; etc.
Sulphites; hyposulphites.
Decomposition of the nitrates of the
heavy metals.
Carbonates.
Oxalates and formates.
Cyanogen compounds.
Sulphocyanates.
Sulphides ; sulphites; hyposulphites.
;
3. Heat a portion with two or three times its bulk of sulphuric acid.
Acid. Results.
Carbonic Substance effervesces immediately; gas evolved whitems
lime water.
Hydrochloric Fumes inritating. The gas evolved turns white when
ammonia is brought near it.
Acetic . . . . Winegar odor.
Sulphurous . . . . . . Brimstone odor; blues starch and iodic acid.
Hyposulphurous (thio-
sulphuric) * * Brimstone odor, with the separation of sulphur.
Hydrosulphuric .. Rotten egg odor; blackens lead paper.
Hydrofluolic Irritating odor; corrodes glass.
Oxalic . .
Cyanic.. Evolve CO, which burns with a lavender flame.
Ferrocyanic
Chromic Evolves O ; solution becomes brown.
Chloric Evolves a greenish yellow explosive gas. [Further test—
Precipitate any chloride present in a solution of the salt
with AgNO, ; evaporate the clear filtrate to dryness;
fuse the residue, whereby the chlorate is converted into
chloride, and precipitate with argentic nitrate.]
Hypochlorous Evolves the yellowish-green chlorine.
Hydriodic |Bvolves violet vapors, which turn starch paper blue; so-
Hydrobromic ..
Nitrous * * * *
[Also, under certain
conditions, Nitric.]
lution turns dark colored.
Evolves reddish vapors, which turn starch paper yellow ;
solution turns red.
Reddish-brown fumes. [Further test for nitrous acid—
Mix a little of the solution with starch paste and KI;
add to the solution a drop of H2SO4, when the blue
iodide of starch is formed.]
[No action results with the following acids:-Sulphuric, phosphoric, silicic,
boric, arsenic, iodic, and titanic.
460 HANDBOOK OF MODERN CHEMISTRY.
\
4. Test for Nitric Acid.
(a.) Dissolve a small portion of the substance in water, and add
H2SO, to set free the nitric acid. Float a solution of FeSO, on the
surface of the mixture. A brown line at the junction of the liquids
indicates nitric acid. !
(3.) Add to the solution a little sulphindigotic acid to color it, and
then H2SO4 and heat. If nitric acid be present, the indigo will be
bleached. Chloric, bromic, iodic, and also nitrous, chlorous and
hypochlorous acids, produce a similar reaction.
5. Systematic Examination for Acids.
Boil a considerable quantity of the substance with a slight
excess of sodic carbonate. This removes all bases (other than the
alkalies), as carbonates, basic carbonates, or oxides, the presence of
which would interfere with many reactions (e.g., BaCl2 would
precipitate Ag or Pb as well as H2SO4, etc.).
Filter off the precipitate, and boil the solution.
(A.) A preliminary examination of a small quantity, neutralized
with nitric acid, and divided into two parts, is to be made as follows:–
A.—Add BaCl, or B.—Add AgNO3.
Ba(NO3)2.
Sulphuric ; white ppt., insol. Precipitates; sol. in Precipitates; insol. in
in )3. HNO,. IIN0.
Boric h
Phosphoric - -
§. Yº, Sulphurous | Hydrochlorie; white ppt.
Hydrofluoric - 3' | Boric White (sol. in ammonia).
Sulphurous Silicic | ppts. | Hydrobromic ; yellowish
Chromic ; yellow ppt., sol. in Metaphosphoric white pp. (slightly sol.
HN0. Phosphoric ; yellow ppt. in ammonia).
Chromic ; red ppt. Hydriodic; yellow ppt. (in-
Sol. in ammonia).
Hydrosulphuric; black ppt.

Boil the solution.
Sulphurous
IIyposulphurous
(also Ferrous salts) |
give black ppts. of
reduced silver.
(B.) The remainder of the solution is to be divided into four
parts, and treated as in the following table:–
PART NO. 3.
Portion acidulated with acetic acid (1).
PART No. 4.
Portion rendered neutral.
[Add a slight excess of [INOs ; boil; and
exactly heutralize with ammonia.]
Yeagent. Results. Aºi. Reagent. łesults, Aºi, ºil. | Reagent. Results. Aºi. | Reagent, Results. Aºi.
t | # * **, *, a
BaCl2 | A white pnt. ; insol. H2SO, AgNO,(6) A white pot. ; soi. HCl (1) C.C.I., A white gelatinous HF CaCl, White ppt. ; sol. in Tartatic
on boiling (1) (2) in NH, HQ & ppt. (2) (CaF2) & NH,Cl & KHO (1) -
Fe. Cle A deep blue ppt. (3) Ha FeCyc * } A yellowish white HBr (2) (3) CaSO, A white ppt. Oxalic (3) y 3 White ppt. after Citric
ppt.; slightly sol. NH, H0 has been
in NHAHO i added and the
& & | solution boiled
p 7 A brown color only Ho Fe2Cy 12 ; , A sºvº shift HI (4) Pb(C.H.Q.), A yellow ppt. Chromic Fee Cle | A pale yellow ppt. Benzoic
(4) bpt. ; ltlSOI. 1n
NH,
5 y A blood red color | CNEIS 3 3 A white curdy pot.; IICy (5) Fo,Clo A yellowish white Phosphoric 3 * A reddish brown | Succinic
(5) sol. in NH, Hſ), ppt. (4) ppt.
and in alkaline
cyanides.
For reactions of special acids free and in combination see Index.


PART NO. J.
Portion acidulated with HC1.
[The acid is to be added until all CO2 is
evolved, and the solution after boiling
remains very acid.]
PART No. 2.
Portion acidulated with HNOa.
[Boil after the acid is added.]
(1) A trace of Na2SO, may have been
present in the Na2COa.
(2) BaCl2 also gives a gelatinous ppt.
with 2HF,SiF,. This ppt. is decom-
posed by strong acids, and when
heated, SiF, is evolved.
(3) FeSO, gives a light blue ppt. with
H. FeCyg.
(4) FeSO, gives a very dark blue ppt.
with Ho Fe2Cy; 2.
(5) Color destroyed by HgCl2, unaffected
by HC1. [In this way the color may
be known from that produced by the
action of acetic acid on Fe2Cla.]
the HCl with Ag.,80, ; filter, add
excess of Na2COa, evaporate to dry-
ness ; ignite the residue; and add
AgNOa.
(2) Confirm the presence in the original
solution by adding a little chlorime
water and shaking up with ether.
(3) AgBrOa is Sol. in water ; AgBr is insol.
On adding H, SO, to a solution of
AgBrO2 a. ppt. of AgBr is thrown
down.
(4) AgIOa is sol. in ammonia, from which
solution HaS0, precipitates Agſ. An
iodate, unlike an iodide, is decomposed
by acetic acid, setting free iodine.
(5) A cyanide (and that only) yields HCy
with dilute H2SO4.
(6) H. FeCyo, He Fe, Cy, g, and CNHS are
also pptol. by AgNOa, the ppts. being
insol. in HNO2.
in No. 1.)
For the separation of these acids see Table,
NoTE.-HF is not precipitated by AgNOa.
(1) If HC10, be present with HCl, ppt.
(These are detected
(1) Boiling with Na,COa only partially decom-
poses the phosphates of the alkaline
earths. Hence examine the original solu-
tion for phosphoric acid with ammonic
molybdate.
A similar reaction occurs with sulphuric.
The power therefore of the vapor given off
whon the ppt. is heated with hydric
Potassic sulphate to corrode glass must in
all cases be tested.
(3) Calgic oxalate when ignited leaves CaCO,.
which dissolves
8. g with effervescence in
acetic acid.
(4) This retuction is evidence only of the
presence of a sol. phosphate, or
of a
phosphate decomposed by Na,C02.
(1) This reaction is valueless in the pre-
sence of Sulphuric, oxalic, hydrofluoric,
phosphoric, arsenic,
earbonic,
boric,
and Sulphurous acids, all of which are
precipitated by CaCls in a neutral
Solution.
(See Organic Acids for special tests.)
..ºf
A Solution contains Hydrochloric, Hydrobromic, Hydriodic, and Hydrocyanic Acids.
A. To a portion (about one-third of the whole) add AgNO3; collect and wash the ppt.
Boil with dilute HCl and place over the vessel on a glass plate ;-first a drop of AgNO3 solution, and secondly a
drop of a solution of potassic hydrate.
(1.) The argentic solution becomes white (AgCy); Sol. in ammonia,
(2.) The potassic hydrate solution is to be touched with a mixed solution of a ferric and ferrous salt, when a greenish
blue ppt. is formed, which on the addition of HCl leaves Prussian blue.
These reactions indicate HYDROCYANIC ACID.
B. To the remainder of the solution, add a solution of CuSO, and H2SOs (=Cu2SO4); a dirty white ppt. of Cu. Ie insoluble
in water, but soluble in NH4HO indicates HYDRIODIC ACID.
C. Add sufficient NaHO to precipitate the iron and copper compounds present; filter; evaporate the filtrate to dryness.
- Divide the residue into two parts 1 and 2.
Part 1. Part 2.
Add K2Cr2O, and H2SO4. A brownish red gas is evolved (chloro- Add a little chlorine water and shake up with ether. A red
chromic acid; CrO2Cl2) which condenses to a red liquid, de- solution indicates
composed by water into chromic acid (which gives a yellow
precipitate with a lead salt) and hydrochloric acid. This HYDROPROMIC ACID.
indicates the presence of
IBIYDRO CHILORIC ACID.
463
SECTION III.—ORGANIC CHEMISTRY.
CHAPTER XIX.
Organic Compounds and Organised Bodies — Definition of Organic Chemistry —
ORGANIC ANALYSIs – Ultimate Analysis — Vapor Density – Method of
determining Vapor Densities — Proximate Analysis.
DISTINCTION BETWEEN AN ORGANIC CoMPOUND AND AN
ORGANISED BODY.
By an organic compound, such, e.g., as sugar, urea, etc., we mean a
body of definite chemical constitution, exhibiting frequently, if solid,
a crystalline structure, and possessing, if liquid, a fixed boiling point.
Many organic compounds have been formed artificially.
By an organised body, such, e.g., as tissue, we imply a solid non-
crystalline substance, of a fibrous or cellular nature (i.e., non-crystal-
line), suffering decomposition when heated, so that it can neither be
liquefied nor vaporised intact. No organised bodies have been formed
artificially.
DEFINITIONs of ORGANIC CHEMISTRY.
(1.) Organic chemistry was originally defined as “the chemistry
of compounds produced under the influence of a vital force,” that is, of
a force residing only in the bodies of living plants and animals. Those
who held this doctrine of a vital force, divided organic bodies into two
classes:—
(a.) Direct organic bodies; that is, bodies like sugar, starch, etc.,
actually formed in the living plant or animal; and
(3.) Indirect organic bodies; that is, bodies formed from direct
organic bodies, by chemical or physical means. Thus oxalates and
formates were regarded as belonging to organic chemistry, because
the formates were prepared from the oxalates, and the oxalates from
starch. Similarly, olefiant gas and alcohol were considered organic,
because olefiant gas was produced from alcohol, and alcohol was
formed from sugar. Starch and sugar being direct organic bodies, the
products derived from them were regarded as indirect organic bodies.
Recent researches, however, have shown that some organic bodies
may be prepared artificially; we mean by that, without the medium
of any organic body. Thus cyanogen may be obtained from sodic
cyanide (NaCN), a salt which may be prepared by passing nitrogen
over a heated mixture of carbon and sodic carbonate. Alcohol (as
464 HANDBOOK OF MODERN CHEMISTRY.
Berthelot has shown) and urea, may also be built up artificially from
their elements; and so with many other substances. Hence “the
vital force ’’ scarcely serves to mark the division between organic and
inorganic chemistry. -
2. Organic chemistry was defined by Laurent as “the chemistry of
carbon and its compounds.” All organic substances contain carbon, com-
bined sometimes with hydrogen only, as in benzene (C6H6), and some-
times with nitrogen only, as in cyanogen (CN). Sometimes the
carbon is combined with hydrogen and oxygen, as in sugar, alcohol,
etc., and not unfrequently with nitrogen in addition, as, for example,
in the vegetable alkalies. Heating a substance in a test-tube, to see
whether it chars, is our usual rough test for an organic body, and
unless the body be volatile without decomposing, the result is accurate.
To accept this definition, however, in its integrity, would involve
our placing carbonic oxide (CO) and carbonic anhydride (CO2)
amongst organic compounds. To meet this difficulty, Frankland
defines an organic body as “a substance where one or more atoms of
the carbon of a molecule are directly combined with carbon, nitrogen
or hydrogen.” Thus he excludes carbonic anhydride, as a body in which
the carbon is combined directly only with oxygen (O = C=O). Cyanic
acid is an organic compound, because the carbon is directly combined
with nitrogen (N=C–0–FI). The objection to this hypothesis is
that it takes for granted our power of examining the internal atomic
and molecular structure of bodies, whereas at present such an in-
sight is nothing more than mere speculation.
3. Organic chemistry was defined by Liebig as “the chemistry of
compound radicals.” But compound radicals, as we have already
seen, are not unknown in mineral chemistry. Silver nitrate Ag(NO3),
which consists of silver and the compound radical (NO3), bears a
close resemblance to silver acetate Ag (C.H.O.), consisting of silver
and the compound radical (C.H.O.). Both salts part with their
compound radicals when a soluble chloride is presented to them, to
form AgCl, Again succinic acid
cº } O2(=C.Hö0,)
bears a close resemblance to sulphuric acid
§ 0–H.so) N.
each body containing a compound radical.
But although the existence of compound radicals can scarcely be
regarded as peculiar to organic chemistry, nevertheless their presence
is a very striking characteristic of it.
By a compound organic radical we mean “a group of atoms con-
taining one or more atoms of carbon of which one or more bonds are
unsatisfied.” (Frankland.) As in inorganic chemistry we have ele-
ments of different atomicities, so in organic chemistry we have
ORGANIC CHEMISTRY. 465
radicals of different atomicities. For example, we find univalent radi.
cals, such as methyle (CH3), forming methylic chloride (CH3)'Cl; di-
valent radicals, as ethylene (C2H4), forming ethylic chloride (C2H4)"Cl2;
trivalent radicals, as glycerile (C3H5), the radical of glycerine
(CAH3(HO)s), etc. Basic radicals are sometimes found combined
with chlorous radicals, the whole body being in such case made up of
compound radicals; as e.g., in methylic acetate C.H.30(OCH3).
No mono-, tri-, or quinqui-valent radical can exist as a separate
group, any more than a monad (as hydrogen), a triad, or a pentad
element (as nitrogen) can exist as a separate atom.
Having seen that it is impossible to draw any exact line dividing
organic from inorganic chemistry, we may here note one or two special
characteristics of organic bodies:—
1. The principal elements entering into the composition of organic
bodies are few, viz., carbon, hydrogen, nitrogen, and oxygen ; at the
same time nearly, if not every element, found in the mineral kingdom,
is also to be found in the organs of the plants or of the animals that
serve to elaborate these compounds.
2. Although the elements of which organic bodies are formed, are,
as we have said, few, nevertheless the number of atoms constituting a
molecule is frequently very large. No organic compound is known
containing only two atoms in a molecule, and only one, viz., hydro-
cyanic acid (HCN), containing three. In sugar 45 atoms, and in mar-
garin 217 atoms, make up the molecule of these bodies respectively.
(3.) Organic bodies are remarkable for their complicated and elabo-
rate constitution. This depends on two circumstances: — (a), the
frequent occurrence of compound radicals in organic bodies; and
(B), the chemical characteristics of the four elements of which organic
compounds are chiefly composed.
Respecting this latter point, viz., the chemical values of the four
elements of which organic bodies are chiefly composed, it is to be
noted that carbon is a tetrad; nitrogen, a triad; oxygen a dyad, and
hydrogen, a monad.
The tetravalent atomicity of carbon is important. It is regarded as
“fully saturated” when it is combined either with 4 monads (as in CHA),
or with the equivalent of 4 monads, such as 2 dyads (as in CO.); or
1 triad and 1 monad (as in CNH), etc.) It is regarded as “not
Saturated ” in compounds that contain less than 4 monads or their
equivalent, such as CO. Under slight physical influences, however,
such as light, the non-saturated compound CO will combine with Cle,
forming phosgene gas (COCl), in which compound the carbon is fully
Saturated,
But a carbon atom will also combine with a carbon atom. (Dupli-
cation.) Two separate carbon atoms possess 8 unsatisfied bonds,
(four to each); when combined, however (forming a dicarbon atom),
they have only 6 unsatisfied bonds, because it will be seen that one
H. H.
466 HANDBOOK OF MODERN CHEMISTRY.
bond from one carbon atom combines with and satisfies one bond from
the second carbon atom, thus satisfying 2 of the 8 bonds. Similarly,
a combination of 3 carbon atoms (a tricarbon atom) has only 8 unsa-
tisfied bonds instead of 12. Thus —C— = a carbon atom ;
|
| |
—C–C– = a dicarbon atom; –C–C–C– = a tricarbon atom;
| | | | |
Thus the addition of every carbon atom increases the non-saturated
bonds of a compound, by 2. It will be seen, therefore, why we regard
a series of bodies, that increase by an addition of CH2, as an homo-
logous series; as, for example, in the monatomic methyl series:
Methyl (CH.)
Ethyl (C.H.)"
Propyl ( } H1)'
Et
C.
Methyl-hydride (CH.) H
Ethyl-hydride (C.H.) H
rºyº (C, H,) H.
to.
Methyl-chloride (CH.)01
Ethyl-chloride (C.H.)Cl
Propyl-chloride (C.H.)Cl
Etc.
Methyl-alcohol(CH.)(HC
Ethyl-alcohol (C.H.)(BU
Propyl-alcohol (ółłºń.
Etc.
Types founded on carbon as the grouping agent in non-nitrogenized bodies,
and on nitrogen in nitrogenized bodies. (Frankland.)
It may be conveniently noted here that Frankland regards these
carbon groupings to which we have referred, as constituting a series
of types of non-nitrogenous bodies, nitrogen forming a grouping
element for nitrogenized bodies. Thus—
(1.) The single carbon atom type has been termed the monadelphic
or marsh gas type.
EI
|
H–C–H = CH4 Marsh gas.
|
H
(2.) The dicarbon atom type has been termed the diadelphic or
methyl type.
EI H.
H--
|
- CH,
(3.) The tricarbon atom type has been termed the triadelphic type.
H EI H
| | | CH, dº tº
H–C–C–C–H as for example {CH2=C3Hs Propyl-hydride,
| | || loſſ;
H TH H
and so on. - -
On the other hand nitrogenized bodies may be arranged under
one of either of the following forms:—
3
ORGANIC ANALYSIS. - 467
(4.) The ammonia type ; represented thus—
H
|
N = N*Ha Ammonia.
/ N
FI EI
(5.) The ammonic chloride type represented thus—
Cl
|
H–N–H =NVH,Cl
/ N
H EI
Frankland also describes—
(6.) The double monadelphic type.
H H
|
H–C–0–C–H
| |
EI H
(7.) The condensed diadelphic or olefine type,
H EI
| |
C=C
| |
EI EI
4. A great variety of property naturally occurs as the result of the
complicated chemical constitution of organic bodies, some consti-
tuting our daily food, and others actively poisonous substances.
ORGANIC ANALYSIS.
The analysis of an organic body is of two kinds, viz., proximate and
tiltimate.
(1.) A proximate analysis of a body implies “the separation and
estimation of its component or proximate principles”—
Thus: determining the presence and relative proportions of sugar,
fat, casein, and salts in milk, constitutes “a proximate analysis” of
milk.
(2.) An ultimate analysis of a body implies “the separation and the
estimation of the constituent or ultimate elements *-
Thus determining the presence and the relative proportions of
carbon, hydrogen, nitrogen, and oxygen in the casein of the milk,
Constitutes “an ultimate analysis” of casein.
We commence our studies with the principles of, and the method
of conducting, the ultimate analysis of organic bodies.
468 HANDBOOK OF MODERN CHEMISTRY.
ULTIMATE ANALYSIS OF ORGANIC BODIES.
The principle of an ultimate analysis of a body containing carbon,
hydrogen, and oxygen, may be stated as follows, viz. –To burn a
known weight of the organic body in oxygen, and to collect and
Weigh the oxidised products. The carbon is determined as CO2, the
hydrogen as H2O, and the oxygen by difference—that is, by subtracting
the combined weight of the hydrogen and carbon from the total
Weight of the material operated upon.
The conditions necessary for the success of the eageriment are as fol-
lows:–(1.) That the body operated upon should be pure; (2) that
it should be dry; (3.) that it should be perfectly burnt; and (4.) that
the products should be accurately weighed.
The history of ultimate analysis.-The first attempts at organic
analysis were simply destructive distillation, the products of such dis-
tillation being regarded by the older chemists as the elements of organic
bodies. Thus grew the dictum “air, oil, water, and earth (caput
mortuum) are the elements of organic bodies.”
Hales and Priestly were the first who improved this process of
destructive distillation by collecting the gaseous products evolved
during the operation.
In 1810, Gay Lussac and Thénard suggested (in principle) the
process of analysis which is now adopted, viz., burning the body in
oxygen and collecting the products. Their process was as follows:–
A glass tube, containing a weighed quantity of the organic body to
be examined was placed in an upright position in a furnace. When
the tube was sufficiently heated, oxygen was supplied to the organic
matter by dropping potassic chlorate into the tube. The gases
evolved were collected over mercury and measured.
The objections to this process were its practical difficulties, namely,
(1.) the constant Cracking of the tube, (2.) the frequent loss occasioned
by the substance being blown out of the tube, (3.) the difficulty of
ensuring the complete combustion of the organic matter owing to
the immediate and rapid generation of oxygen from the potassic
chlorate, and (4.) the inaccuracies resulting from measuring the pro-
ducts. -
Berzelius suggested the following improvements in the process, viz.
(1.) placing the tube in a horizontal position; and (2) modifying the
violent action of the potassic chlorate by mixing it with common salt.
Further (3.), he weighed the products, using for this purpose a chloride
of calcium tube to collect the water, and fragments of caustic potash
contained in a large glass bulb to collect the carbonic anhydride.
Gay Lussac and Thénard, Berard, Berzelius, and, lastly, Thompson,
suggested the use of cupric oxide, instead of potassic chlorate, for
the supply of the oxygen. Its advantages were—(1) the comparative
ease with which it could be obtained pure and dry; and (2.), more
EXPERIMENTAL DETERMINATION OF CONSTITUENTS. 469
particularly, that when heated alone it required a high temperature
for its decomposition, but that, when heated with organic matter, it
readily imparted its oxygen to it.
Lavoisier, Saussure and Prout suggested passing a stream of pure
oxygen through the combustion tube instead of using cupric oxide.
Finally, Liebig improved the process in many of its details. He
suggested the use of plumbic chromate as an oxidising agent, instead
of cupric oxide, under the following circumstances—
(a.) When the compound contains chlorine or bromine. When cupric
oxide is used, the volatile bodies CuCl2 and Cubre are formed, which,
condensing in the calcic chloride tube, introduce a source of error.
This is avoided by the use of plumbic chromate.
(3.) When the compound contains sulphur. The sulphur, when burnt
with cupric oxide forms SO2, which would be absorbed by the potassic
hydrate solution, thus falsifying the results obtained by weighing the
potash bulbs. With plumbic chromate, on the contrary, the sulphur
does not form SO2, but the non-volatile body plumbic sulphate.
(y.) When the compound contains alkaline salts. The alkaline car-
bonates into which these alkaline salts are converted by heat, are not
decomposed by contact with cupric oxide (thereby decreasing the
quantity of free CO2 formed), whilst they are decomposed by the
action of plumbic chromate.
(3.) When the compound is difficult of combustion.
(I.)—The Experimental Determination of the Carbon, Hydro-
gen, and Oxygen of an Organic Compound, not containing
Nitrogen.
This is conducted as follows:—A tube of hard glass, eighteen
inches long, and closed at one end, is filled for the first five
inches with pure cupric oxide. An accurately-weighed quantity of
the organic body to be examined, mixed with cupric oxide, is then
introduced, the remainder of the tube being filled up with pure
oxide. To this combustion tube is attached—
First, an accurately weighed tube, containing calcic chloride, for the
purpose of absorbing the moisture, calcic chloride not absorbing
carbonic anhydride; and
Secondly, an accurately weighed bulb-tube containing a solution of
potassic hydrate, for the purpose of absorbing the carbonic anhydride
formed during the experiment.
The front part of the combustion tube (that is, the part containing
pure cupric oxide) is first heated to redness. This done, the heat is next
applied to the mixture of the oxide and the organic matter, com-
mencing at that part of the tube furthest from the absorption tubes.
Thus the organic body is burnt by the oxygen of the cupric oxide.
The hydrogen of the organic body, as water, will be absorbed by the
470 HANDBOOK OF MODERN CHEMISTRY.
calcic chloride, and the carbon as carbonic anhydride will be absorbed
by the potash solution. - -
Finally, the sealed end of the combustion tube is broken off, and
pure dry air or oxygen is drawn through the apparatus, so that
any moisture or carbonic anhydride remaining in the tube unab-
sorbed may be displaced.
When the apparatus is cool, the tubes are again weighed. The in-
crease in the weight of the chloride of calcium tube represents the
water formed by the combustion of the hydrogen of the compound,
and the increase in the weight of the bulbs containing the solution
of potassic hydrate, represents the carbonic anhydride formed by the
combustion of the carbon of the compound.
Determination of Oxygen.—The oxygen is calculated by differ-
ence; that is, having proved the body to contain only hydrogen, car-
bon, and oxygen, the combined weights of the hydrogen and the
carbon are subtracted from the total weight.
Method of Calculating Results,
Say 10 grains of sugar is burnt :—
(a.) The calcic chloride tube after experiment weighed 205-78grs.
2 3 3 y before 25 72 200.00grs.
Therefore the product of the combustion of the hydrogen 5.7sgrs
of 10 grains of sugar yields H2O - grs.
It follows therefore—
Wt. of H2O in 10
H2O H2 grs. Of Sugar.
18 : 2 : : 5.78 : a = 0.643 grs. of hydrogen in 10 grs. of sugar.
(3.) The potassic hydrate solution after expt, weighed 815: 399 rs
2 y 3 y 3 y before y 9 800,00grs.
Therefore the product of the combustion of the carbon l 15-39QTS
of 10 grains of sugar yields CO2 * grs.
*
If follows therefore—
Wt. of CO2 in 10
G02 C grs. Of Sugar.
44 : 12 : ; 15:39 : a = 4, 198 grs. of carbon in 10 grs. of Sugar.
(y.) 10 grs. — 4.854 grs. (0.643 grs. of H+4'211 grs. of C)=5.146
grs. of oxygen.
(3.) Multiplying these quantities by 10, we find that there are in
every 100 parts of Sugar—
Carbon • * * • * * * @ tº 41-98 parts.
Hydrogen ... e - © tº e e 6'43 , ,
Oxygen • e & • * * * @ e 51'59 ,,
ULTIMATE ANALYSIS. 471
Eacperimental errors.—Usually our estimation of the carbon in a
body is 0.1 to 0.2 per cent, too low, the error arising from the incom-
plete combustion of the body, whilst our estimation of the hydrogen
is 0.1 to 0.2 per cent. too high, arising from the impossibility of
effecting the entire removal of moisture.
In the case of a liquid it is commonly placed in the combustion-tube
in a glass bulb, the exact weight of the liquid introduced being pre-
viously determined; whilst in the case of a fat or wax, etc., a little
glass boat is usually employed for the same purpose.
(II)—Estimation of the Hydrogen and Carbon in a Body
containing Nitrogen.
If the nitrogen be evolved as free nitrogen from the organic body,
its presence would not signify, inasmuch as pure nitrogen would
neither be absorbed by the calcic chloride, nor by the solution of
caustic potash. But as a rule, during a combustion analysis, a small
quantity of the nitrogen of nitrogenised bodies becomes oxidised to
nitric oxide (N2O2), which, on coming into contact with the air in the
potash-bulb apparatus, would be further oxidised to nitric peroxide
(N2O4), and would then be absorbed by the solution of potassic
hydrate, and so interfere with the estimation of the CO2.
To remedy this it is usual to place some copper turnings in the
front part of the combustion-tube, and to maintain the metal at a red
heat during the whole experiment. The action of the copper is as
follows:—The red-hot copper decomposes any oxide of nitrogen
formed, itself absorbing the oxygen, and setting free pure nitrogen,
which merely escapes into the air, unabsorbed either by the chloride
of calcium or by the potassic hydrate.
(III.)—The Recognition and Estimation of the Nitrogen
in an Organic Body.
The carbon and hydrogen of the substance having been first esti-
mated by the process described above, the nitrogen is to be determined
by a separate experiment.
(1.) The Recognition of Nitrogen in Organic Bodies.-The
presence of nitrogen may be known,
(a.) By heating the substance with a small piece of potassium (or
sodium), dissolving the residue in water, adding to the clear filtrate
a few drops of a mixed solution of ferrous sulphate and ferric chloride
and an excess of hydrochloric acid. A blue precipitate (Prussian
blue) indicates the presence of nitrogen.
(6.) By the generation of ammonia when the organic body is heated
with potassic hydrate.
(2.) Estimation of Nitrogen.—(a.) By volume (process of Dumas).
This process is applicable to the analysis of all nitrogenised substances.
472 HANDIBOOK OF MODERN CEIFMISTRY.
The combustion-tube, sealed at one end, is prepared as follows:
—The first five or six inches of the tube is filled with hydric sodic
carbonate (NaHCO3). The mixture of cupric oxide and the organic
matter is next introduced, and afterwards some pure cupric oxide, the
last two inches of the tube being filled up with copper turnings.
A delivery-tube, the further end of which dips under mercury, is now
fitted to the combustion tube. The apparatus having been proved to be
air-tight, a portion of the hydric sodic carbonate is heated. The
carbonic anhydride generated, sweeps the air out of the tubes.
If this were not done the atmospheric nitrogen would vitiate the
results. This done, a graduated tube filled two-thirds with mercury
and one-third with a solution of potassic hydrate (the latter to absorb
the CO2 generated during the experiment), is inverted over the
delivery-tube. The copper in the combustion-tube is now made red
hot, so that it may effect the decomposition of any oxides of nitrogen
formed during the process. The pure cupric oxide is next heated,
and then the mixture of the cupric oxide with the organic matter.
The H2O formed is condensed, whilst the CO2 is absorbed by the
potassic hydrate solution, the nitrogen alone collecting in the receiver.
The combustion being complete, the undecomposed carbonate is
heated, the carbonic anhydride generated sweeping any residual
nitrogen from the combustion and delivery-tubes into the graduated
receiver.
The volume of nitrogen formed is then read off, and corrections
having been made for moisture, for temperature, and for barometric
pressure, its weight is estimated from the corrected volume.
A slight experimental error, not exceeding 0-3 to 0.5 per cent.,
arises from a trace of nitrogen remaining in the tubes, and also
being retained within the pores of the copper. -
(3) (Process of Warrentrapp and Will.) We have noted that when
nitrogenized organic matter is heated with sodic or potassic hydrates,
the nitrogen is evolved as ammonia.” Advantage is taken of this
reaction in estimating the nitrogen as follows:—
A known weight of the organic body is mixed with soda-lime. This
is prepared by slaking lime (CaO) with a solution of sodic hydrate,
and afterwards drying and igniting the product formed. The advan-
tages of soda-lime over caustic soda are manifest. Caustic soda is very
fusible, very deliquescent, very difficult to powder, and hence very
difficult to mix with the organic body. Soda-lime, on the contrary, is
infusible at a red heat, is not deliquescent, and, owing to the ease
with which it can be reduced to a fine powder, admits of ready admix-
ture with the organic body. The mixture of the organic matter with
the soda-lime is now placed in a glass combustion tube, and heated.
* When a non-nitrogenized organic body is heated with potassic hydrate, the
carbon of the organic matter burns at the expense of the oxygen of the water of the
hydrate, the carbonic anhydride formed combining with the alkali, and the hydrogen
escaping. -
TJLTIMATE ANALYSIS. 473
The ammonia evolved is conveyed into a tube containing hydrochloric
acid, and the quantity of ammonia collected estimated as ammonic
platinic chloride ((NHA). PtCl6), which may be either collected and
weighed on a balanced filter (100 grs. = 6.27 N), or else ignited in
a crucible and the weight of the nitrogen estimated from the reduced
platinum (100 grs. of Pt. = 1418 N).
The ammonia may also be estimated by collecting it in a measured
quantity of dilute sulphuric acid of known strength, the amount of
acid unneutralized, being determined by titration (Peligot). This pro-
cess of estimating the nitrogen as ammonia is not practicable, however,
when the nitrogen is present as a nitro-compound, as, e.g., in nitro-
benzol, ethyl nitrate, etc., or in the case of certain alkaloids, etc.
(IW.)—The Estimation of the Sulphur, Phosphorus and
Haloid Elements in an Organic Body.
(1.) Estimation of Sulphur.—This is effected by one or other of
the following processes:–(a.) By igniting a known weight of the
organic substance with a mixture of nitre and potassic hydrate. An
alkaline sulphate is thus formed, the sulphur of which may be esti-
mated by precipitating its solution with baric nitrate (100 grs. BaSO4
= 13.67 grs. of S.).
(3.) By interposing between the calcic chloride tube and the potash
bulbs in the combustion apparatus, a tube containing lead oxide, the
sulphurous acid formed combining with the lead oxide to form a sul-
phate of lead (PbO2+SO2=PbSO4).
(The presence of sulphur vitiates the accuracy of the carbon deter-
mination, when cupric oxide is used as the oxidising agent. This
does not occur when plumbic chromate is employed. See page 369).
(2) Estimation of Phosphorus.—This may be effected in a
similar manner to the process (a.) already described for the determina-
tion of sulphur. After precipitating the sulphuric acid as BaSO4,
the excess of barium is to be thrown down with dilute sul-
phuric acid. The phosphoric acid present, the form in which the
phosphorus now exists, is then to be estimated by supersaturating the
solution with ammonia and adding magnesic sulphate. The am-
monic magnesic phosphate precipitated is then collected, ignited, and
weighed as Mg., P.O. (100 grs. =27-92° P).
(3.) Estimation of Chlorime, Bromine, and Iodine,—This is
effected by heating the organic body in a tube with quick-lime,
whereby CaCl2, or Cabra, or Caſe, is formed. The product is then dis-
solved in dilute nitric acid, and the chlorine, bromine, or iodine pre-
cipitated with argentic nitrate.
(4.) Estimation of Chlorine, Bromine, Iodime, Sulphur, and
Phosphorus in an Organic Body-A mixture of three or four
grains of the organic body with eighty grains of nitric acid (Sp. Gr.
474 HANDBOOK OF MODERN CHEMISTRY.
1-5), and a few crystals of argentic nitrate, contained in a sealed tube,
is to be heated for three or four hours in an oil bath. When the
tube is cold its contents are to be washed into a beaker. The in-
soluble AgCl, or AgBr, or AgI, which will be formed if the sub-
stance contains chlorine, bromine, or iodine, is then filtered off,
The excess of silver present must then be thrown down with
hydrochloric acid, and the sulphur and phosphorus in the clear fil-
trate estimated as baric sulphate and ammonic magnesic phosphate.
(5.) Other constituents remain as ash, and must be estimated in
the usual manner.
WAPOR, DENSITY.
Having determined by an ultimate analysis the exact chemical
composition of a body, it is necessary (if the substance under exami-
nation be volatile) to determine the specific gravity of its vapor. We
shall notice hereafter the important control that this determination
exercises over the calculations derived from the ultimate analysis.
We should here remark—
(a.) That with an organic, as with an inorganic compound, “its
vapor density is one-half its molecular weight; ” in other words,
that the molecule of a compound body (no matter what number of
atoms be present in the molecule) occupies in the state of gas twice
the volume occupied by one atom of hydrogen (H=1) under like
conditions of temperature and pressure. Thus a molecule of water
gas (H2O) occupies two volumes, or [T], the atom of hydrogen
(H) occupying one volume, or II.
(3.) It follows, if the molecule of a compound body in the state of
vapor be twice the volume of an atom of hydrogen, that “the specific
gravity of any compound gas or vapor referred to hydrogen as unity, must be
one-half its molecular weight.” Thus—
The molecular weight of H2O=18. This, we have seen, occupies
2 volumes, i.e., twice the volume occupied by H.;-
Therefore = 9, the relative weight or vapor density of water
gas, hydrogen being 1.
(y.) But to this general law we find certain exceptions. These
exceptions are probably more apparent than real, and may be
explained by the circumstance that many bodies, when heated to their
boiling point, decompose, so that the vapor experimented upon is not
the pure vapor of the original body, but a mixture containing
the vapors of the new compounds of decomposition. This form of
decomposition is termed “dissociation" (see page 13). For example,
a molecule of sulphuric acid (H2SO4), as a gas, is found to occupy not
(as it should do) 2 volumes, but more than 2 volumes, the reason
being that when sulphuric acid is heated above its boiling point, it is
decomposed more or less completely into sulphuric anhydride and water
WAPO.R. DENSITY. 475
(H.S.O. = H.04-SO). Hence, if we were determining its vapor
density, our experiment would be conducted, not with pure sul-
phuric acid vapor, but with a vapor containing the mixed decom-
position products, water and sulphuric anhydride.
It will be evident that if dissociation was complete, the molecule of a
substance (such, e.g., as H2SO4) would occupy, in a state of vapor,
4 volumes instead of 2 volumes; that is, the H2O formed would
occupy 2 volumes, and the SOs 2 volumes. This being the case, the
observed specific gravity would be one-fourth (and not one-half) the
molecular weight, the molecule appearing to occupy 4 times the
volume of a hydrogen atom. But dissociation may be, and usually is,
only partial, commencing at, or a little above, the boiling point, and
becoming more and more perfect as the temperature is increased.
The difficulty in determining vapor densities arising from disso-
ciation, has been in some cases overcome by altering the relationship
between the relative quantities of the products of dissociation, the
tendency of compounds to combine being augmented by the
presence of one of the compounds in excess. Thus, if we attempted
to determine the vapor density of phosphoric chloride (PCls), we
should find that it would split up into PCls and Cl2. If, however, we
mix phosphorous chloride (PCl3) with phosphoric chloride (PCls) the
chlorine set free by heat from the PCls, being in the presence of a
large excess of PCls, instantly combines with it to form PCls, enabling
us at once to obtain the true vapor density of the phosphoric chloride
Thus in some cases the difficulties arising from dissociation have been
Imet.
We now proceed to consider the determination of vapor densities.
Determination of Wapor Densities.
This may be effected in one of two ways; either
I. By determining the weight of a given volume of vapor; or
II. By determining the volume of a given weight of the
substance.
I.—By determining the weight of a given volume of vapor (process of
Dumas).
(a.) Provide either a clean dry glass flask, or one of porcelain, if
glass will not stand the necessary heat. The flask must have a long
and finely drawn out neck, and be capable of holding from 200 to
300 c.c. Weigh the flask accurately, noting at the time the tempera-
ture and pressure.
Thus we learn the weight of the flask filled with air at a definite tempera-
ture and pressure.
(6.) Introduce now into the flask a quantity (say 50 to 100 grains)
of the substance to be examined, and place the flask containing the
compound in a water, oil, or mercury bath, the neck of the flask being
476 EIANDIBOOK OF MOIDERN CHEMISTRY.
external to the bath. The temperature of the bath employed
must be considerably above the boiling-point of the body under
examination. Hence the vapors of cadmium (860° C.), or of zinc
(1040°C.), must be used if necessary. The vapor of the substance,
as it is evolved, expels the air of the flask. When the evolution of
vapor from the flask ceases, the neck of the flask is to be sealed,
the temperature of the bath and the atmospheric pressure being noted
at the time. When the flask is cold it is to be weighed, the tempera-
ture and pressure being again recorded.
Thus we learn the weight of the flask filled with the vapor of the substance
under eacamination, at a definite temperature and pressure,
(y.) The extreme point of the flask is now to be broken off under
mercury. If the air of the flask has been entirely expelled, the
mercury immediately rushes into, and completely fills the flask. By
weighing the mercury that thus enters the flask, the capacity of the
flask may be determined.
Thus we learn the capacity of the flask.
If, however, the mercury does not completely fill the flask, it proves
that the expulsion of the air by the vapor was not complete. Under
these circumstances, weigh first the mercury that enters the flask, and
secondly, the total mercury required to fill the flask.
Thus, by the difference between these two weighings, we learn the quantity
of residual air in the flask at the time of the eaſperiment, whilst the weight of
the mercury required to fill the flask, gives us the gross capacity of the flask.
Eacample (from Roscoe).—A volatile hydro-carbon (C6H14) is taken
for the experiment. The barometric pressure is throughout taken
at 760 mm.
Weight of the flask filled with air (tempera-
ture 15-5°C.)... 6 g º e e e tº º
Weight of the flask filled with the vapor of
the hydro-carbon (temperature 110°C.) = 23:720 grims.
Capacity of the flask ... tº º º tº gº º 178 c.c.
From these data we enquire, L- -
(1.) What bulk would 178 c.c. of air at 15:5°C. (the temperature at
which the flask containing air was weighed) occupy at 0°C. (the
standard temperature, see p. 33) Ans. 168.4 c.c.
(2.) What is the weight of this volume of air 2 Every c.c. of air at
0° C. and 760 mm. weighs 0-001293 grims. Therefore 0-001293 x 1684
=0-218 grims, the weight of 168.4 c.c. of air at 0°C., and 760 mm.
pressure; in other words the weight of the air the flask contains at 0°C.
(3.) The weight of the flask without air is therefore 23:231 grims.
[23:449 grims. (flask+ air)–0-218 grim. (weight of air)=23:231 grims.
(weight of flask).] -
(4.) The weight of the flask filled with vapor is 23-720 grims. If we
subtract from this, the weight of the flask, we obtain the weight of
the vapor in the flask [23.720 (flask+vapor) – 23:231 (weight of
flask)=0.489 grim. (the weight of the vapor).]
= 23:449 grims.
ORGANIC BODIES. 477
(5.) 178 c.c. of hydrogen at 110°C. weighs 0.01134 grm. (1 c.c. of
hydrogen at 0°C. and 760 mm. weighs 0.0008936 grim. (see page 35).
0.489 The density of the vapor of CaFI
Therefore 0.01134 T 43-13 | tº: to hº a.S unity. 14
In this example we have omitted such minor details as the expan-
sion of the glass flask, the errors of the thermometer, etc. If the
pressure varied during the experiment, due allowance must be made.
If the air be not wholly expelled from the flask by the vapor, the
residual air must be deducted from the total capacity of the flask, and
the calculation made on the result.
II.-The vapor density may also be estimated “by determining the
volume of a given weight of the substance.” (Process of Gay Lussac.)
A sealed glass bulb, containing a known weight of the substance
to be examined, is introduced into a graduated tube full of, and stand-
ing over, mercury. The whole apparatus is then lowered into a bath
of hot oil or other liquid, the heat of which bursts the glass bulb, and
converts the whole of the volatile substance contained therein into
vapor. The volume of vapor is then noted, and also the temperature
of the bath, the atmospheric pressure, the height of the mercury in
the graduated tube (the downward weight of which tends to expand
the vapor), and the depth of the oil bath pressing on the mercury (the
downward weight of which tends to contract the vapor). From these
data, the vapor density may be calculated.
Hofmann's modification of the above process, consists in enclosing
the graduated glass tube in a second and larger tube, through which
currents of the vapor of water or other body can be passed. In this
way the trouble of lowering the whole apparatus into the oil bath is
avoided. The volume of the vapor, the temperature, the pressure,
and the height of the mercury column must be noted. The weight
of hydrogen, which under the same conditions would occupy a similar
volume is then estimated, and
the weight of substance examined _ ſ the vapor density
the weight of hydrogen – required.
We have now to consider
The Application of the Facts deduced from the Ultimate
Analysis, and from the Determination of the Wapor
Densities of Organic Bodies.
(1.) We learn firstly, the percentage composition of a body. This, as
we have noticed, is at once deduced from the analysis (page 370).
Thus it was shown that every 100 parts of sugar contained—
Carbon, 41-98; hydrogen, 6:43 ; oxygen, 51°59.
(2.) From this percentage composition is deduced the empirical
formula of the body, i. e., the simplest possible expression of the rela-
78 HANDBOOK OF MODERN CHEMISTRY.
tive quantities of the several elements present. Thus the empirical
formula for sugar is Ciołł2,011. The rule for estimating the empirical
formula from the percentage composition is as follows (see page 44):—
“Divide the percentage numbers by their respective atomic weights,
and divide these quotients by their greatest common divisor,” thus—
Percentage com- At. Wt. of
position of sugar. element.
Carbon............ 41-98 - 12 = 350.
Hydrogen ..... , 6'43 + 1 = 643.
Oxygen ......... 51:59 + 16 – 323.
The relationship between Caso H54309aa (dividing each by 30) is very
nearly expressed by the formula C12H22O11.
Very nearly, we say, but not eacactly, for it has been already remarked
(page 371) that slight experimental errors are inseparable from an
ultimate analysis. This experimental error may be checked, amongst
other methods mentioned under the determination of the molecular
formula (page 379), by reckoning back the formula deduced to the
percentage composition, as well as calculating the percentage com-
position into the formula. The question is-Do the errors fall, both
as regards (1) direction and (2) amount, within the recognised expe-
rimental errors, remembering that as regards (1) direction, the
carbon is commonly deficient and the hydrogen in excess, and that as
regards (2) amount, the deficiency of the one or the excess of the other,
should not exceed 0-2 or 0.3 per cent. ”
Thus in the case of sugar—
I. II.
From the percentage composition :- From the formula C12H22O11, we
Carbon . . . . 41'98 calculate the percentage composition
Hydrogen . . . . 6:43 as follows:–
Oxygen . . . . 51:59 Carbon . . . . 42° 11
we calculate the formula:— Hydrogen .. 6:43
CiºłI,011 Oxygen . . . , 51-46
This close correspondence of results proves the accuracy of the
formula C12H22O11.
. (3). Our results, further, help us to determine the molecular formula
of the body. By this we mean “the atomic constitution of the molecule,
which, converted into vapor, corresponds to the volume formed by 2 atoms of
hydrogen (hence called a “two-volume formula') under similar con-
ditions of temperature and pressure.” The advantage of the molecular
over the empirical formula is, that it represents not only the number
of parts by weight, but also a quantity which, as a gas, occupies a
known volume (viz., 2 volumes). Comparison is thus simplified.
(a.) What is the relationship between the empirical and the molecular
formula of a body ?
(1.) They may be identical;
(2.) If not identical, the molecular formula is always some simple
multiple of the empirical formula. Thus—
ORGANIC BODIES. 479
CH represents the empirical formula for benzene;
C6H6 7 3 molecular 3 y 2 3
We next enquire—
(3.) How is the molecular (or two-volume) formula determined 2
(1st.) By the actual determination, when possible, of the vapor
density of the body. The vapor density of a body (that is, the relative
weight of one volume) is always one-half its molecular weight, (that
is, the actual weight of two volumes).
CH, we learn from its ultimate analysis, represents the simplest
expression of the relative amounts of carbon and hydrogen in the
liquid called benzene. From this formula we should estimate the
vapor density of benzene as 6'5 thus—
Experiment, however, shows that the vapor density of benzene is 39
or 6.5 + 6. Hence C6H6 must be the molecular formula—
C6H6 F tº — 39'0
Or we may state the facts thus : —the parts by weight of benzene
represented by the formula CH, when converted into vapor, only
measure one-sixth of the volume produced by 2 unit weights of
hydrogen; whilst the parts by weight represented by the formula
C6H6, measure, when converted into vapor, the volume produced by
2 unit weights of hydrogen, under similar conditions of temperature
and pressure. Hence C6H6 is regarded as the molecular formula for
benzene.
(2ndly.) It is, however, not always possible to estimate the vapor
density of a body, for it may be non-volatile, or it may decompose
when heated. Hence other means must be adopted to determine the
parts necessary to form two volumes, if the substance could be volatilized
wnchanged.
(a.) Such means consist, in the analysis of the compounds it forms
with well-known bodies, in other words, its powers of combination and
Saturation.
(1.) In the case of organic acids or salt radicals, the silver or lead
salt is commonly examined. For example, suppose we were determin-
ing the molecular formula of acetic acid. From the ultimate analysis
We learn that CH20 constitutes its empyrical formula. One atom of
silver will replace (we know) one atom of the hydrogen of the acetic
acid to form acetate of silver. By analysis we find that every 100
parts of this acetate of silver contains—
Silver jº e e tº e tº tº e - & e & 64-68 parts.
Carbon, Hydrogen and Oxygen 35'32 ,
Hence the atoms of C, H and 0, combined with 108 atoms of silver
(108 being the atomic weight of silver), may be found by the
equation—
64-48 : 36.32 : : 108 : a = 58.98.
480 HANDBOOK OF MODERN CEIEMISTRY.
To this 58.98 add 1 (=59-98), to allow for the hydrogen displaced
by the silver. Hence the molecular weight of glacial acetic acid is
59-98, and its molecular formula (allowing for experimental error)
must be C3H4O2. Thus—
C2 - 24,
H4 = 4,
O2 = 32 = 60:00, or 59.98 nearly.
(2.) In the case of organic bases, the neutral compounds formed
with well-known mineral or organic acids, must be examined.
(ſ3.) The study of the substitution products the body forms.
(y.) The action of reagents.
(3.) The calculation of the specific heat, and of the specific gravity
of the body.
It is most important to bear in mind exactly what a molecular
formula teaches, and what it does not teach :—
(a.) It teaches the actual chemical composition of a body, and its
vapor density.
(6.) It does not teach the chemical formation of a body, nor its mode
of decomposition; nor does it help us in the least degree to distinguish
between isomeric compounds (see page 48).
To supply these wants, Rational, Constitutional or Structural Formula:
are employed. A rational formula is designed to teach something of
the nature and properties, and also of the formation and decomposition
of a substance.
It will be, of course, understood that rational formulae are purely
theoretical formulae, and merely represent probabilities. They are
not to be regarded as actual representations of the constitution of a
body, but merely as the best representations our present knowledge
enables us to form.
One compound may possess many rational formulae, and we use them
according to the decomposition or reaction we desire to represent.
Thus, acetic acid (C2H4O2) has numerous rational formulae, amongst
which we may mention the following :-
(1.) H(C,EI,02): This implies that acetic acid is a monobasic acid,
the one H placed on one side, implying that it may be replaced by a
monovalent metal, or by a univalent alcohol radical. Thus we have
the bodies— -
Ag'.C., H3O. º e & tº e & Argentic acetate.
Ba".(C, H2O2), * c te * * * Baric acetate.
(C2H5)'.(C2H5O2) ... • * * Ethyl acetate.
(2) C.H.O(HO): When phosphorus pentachloride acts on acetic
acid, one of chlorine takes the place of one of the group (HO) (a.); and
when the acetic chloride thus formed is acted on with water, one of the
ORGANIC BODIES. 481 -
group (HO) takes the place of 1 of chlorine (ſ3.), as will be seen in
the following equations. This formula denotes, therefore, the dis-
placement of HO by Cl.
(a.) C.H.O.(HO)+PClg=C.H.O.C1+HCl·H POCl3.
(3.) C.H.O.C1+ H2O=C.H,0(HO)+HCl,
(3.) CH3.CO2.H. : This represents that on electrolysing acetic acid,
hydrogen is given off at the – pole, and ethane (C2H6) and carbonic
anhydride at the + pole (20EIs. CO2. H=H2+C2H6+ 2CO2).
(4.) CEIs.CO.HO: This formula represents the fact that the radical
acetyl (C2H5O) consists of carbonyl and methyl. It shows how marsh
gas (CH4) is evolved when potassic acetate is heated with potassic
hydrate, CH3CO.KO-F KHO=CH,--(CO)"(KO). Also that acetic
acid forms metallic salts, as potassic acetate (CH3.CO.KO); also that
by the action of PCls, the HO may be exchanged for Cl, etc.
PROXIMATE ANALYSIS OF ORGANIC BODIES.
By a proximate analysis is implied the separation of the proximate
principles of bodies, as, e.g., the separation of milk into fat, sugar,
casein, etc. We can lay down no general rules for a proximate, as
we are able to do for an ultimate analysis, each substance requiring
special treatment.
The microscope and microscopic reactions, afford great aid in proxi-
mate analysis, enabling us to detect and to identify various bodies,
such as, e.g., starch cells by their appearance and reactions with
iodine; cellulin, by its turning blue with iodine, after having been
first moistened with dilute sulphuric acid; woody tissue, by its being
darkened by sulphuric acid, and turning brown on being afterwards
treated with iodine ; corky tissue, by the absence of any change with
sulphuric acid or with iodine, etc., etc. Further in separating crys-
tallizable bodies, the microscope enables us to detect admixtures by
the presence of crystals of different orders.
Dialysis, again, as a means of separating crystalloids from colloids,
affords invaluable aid.
The following are the chief physical and chemical means adopted
for separating the proximate principles of organic bodies.
1. By spontaneous easudation, as, e.g., gums, resins, etc.
2. By mechanical pressure, as, e. g., oils (linseed, castor, etc.).
3. By the action of heat.—This may be employed either—
(a.) To melt out resins and fats, or
(3.) To sublime the volatile acids (benzoic), or
(y.) To distil the volatile oils, or
(6.) To separate admixtures of volatile liquids by fractional distil-
lation.
I I
482 HANDBOOK OF MODERN CHEMISTRY.
4. By the action of solvents:—
cold—to dissolve gums, sugar, certain coloring
(a.) Water matters, etc.
boiling—to dissolve starch, salts, etc.
(6.) Alcohol—to dissolve volatile oils, resins, certain alkaloids,
coloring matters, etc.
(y.) Ether, chloroform, or benzol—to dissolve fixed oils, camphor,
caoutchouc, certain alkaloids, etc.
(6.) Dilute acids and alkalies—the use of which, however, is generally
to be avoided, owing to the changes they induce in the organic body
itself.
483
CHAPTER XX.
TEIE NATURAL AND ARTIFICIAL CHANGES OF ORGANIC
BODIES.
FERMENTATION.—Warieties—I. Alcoholic—II. Lactic—III. Butyric—IV. Mucous—
W. Acetous—Conditions necessary for Fermentation—Circumstances influencing
Fermentation—Theories to account for it—Practical applications. PUTREFACTION
—Disinfectants. EREMACAUSIs. Action of Heat—Action of Acids—Action of
Alkalies—Action of Haloid Elements—Action of Nascent Oxygen and Hydrogen—
and of other Reagents—Action of Light and Electricity.
The transformations which organic bodies undergo are twofold:—
(A.) Natural or Spontaneous; and (B.) Artificial.
A.—NATURAL AND SPONTANEOUS.
It may be stated generally, that all organic substances are naturally
prone to resolve themselves into simpler parts or groups. This reso-
lution is effected in one of three ways:—
I. By fermentation.
II. By putrefaction.
III. By eremacausis or decay.
I. FERMENTATION.
Definition.—“A process whereby certain organic substances, under
the influence of contact with a nitrogenous body called a ferment,
are resolved into simpler groups.” We may note that fermentation is
accompanied by the development of certain minute living organisms,
the existence of which may be either a cause or a consequence of the
chemical change; that no offensive odors are evolved during the
process; and that the products are most often of a useful nature.
We shall investigate the subject of fermentation in the following
order :—
1. Its principal varieties.
. The conditions necessary for its existence.
. The conditions influencing its action.
. The theories to account for it.
. Its practical applications.
:
(1) The Warieties of Fermentation.
There are five varieties of fermentative action, their distinctive
names being derived from the principal product furnished:—
484 HANDBOOK OF MODERN CHEMISTRY.
(a.) The alcoholic or vinous fermentation, in which alcohol is formed.
(3.) The lactic fermentation, in which lactic acid is formed.
(y.) The butyric fermentation, in which butyric acid is formed.
(6.) The mucous or viscous fermentation, in which a gummy matter is
formed.
(e.) The acetous fermentation, in which acetic acid is formed.
(a.) The Alcoholic or Winous Fermentation: i.e., a fermenta-
tion characterised by the formation of alcohol. This results from the
action of yeast on a solution of grape sugar, ethylic alcohol and
carbonic anhydride being the chief products. The change of 95 per
cent. of the sugar thus fermented may be represented as follows:–
C6H12O6 = 20. HoO + 2CO3.
Grape sugar = Ethylic alcohol + Carbonic anhydride.
But besides these, other products are formed from the remaining 5
per cent. of sugar; viz., free hydrogen, the homologues of ethylic alcohol
(as propylic alcohol, etc.), a hydrocarbon of the CAH2n+2 series, glyce-
rine (to the extent of 3 per cent. of the sugar fermented (Pasteur)),
mannite, acetic acid, succinic acid (0.5 per cent.), etc. Many of these
products are, however, no doubt the result of secondary action, either
of the nascent hydrogen (as, e.g., in the production of glycerine,
mannite, etc.), or of the nascent oxygen (as, e.g., in the production of
succinic acid) resulting from the decomposition of water, which de-
composition it is believed always occurs during the process.
The active agent of alcoholic fermentation is believed to be the cells
of the torula cerevisiae.
It is to be specially noted that cane-sugar and its isomerides (i.e.,
the C12H22O11 group) will not undergo vinous fermentation, this action
being limited to grape-sugar and its isomerides (i.e., the C6H12O6
group). The change, however, of cane-sugar into grape-sugar, under
the influence of a ferment, is rapid, the specific gravity of the liquid
increasing as the change takes place, a solution of cane-sugar having
a lower gravity than one containing an equivalent amount of grape-
Sugar. -
(3.) The Lactic Acid Fermentation; i.e., a fermentation charac-
terised by the formation of lactic acid. This results from the action
of putrefying cheese or milk on grape or milk-sugar. It is necessary,
in order to neutralize the lactic acid as soon as formed, that the
solution should contain either chalk (in which case a calcic lactate is
produced), or zinc white (when a zincic lactate results), the presence
of a trace of free acid entirely preventing the continuance of the fer-
mentation by coagulating the casein and rendering it insoluble. This
change into lactic acid may be represented as follows:–
(a.) C6H12O6 (glucose) = 20, HGOs (lactic acid).
(3.) C12H22O11 (lactose) + H2O = 4C, H50s (lactic acid).
Mannite is also formed during the process. It is necessary that
FERMENTATION. g - 485
the lactates themselves should be removed from the action of the
ferment as soon as possible, otherwise they are converted into
butyrates. The lining membrane of the stomach of the calf (rennet)
and animal membranes generally, are specially active in inducing
this variety of fermentation. In the case of milk, the casein acts as
the ferment on the milk-sugar. Hence milk contains both the fer-
ment itself, and the body to ferment.
The active agent of the lactic acid fermentation is believed to be
the penicillium glaucum.
(y.) The Butyric Fermentation, i.e., a fermentation characterized
by the formation of butyric acid.
This results from the prolonged action of the lactic acid ferment
on the lactic acid, whereby butyric acid (which by the action of chalk
is converted into butyrate of lime) together with free hydrogen, car-
bonic anhydride, acetic and caproic acids, are formed. The butyric
fermentation is in fact the advanced stage of the lactic acid fer-
mentation. Thus :-
2C3H60s = C, HsO2 + 2002 + 2 H2.
Lactic acid = Butyric acid + Carbonic anhydride + Hydrogen.
The active agent of the butyric fermentation is believed to be the
same as that of the lactic fermentation, viz., the penicillium
glaucum.
(6.) The Mucous or Wiscous Fermentation, i.e., a fermentation
characterized by the formation of gummy matters. This results from
the action of certain nitrogenous substances on sugar, a gum (arabin),
mannite (C6H1406) a non-crystallizable sugar, and lactic acid, forming
the products. This fermentation commonly results in fermenting the
juice of the sugar beet. It sometimes occurs in sweet white wines that
have been kept too long, the action being capable of arrest by the
addition of a little alum or sulphurous acid to the wine. It does not
occur in red wines, the astringent matter derived from the grape
skins preventing them from becoming “ropy.” *
(e.) The Acetous Fermentation, i.e., a fermentation characterized
by the formation of acetic acid.
This results from the action of the acetous ferment, (the mycoderma
aceti,) on alcohol. The action does not take place with pure alcohol,
or when the alcohol is simply mixed with water, its admixture with
Some changeable organic substance being an essential condition.
C.H.80 + O2 - C.H.O., + H.O.
Alcohol + Oxygen = Acetic acid + Water.
This action, however, can scarcely be considered fermentation, but
simply a process of oxidation (decay), the mycoderm acting (1) as
a carrier of oxygen to the alcohol, and (2) as the means of bringing
the oxygen and the alcohol into actual contact. This action is analo-
gous to that which occurs in the oxidation of alcohol to aldehyde
and to acetic acid by spongy platinum.
486 HANDBOOK OF MODERN CEIEMISTRY.
The active agent, as we have said, of this change is the mycoderma
aceti.
Thus it would appear that elementary plants have the power
of breaking up organic bodies, each little organism having its own
special soil on which to work, the products formed, being dependent
both on the organism and on the soil,
(2.) The Conditions Necessary to Produce Fermentation.
(a). The presence of a ferment; that is of a nitrogenous albuminous
body in a state of active decomposition. Illustrations of ferments are
found in Emulsin, the active agent of the bitter almond in converting
the amygdalin into hydrocyanic acid, &c.; in Myrosin, a ferment-like
substance present in the seeds of the black and white mustard, which
converts the myronate of potassium into the oil of mustard (CAH3CNS)
together with glucose and hydric potassic sulphate; in Diastase, a
body found in malt, saliva, &c., and by the action of which starch is
converted into glucose; in Casein, which in milk induces lactic acid
fermentation of the sugar; and, amongst many other illustrations
that might be quoted, in Yeast, which is the ordinary ferment employed
for setting up alcoholic fermentation.
This last ferment, the ordinary beer yeast, has been specially
studied. When the yeast is merely dried at a low temperature,
(forming what is called “dried yeast,”) its power as a ferment is not
impaired, but if the yeast be boiled in water it is then completely
destroyed. “German dried yeast,” consists of the dried yeast
cells produced in the fermentation of rye for making Hollands.
Yeast, however, is a complicated ferment. It consists of two
kinds of cells, (1) large round granular cells (torula cerevisiae), and
(2) certain oval-shaped cells of a much smaller size (penicillium
glaucum). If the yeast be mixed with water, and then filtered through
paper, the smaller cells pass through with the water, leaving the
larger cells on the filter paper. It is found that the large cells
generate vinous, and the small cells lactic fermentation, when they are
added respectively to a solution of sugar.
When yeast is added to a solution of pure sugar it sets up fermenta-
tion, but the yeast-cells are for the most part destroyed as fermentation
proceeds. A few fresh yeast-cells may be formed, but if so, it is at the
expense of the materials produced by the disintegration of other yeast-
cells, Hence, a given quantity of yeast can only convert a limited
quantity of pure sugar into alcohol. When the yeast is added to a
solution of sugar, the Solution also containing nitrogen in some form
or another, and phosphates, it then not only ferments the sugar, but
propagates itself. Under such circumstances the addition of a little
yeast, owing to its rapid growth, will convert an almost unlimited
amount of sugar into alcohol. Thus the presence of nitrogen and
FERMENTATION. 487
phosphorus, in a combined form, are essential conditions for the
growth and propagation of yeast-cells.”
In the case of grape-juice no ferment need be added, as, after ex-
posure to the air for an hour, or even less, the vegetable albumen in
the juice undergoes decay by Oxidation, and acts as a ferment to the
Sugar.
It has been suggested that certain miasmas act as blood-ferments,
and induce the diseases ordinarily known as zymotic ({{pm, ferment)
or ferment-diseases.
We have remarked that all ferments contain nitrogen. Nitrogen
is an element remarkable for rendering the bodies in which it occurs
unstable. The chemical relationships of nitrogen are worthy of note :
it stands mid-way in the chemical scale between metals and metalloids,
without any great affinity for either the one or the other. It combines
both with oxygen and with hydrogen (and indeed with most bodies),
but its direct union is not easily effected. Hence, its attractions
being equally powerful in opposite directions, great instability
invariably characterizes the compounds in which it is present,
(3.) A body to ferment. The sugars (glucoses) are, par excellence,
the bodies peculiarly liable to ferment. If yeast be added to a solu-
tion of gum no action will be apparent, nor will the yeast itself be
propagated. The action of yeast, however, is not confined to sugar;
for if it be added to a solution of malic acid, succinic, acetic and
carbonic acids are formed, although it is to be remarked that in this
case the yeast itself does not propagate.
(y.) The actual contact of the ferment and the body to be fermented.—
The necessity for actual contact was proved by Mitscherlich as follows:
A glass tube, the bottom of which consisted merely of a piece of fine
filter-paper, was partially immersed in a solution of sugar. The
solution rapidly penetrated the pores of the paper, and filled the tube
to the level of the external liquid. A small quantity of yeast was
then added to the liquid in the tube, when the solution contained in the
tube, after a short time, commenced fermenting, but there were no
signs of fermentation in the solution external to the tube, the piece
of bibulous paper stopping the actual contact of the yeast-cells with
the external fluid by stopping the passage of the yeast globules,
although it did not interfere with the intercommunication of the liquids.
(3.) A certain temperature. At 32°F. (0°C.) fermentation is ar-
rested. From 32°F. to 68°F. (0°C. to 20°C.) it gradually increases
in intensity with the rise of temperature. From 68°F. to 104°F.
(20° C. to 40°C.) it is most active. At 120° F. (49°C.) the process is
again stopped. Hence certain times of the year are preferable for
brewing (especially the autumn), the temperature at such times
falling within the proper limits.
* Yeast yields from 6 to 8 per cent. of ash, which consists entirely of alkaline and
earthy phosphates. (Mitscherlich).
488 HANDBOOK OF MODERN CHEMISTRY.
(e.) The presence of moisture. Water is necessary to bring the
particles into contact. Dry yeast and dry sugar cannot ferment.
We may note, lastly, that the presence of air is not necessary for
fermentation, provided the previous conditions be fulfilled.
It has nevertheless been proved by Pasteur, that the action of the
air in the process of fermentation is not to be disregarded. For it
may act either (1) as a carrier of the ferment germs, or (2) as an
oxidiser, inducing the decay of certain nitrogenous bodies present in
a solution, thereby rendering them capable of acting as ferments.
(1) If a solution of sugar, no yeast having been added, be exposed
to the atmosphere, it becomes loaded before long with the lower forms
of organic life, and the solution begins to ferment. If, however, the air
before being allowed to come into contact with the sugar solution, be
passed either through a red-hot tube, or through a tube containing
cotton-wool (care being taken that the saccharine liquid itself has
been absolutely freed from germs by previous boiling), no fermenta-
tion will occur; but if the dust strained from the air by the cotton-
wool be placed in the solution, rapid decomposition of the sugar
results.
Hence Pasteur concludes that the air may act as the carrier of the
seeds necessary to start fermentation in a solution disposed to ferment.
(2.) In the case of wine juice, which ferments spontaneously, the
air is supposed to oxidise the vegetable albumen, which in a decom-
posed state is capable of acting as a ferment on the Sugar.
(3.) The Circumstances Influencing Fermentation.
The following circumstances prevent fermentation :-
(a.) The presence either of an eaccess of strong mineral acids, or of a
trace of free alkali.
(3.) The presence of certain salts in the solution, such as the sulphites,
NaCl, AgNO3, CuSO4, etc.
(y.) The presence of certain alkaloids, such as strychnia, quinia, etc.
These do not, however, stop fermentation, if added after the process
has commenced.
(3.) The presence of certain essential oils, such as kreasote, turpentine,
etc.
(e.) A solution containing more than one-fourth its weight of sugar. The
strength of the sugar solution is important. If it be too strong,
fermentation is arrested, or rendered imperfect; if it be too weak, the
action is slow and irregular.
(4.) A solution containing more than 20 per cent. of alcohol. Hence no
fermented liquor can contain more than 20 per cent. of alcohol natu-
rally. Anything in excess of this is evidence that spirit has been
added (fortification) after the fermentation of the liquid was com-
plete.
FERMENTATION. 489
Eermentation is influenced by many other causes. Thus—
(1.) The products formed at different temperatures vary. Thus, if
yeast be made to act at a temperature of 70°F. (21.1°C.) on malie
acid, it forms amongst other things succinic acid, whilst at a higher
temperature it yields butyric acid.
(2.) The alteration of pressure. Fermentation is not stopped by
placing the solution in a vacuum, but it is stated that under such
circumstances the ratio of the alcohol to the carbonic anhydride
formed, is different to that which occurs under ordinary atmospheric
pressure, the CO2 as well as the hydrogen, acetic acid, etc., becoming
proportionately greater. (H. Brown.)
(4.) The Theories to Account for Fermentation.
We may note, First, that the ferment is destroyed during the fer-
mentative process, the propagation and growth of new buds being
due, partly to the disintegrated cells that have done their work, but
principally to the nitrogenized matters and phosphates present in
the solution. Secondly : that during the disintegration of the ferment
cells, the body undergoing fermentation breaks up into simpler
groups. .
These being admitted facts, we may now notice the theories to
account for the action of the ferment.
1. Berzelius explained it by the influence of a force which he called
Catalysis, a word signifying Fermentation. He thus assumed the
existence of a new force, but at the same time acknowledged in-
directly his inability to perceive, or to detect the force, and the im-
possibility of explaining its action.
2. Pasteur’s theory is as follows. The ferment, he considers, grows
and multiplies at the expense of the sugar. This act of the ferment
in withdrawing from the sugar a portion of its constituent matter, he
regards as essential to the process of fermentation, and the primary
cause of the sugar itself breaking up into simpler groups.
3. Liebig admits that the ferment may multiply at the expense of
the sugar, but at the same time refuses to admit that the withdrawal
of the matter from the sugar necessary for the propagation of the
yeast cells, is the cause of the phenomena of fermentation. He con-
siders that fermentation is due to the active state of change going
on within the yeast cell, being communicated to the sugar in actual
contact with it, thereby inducing in the sugar the breaking up process
that the yeast cell itself is undergoing; in other words, that the dis-
turbance going on in the yeast is mechanically communicated to the
Sugar, thereby effecting its breaking up and re-arrangement. Hence,
according to Liebig, if the yeast grows at the expense of the sugar, it
is merely to maintain a supply of the material necessary to keep it in
a continuous state of disturbance.
490 HANDBOOK OF MODERN CHEMISTRY.
This theory is not unphilosophical although it is theoretical. That
one body in motion may communicate its motion to another body not in
motion, thereby overturning the existing equilibrium of that body, is
a phenomenon of constant occurrence.
(5.) The Practical Applications of the Process of Fermentation,
(a.) Alcoholic Fermentation. (1.) Wine-making. The expressed grape-
juice (the must) is first of all freely exposed to the air. The air
decomposes the vegetable albumen of the juice, and this at once acts
as a ferment on the grape sugar. If the sugar be in excess and the
albumen deficient, we obtain a sweet wine; if the sugar be deficient, and
the albumen in excess, a dry wine results. During fermentation, argol
(acid potassic tartrate) is deposited, owing to its insolubility in dilute
spirit. This circumstance constitutes the superiority of the grape
over all other fruits for wine-making—the separation of the acids of
other fruits, such as of gooseberries and currants (viz., malic and citric
acids) not being effected during fermentation, and their taste conse-
quently requiring to be masked by the addition of an excess of
Sugar.
The colour of red wines is derived from the grape skins. Effer-
vescent wines are bottled before fermentation is complete.
(2.) In brewing—the barley has first to be malted. Malting consists
in setting up germination, by the combined action of air, heat, and
moisture on the seed, and then stopping germination by drying the seed
at 140°F. (60°C.). The object of this is to convert (by oxidation) the
gluten of the seed into Diastase (6táaraac decomposition) a peculiar,
ferment-like body which has the power of changing the insoluble
starch of the seed first into dextrin, and finally into soluble grape
sugar. In nature, this process is necessary in order to supply the
germ with its first food, which must be presented to it in
a soluble form. The malt is then bruised, treated with water, and
the liquid set aside for some time—any unconverted starch in the
malt being thus brought into contact with the diastase, and its complete
conversion into sugar effected. One part of diastase will convert
2,000 parts of starch into grape sugar, but the power of the diastase
is itself exhausted during the process. The malt-mash is now
strained, the clear liquor constituting what is called “the wort,” and
the undissolved portion “brewer's grains.” The clear liquor is now
boiled with hops, the bitter resinous principle of which (lupuline) not
only gives flavour to the beer, but prevents it undergoing acetous
fermentation. It is finally mixed with yeast, when the beer “works,”
that is “ferments,” the sugar splitting up into alcohol and carbonic
acid.
The malt used in the manufacture of porter is partially caramelized
or “high dried.” -
FERMENTATION. 491
(3.) In spirit-making, the distiller prepares a wort or “wash,” like the
brewer, with this exception, that he mixes 4 parts of unmalted with 1
part of malted grain, the diastase of the latter being sufficient to
convert the whole of the starch of the former into sugar. Thus, much
of the labour and expense of malting is avoided. Moreover the
distiller has no need to add hops to his wort, nor to consider the
details of fermentation as the brewer is compelled to do, except that
it should be as complete as possible. A large quantity of spirit is
prepared from potatoes and also from corn, the starch of which
may be converted into sugar by admixture with a little malt. In
both cases, however, a small quantity of a very acrid oil (fusel oil)
accompanies the ethylic alcohol, and this it is the duty of the rectifier
to separate by careful distillation, the fusel oil being less volatile
than the alcohol. -
(4.) In bread-making, a little yeast is mixed with the dough, the
object being to render the bread light and spongy. The sugar of the
flour ferments, generates carbonic anhydride, which causes the bread
to “rise,” the spirit formed during “the working,” escaping when
the bread is baked.
Ammonic carbonate, sodic carbonate and hydrochloric acid, and
lastly a stream of pure carbonic acid (Dauglish), have been suggested
in bread-making in the place of yeast. In ancient days, a piece of
dough in a state of incipient putrefaction (leaven) was used as a
ferment, respecting which it was known that “a little leaven leaven-
eth the whole lump.”
(B.) The lactic fermentation.—This is seen in the ordinary decomposi-
tion of milk into curds and whey. Koumiss is fermented mare's milk.
It is a spirituous liquor.
(y.) The acetous fermentation.—Illustrations of “acetification” may be
noticed in beer turning sour, the acidity of which is due to acetic acid;
and also in what is called the “quick vinegar process.” This latter
consists in allowing a heated mixture of alcohol and yeast (the yeast
being added to supply the necessary nitrogenous matter) to trickle
over wood shavings soaked in vinegar, the wood shavings serving as
points of attachment for the mycoderm. It is essential that the supply
of air be very free. If the supply of air be limited, aldehyde is formed,
and much loss of vinegar results:—
C.H6O + O = C.H.O + H2O.
Alcohol + Oxygen – Aldehyde + Water,
but if the supply of air be free, aldehyde is not formed, or if it be
formed, is immediately oxidised :-
C.H6O + Os C.FI,02 + H2O.
Alcohol + Oxygen Acetic acid + Water.
The French wine-vinegar is prepared from light wines, by first
mixing them with a little boiling vinegar, and then allowing the
mixture to trickle over wood shavings into casks.
492 EIANDBOOK OF MOIDERN CHILMISTRY.
The English malt vinegar is prepared from an infusion of malt,
which is allowed to undergo both the alcoholic and the acetous fer.
mentation. Commercial vinegar may by law contain the thousandth
part of its volume of sulphuric acid, for the purpose of preventing its
turning mouldy.
II. PUTREFACTION.
Definition.—A spontaneous change common to all nitrogenised
organic bodies when exposed to the air, whereby they are resolved
into new and simpler products. The action is accompanied by the
evolution of unpleasant gases, which are for the most part compounds
of sulphur and phosphorus.
It differs from fermentation, in that unpleasant products are evolved,
as, e.g., in the decomposition of a dead body. Moreover, a putrescible
body is always a nitrogenised body, which at a certain temperature
in contact with air and moisture, decomposes, and then becomes
capable of acting as a ferment.
It differs from eremacausis or decay in that it is not oxidation, although
air is necessary in the first instance to start the action. Modern in-
vestigations lead us to believe that the air may be the carrier of spores
or ova, having the power of inducing the change. This is assumed
because a body liable to putrefaction, does not putrefy if it be boiled
in a flask, and when boiling, the neck of the flask plugged with cotton-
wool. Nevertheless, we see a relationship between eremacausis, putrefac-
tion and fermentation. Putrefaction is commenced, like decay or
eremacausis, by the action of the air, whilst the putrescent body is
capable of inducing fermentation in fermentable solutions. Moreover,
like fermentation, putrefaction is always accompanied by the develop-
ment of certain minute living organisms, fungi and infusoria.
(1.) The Conditions Necessary for Putrefaction.
(a.) Air.—The presence of air is essential only at the commencement
of the process, and not when putrefaction has fairly commenced. Its
progress is then independent of any aid external to itself. Thus
fruits and meats are preserved in sealed air-tight tins.
(3.) Moisture.—A perfectly dry body does not putrefy. Thus
vegetables when perfectly dry may be preserved for a considerable
time (Masson’s patent). The preservative action of sugar and salt
has been ascribed by some to their attraction for moisture, and their
power of withdrawing it from the putrescible body.
(y.) A temperature between 40° and 200°F. (4.5° and 93-5°C.).
Cold prevents putrefaction by increasing cohesion. Thus fish are
preserved in ice. The stories of bodies of men and animals having
been preserved in theice of polar regions for many years are numberless.
Warmth destroys cohesion, and thus aids putrefaction, whilst too
great a heat destroys the body by burning it up.
PUTREFACTION. 493
(2) Means of Preventing Putrefaction.
By the general term “disinfectant” we include antiseptics and
deodorizers. -
An antiseptic is an agent that prevents putrefaction, and entirely
stops the evolution of offensive gases.
A deodorizer is an agent that either absorbs or destroys the offensive
gases after they are formed, but does not prevent their formation—
in other words, does not prevent putrefaction.
Disinfectants are of two kinds—natural and artificial.
1. Natural disinfectants—
(a.) The Atmosphere. This acts both mechanically by its power
of removing foul vapors and other matters, and chemically by effecting
their oxidation.
(6.) Water. Its action is chiefly mechanical. In a river, during its flow,
the organic matter becomes disintegrated, and rapid self-purification
results. Every shower of rain purifies the air. Besides its cleansing
powers, by reason of its endosmic action, water is inimical to the
corpuscular structures of many specific contagia, for, by bursting their
cell-like envelopes, it destroys their vitality.
(y) Soil. The power of soil is manifested in our graveyards.
Owing to its porosity it effects the oxidation of decomposing matter.
In the presence of alkalies, ammonia is rapidly oxidized to water and
to nitric acid, whilst the ferric oxide present acts as a purveyor of
atmospheric oxygen.
(6.) Light.
(e.) Heat and Cold. Vaccine matter loses its power at 140° F.
(60°C.), and the virus of scarlet fever at 204° F (95.5°C.). The
common vibrio is destroyed at 300°F. (149°C.), and the black vibrio
at 400°F. (204-5°C.). Others assert that none of the lower organisms
will bear a temperature of 266° F (130°C.) in air, or of 230° F.
(110° C.) in water. [NotE. A heat of 250°F. (121°C.), aided by a
jet of steam, may be safely used in disinfecting textile fabrics.]
2. Artificial disinfectants.
(a.) Mineral acids, such as sulphurous, nitric, hydrochloric, sul-
phuric, and chromic acids. In this order, they have the power of
stopping the development of infusoria in organic solutions, sulphurous
acid being the least, and chromic acid the most powerful.
(3.) Organic acids, such as carbolic, cresylic, acetic, picric, benzoic
acids; benzoic being the most powerful, and acetic the least so.
(y.) Alkalies. Lime, potash, soda, and ammonia are only active
disinfectants when they are used in a concentrated form. The use of
lime in stables is for the purpose of assisting the oxidation of the
organic matter. Added to sewage it kills infusoria and checks
decomposition. *.
(6.) The haloids. Iodine acts as a mild disinfectant, and chlorine
494 HANDBOOIC OF MODERN CHEMISTRY.
as a powerful one; chloride of soda (“Labarraque's Liquid”); chlo-
ride of zinc (“Sir Wm. Burnett's Fluid’’), the action of which is
due to its power of coagulating albumen and of absorbing ammonia and
sulphuretted hydrogen, chloride of aluminium (“chloralum ”), which
is neither an aérial disinfectant, nor has it the slightest deodorising
power, and common salt and other chlorides are also frequently used.
(e.) Mineral Sulphates. Sulphates of zinc, of iron (“Mudie's Dis-
infectant”), of alumina and of copper act as disinfectants, owing to
their power of coagulating and destroying living organisms, and
neutralizing offensive miasms.
(...) Potassic Permanganate and Chlorozone.—These destroy dead
organic matter, but have very little action, so far as we know, on
living organic matter.
(m.) Volatile Oils.--Camphor, turpentine, etc. These hinder the
development of fungi and animalcules, and generate ozone (?) It
was believed in former times that the planting aromatic herbs about
a house warded off pestilence.
(6.) Charcoal and other porous bodies.—The action of such bodies is
due to their power of absorbing noxious gases, and so bringing them
into contact with condensed atmospheric oxygen, thereby effecting their
destruction. But it must be remembered that it is essential for the
action of charcoal, that there should be a free supply of atmospheric air.
Note, as regards disinfectants, the following practical hints:—
1. Certain disinfectants, such as chlorine, chloride of lime, Sul-
phurous acid, carbolic acid, and volatile oils, are aerial disinfectants,
and may be used for the purification of air; whilst others, such as
chloralum, permanganate of potash, chlorozone, the mineral sulphates,
chloride of zinc, etc., are useless for the purpose of purifying the air
of a sick room, inasmuch as they are not volatile.
2. Neither chlorine, hypochlorous acid, carbolic acid, or sulphurous
acid can be used to disinfect a chamber when a person is living in it,
the quantity of the gas required to effect this object rendering the
atmosphere absolutely irrespirable. Hence perfect disinfection is
only possible when a room is vacated. The combustion of 1% ozs, of
sulphur to every 100 cubic feet of space in a room, is necessary to
effect complete disinfection. !
3. Chloride of zinc and strong carbolic acid being corrosive bodies,
should not be used for the disinfection of textile fabrics, but only
for such purposes as the disinfection of faecal matter, etc.
4. In disinfecting clothing at the sick house, boil the articles in
water and then steep them in a solution of carbolic acid (3iv. to
1 gallon.) To disinfect clothes completely, however, they must be
submitted first to sulphurous acid, and then to a temperature for at
least 6 hours of from 240° to 250° F (115.5° to 121° C).
5. In disinfecting stables, cattle lairs, slaughter-houses, etc., there
is nothing better than lime, on account of its detergent, as well as
its disinfecting properties.
EREMACAUSIS. * 495
6. In the treatment of sewage, lime and alumina act as excellent
defaecatory and precipitating agents.
III. EREMACAUSIS (#pepoc gentle, kaijoric combustion) Decay.
Definition.—The decomposition of moist organic bodies by oa;idation
into simpler groups, or, in other words, the slow burning of organic
bodies. This action is unaccompanied by any sensible elevation of
temperature. It is seen in the decay of wood, when a brown powder
(ulmin or humus) is left, the hydrogen oxidizing before the
carbon ; also in the drying of oils, the solidification being attended
with the absorption of oxygen (which has been known to be so rapid
that combustion has resulted); also in the formation of acetic acid
from alcohol, and in many other processes.
(1.) The Conditions Necessary for Decay.
(a.) The free access of atmospheric air.—There are reasons to believe
that the active agent in inducing eremacausis is Ozone (see page 62).
Thus bodies are found to be specially prone to decay after a thunder-
storm, during which ozone is largely developed. Ozone, however,
never accumulates in the air, but is used up as fast as formed to
oxidize organic matter and vapours of organic origin. It is however
more than probable that ordinary oxygen can carry on the process of
decay when once the action has been started—although it must be
remembered that the development of ozone itself, is a consequence or
result of eremacausis, the decaying body furnishing the active agent
necessary for its further destruction.
(3.) The presence of moisture.—Perfect dryness suspends decay, as
it does fermentation and putrefaction. A body which is incapable of
absorbing oxygen when dry, will often do so when moist. Thus in the
“grass bleaching” of calicoes, where oxidation (eremacausis) only is
relied upon for effecting the destruction of the coloring matters (a
part of the cotton itself being oxidized at the same time), it is found
to be essential to keep the fabrics moistened with water.
Thus again, in the formation of coal and peat, the presence of
moisture is an essential condition. -
(y.) A certain temperature.—Cold by increasing cohesion interferes
with decay; at the freezing point 32°F. (0° C.) decay is arrested.
Warmth by its opposite effect promotes decay.
(2.) The Circumstances Influencing Eremacausis.
(a.) The action is promoted by warmth.
. (3) The action is promoted by the presence of alkalies. Thus in the
formation of nitres the oxidation of ammonia takes place in the
presence of a powerful base (see page 274); or again, in estimating
496 s FIANDBOOK OF MODERN CHEMISTRY.
}
the quantity of oxygen present in a mixed gas, its absorption may be
effected by a mixture of pyrogallic acid and potassic hydrate (See
page 98).
(y.) The action is checked by certain antiseptic salts.
(6.) The action is promoted by the contact of an eremacausing body.
Just as one body on fire is capable of inflaming a body not on fire, so
a body undergoing decay can by contact, produce decay in a substance
liable to it. To prevent this contact oranges are packed in paper,
etc., etc.
(e.) The action is promoted by the presence of porous substances such as
charcoal, etc., whereby the oxygen is absorbed and condensed, and its
actual contact with the body effected.
(...) The action is promoted by an excess of ozone in the atmosphere,
Such as occurs under certain atmospheric conditions.
(B.) ARTIFICIAL DECOMPOSITION.
I. Action of Heat on Organic Bodies.
Heat decomposes all organic matter, whereby new products (called
the products of destructive distillation) are formed. These, on cooling,
never resolve themselves into the same states of combination in which
they existed originally in the organic body. The more complicated
the organic body, the more easily is it decomposed by heat.
Heat acts on many inorganic compounds; sometimes these products
do not re-combine on cooling, but most often the action of the heat is
reversed by cold. For example, calcic hydrate by heat is resolved
into lime (CaO) and water, but these in the cold combine to form
calcic hydrate.
Heated in the open air, some organic bodies sublime, as, e.g., benzoic
acid ; others partially decompose, as for example in the formation of
pyrogallic acid (C6H603) and carbonic anhydride, from gallic acid
(C,EISOs); others simply burn, their carbon forming carbonic acid,
and their hydrogen water, by combining either with their own oxygen
or with the oxygen of the air.
When organic bodies are heated in closed vessels, the process is
known as “destructive distillation.” Simpler and more stable com-
pounds are thus formed, and a residue of carbon mixed with the in-
combustible ash remains in the retort.
The products of destructive distillation vary with the body operated
on, and with the temperature employed:—
(1) This may be noticed, for example, in the distillation of non-nitro-
genised bodies, such as wood:—
(a.) At the lowest temperature, compounds are given off containing
much oxygen, such as water, acetic acid, carbonic anhydride, etc.
(3.) At a higher temperature, the compounds evolved contain less
oxygen, such as carbonic oxide, wood spirit, kreasote, etc.
ARTIFICIAL DECOMPOSITION. 497
(y.) At a still higher temperature, various hydrocarbons distil over,
such as toluene, xylene, and the different forms of paraffin, etc.; whilst
(3.) At a temperature approaching redness, pure hydrogen pre-
dominates.
Products of the Action of Heat on Coal,

§ 3 o tº le P-, 5 . * * * º usi
- # #, # 3 #53 g|Boiling point. º
COMPOUNDS, Etc. Formula. 3-#" | 3 : |# 3 § 3.
3= | #3 º F. • C. °F. 20.
CoAE, GAs.
Marsh gas (Methane). . . . CH, 16 0° 559
Olefiant gas (Ethene). . . . C.H., 28
Acetylene (Ethine) º C2H2 26. 0-92
Hydrogen . . . . . . . . EI l 0-0693
Carbonic oxide . . . . . . CO 28 0-973
Nitrogen . . . . . . . . N 14
Vapors of vol. liquid hydro-
carbons . . . . . . . .
Vapors of carbon disulphide CS, 76 1-272 2-67 109-4 || 43
Sulphuretted hydrogen .. H.S 34 1' 171
Carbonic acid . . . . . . CO, 46 1:524
Tar and volatile oils . . -
Ammonia . . . . . . . . NH, 17
AMMONIA WATER.
Ammonic carbonate . . . .
}} Sulphide
37 cyanide ..
, sulphocyanide
CoAL TAR.
Newtral hydrocarbons.
Liquid. ---
Benzene * * * * * * * CŞHs 78 || 0-85 2:77 | 177 | 80-6 | 40 |4-45
Toluene. . . . . . . . . . C.Hs 92 || 0-881 0-87 230 I 10 -
Xylene . . . . . . . . . . CsPilo . . . 0-87 284
Cumene.. s ºr CoE is 0-85 || 338
Solid. -
Naphthalene.. ºr e º ºs Cld Hs | 128 || 1: 153 || 4-528 || 413-6 212 174 " || 79
Anthracene . . . . . . . . Clºſio || 178 l'I47 6:741 | 680 360 416 213
!hrysene . . . . . . . . CisB12 228 450 || 232
Pyrene . . . . . . . . . . Cashio || 202 - 350 177
Alkaline products. - ~
Ammonia . . . . . . . . NH, 17
Aniline . . . . . . . . . . . C.H.N | 93 |1-02 || 3:21 || 360 | 182
Picoline. * * * * * * * * * CeBI,N 93 0-961 || 3-29 271 . 135
Quinoline . . . . . . . . . C.H.N | 129 | 1.081 4,519 462 || 235
Pyridine . . . . . . . . . . C.H.N. 79 || 0-986 2-92 242 117
, Acid products.
Garbolic acid . . . . . CSH30 94 | 1.065 370 | 187 95 35
Gresylic acid g C.H.0 | 108 397
OSolic acid . . . . Castis:0,
Brunolic acid -v -- -
Cétic acid . C.H.0, 60 I •06 243 117
T--—
498 HANDBOOK OF MODERN CHEMISTRY.
(2.) In the case of nitrogenised bodies, such as coal, a part of the
nitrogen is evolved as ammonia and basic bodies allied to it, such
as aniline (C5H7N), quinoline, pyridine, etc., and also as cyanogen;
whilst a part remains in the still, together with the carbonaceous
residue.
It will be convenient here to notice the products of the destructive
distillation of Coal and of Wood, the former serving as an illustration
of the action of heat on a nitrogenized body, and the latter on a non-
nitrogenized body.
(1.) The Products of the Distillation of Coal (or other nitrogenized
substances).
The coal is distilled in retorts, connected with which are iron
delivery pipes. These ascend perpendicularly for a few feet,
and then curving round, dip below the liquid contents of a large
horizontal pipe, called “the hydraulic main,” which acts both as a
water valve, and also as a receiver for the delivery pipes from nume-
rous retorts. This pipe receives the tar and the gas liquor, through
which the impure gas bubbles. Thus we obtain the coke in the
retort, and the gas, the gas-water, and the coal tar, as the products
of the distillation.
1. Coal Gas.-[A ton of coal yields from 9000 to 9500 cubic feet
of gas.] -
This is, as the table shows, a compound of a variety of gases and
vapors. The relative proportion of the constituents is influenced
greatly by the temperature at which the gas is prepared. The
heat should always be at its maximum at the commencement of
the operation. (a.) If it be too high, the heat of the retort decomposes the
marsh and olefiant gases and the hydrocarbon vapors, carbon being
deposited in the retort (gas carbon). An excess of hydrogen there-
fore escapes, and the illuminating power of the gas suffers in conse-
quence. Hence the use of eachausters in order to hasten the exit of the
gas from the retorts. Moreover, at a high temperature bisulphide of
carbon is formed, the complete removal of which from the gas is prac-
tically impossible. (3.) If the heat be too low, the gas contains too
great an excess of solid and liquid hydrocarbons, which tend to block
up the tubes. These facts are well shown in a table (from Bloxam),
illustrating the composition of coal gas at different periods of its
distillation.

In 100 volumes. 1st hour. 5th hour. 10th hour.
Olefiant gas and volatile hydrocarbons . . 13-0 7-0 0.0
Marsh gas . . . . 82.5 56-0 20-0
Carbonic oxide , , 3-2 11:0 10 : 0
Hydrogen . . (): () 21-3 60-0
Nitrogen I 3 4-7 10-0
DISTILLATION OF COAL. 499
The increase of the carbonic oxide at the fifth hour, may arise from the
carbon decomposing the H2O, and the increase of the nitrogen from
the decomposition of the ammonia at high temperatures.
The gas as it leaves the hydraulic main needs purification. This is
effected by various means:—
(1.) The Condensers (or refrigerators) consist of a series of bent iron
pipes through which the gas is made to travel. By thus exposing a
large surface of the gas to the air, any tar and ammonia liquor that
escapes the hydraulic main, owing to the gas being superheated, is
condensed.
(2.) The Scrubber.—This is a tower filled with wet coke. By this
means the removal of the chief part of the ammonia from the gas may
be effected. [The evil of the scrubber is that it diminishes the illumi-
nating power of the gas, by removing at the same time as the am-
monia, a portion of the more condensable hydrocarbons.]
(3.) The Purifiers.-The object of these is to remove the carbonic
anhydride, (which is said to decrease the illuminating power of the
gas,) and also the sulphuretted hydrogen, and other sulphur im-
purities in the gas, of which CS2 is one.
To get rid of carbonic acid and sulphuretted hydrogen, (and also of the
sulphocyanogen, cyanogen, etc.,) purifiers are constructed containing
either—
(a) Lime, a carbonate and a sulphide of lime being formed, or,
(3.) Owide of iron (Fe2O3) (mixed with sawdust to prevent caking).
The oxide removes sulphuretted hydrogen and hydrocyanic acid only
from the gas. Thus, Fe2O3 + 3 B.S=2FeS--S-H 3H2O.
With hydrocyanic acid, Prussian blue or some similar compound
is formed. .
The great advantage of oxide, is the ease with which the iron
sulphide can be again converted into oxide by mere exposure to air
(revivified), no nuisance being caused by the operation. The oxide may
be used over and over again, the sulphur collecting in the mass until
finally, after repeated revivifications, the percentage of sulphur
present renders it of commercial value for the manufacture of oil of
vitriol (see page 152).
To get rid of the sulphur impurities other than sulphuretted
hydrogen, many processes have been suggested, of which the follow-
ing are the most important, although all have proved more or less
unsuccessful:—
(a.) Sulphide of lime, the evil of which is the nuisance occasioned
by its use.
(3.) By washing with the ammoniacal liquor.
(y.) By steam at a high temperature, whereby CO., and H2S are
formed, both of which are easily removed from the gas.
CS., -i- 2H2O = CO2 + 2.H.S.
Carbonic + Water - Carbonic –– Sulphuretted
disulphide anhydride hydrogen.
500 - HANDBOOK OF MODERN CEIEMISTRY.
(6.) By Red-hot lime.
CS, + 3Ca(O = CaCO, +- 2CaS.
Carbonic + Lime F Calcic + Calcic
disulphide carbonate Sulphide.
(e.) By a solution of lead oaside in caustic soda.
CS., -i- 2PbO + 2NaIHO = 2PbS + Na2CO3 + H2O.
Carbonic + Lead -- Sodic = Plumbic + Sodic + Water.
disulphide oxide hydrate sulphide carbonate
Finally the gas passes to the gasometer.
2. The Gas Liquor.—From this liquor, which contains numerous
ammoniacal salts, but chiefly the carbonate, sulphide, cyanide and
sulpho-Cyanide, the various salts of ammonia in commerce are ob-
tained, either by the direct action of acids on the liquor, or by setting
free the ammonia by its distillation with lime (see page 311).
3. The Coal Tar.—This is distilled in iron retorts.
The tar contains three sets of products: (a) those volatile at a low
temperature; (3) those volatile at a high temperature; (y) those not
volatile at any temperature.
(a.) Those volatile at a low temperature.—That which in the first in-
stance distils over with the steam is called light oil, from its having a
less specific gravity than, and consequently floating on, the condensed
water. Every 100 parts of tar should yield 10 per cent. of light oil.
The light oil contains benzene, toluene, xylene, cymene, etc., con-
taminated more or less with dead oil. The light oil is again distilled,
the distillate forming what is called coal naphtha, a quantity of heavy oil
remaining in the retort. The coal naphtha is purified by shaking it
up, first with sulphuric acid, whereby basic substances are removed,
then with a dilute solution of potash to separate the carbolic acid,
and finally with water. When decanted from the water it forms
“rectified coal naphtha.” This is now separated into its various
constituents by fractional distillation:—
From 175° to 180° F. (79.4° to 82.2°C.) it yields pure benzene.
180°, 230°F. (82.2° , 110°C.) , ,, P.
230°, 23.5°F. (110° , 118°C.) 5 y , toluene.
284° , 293°F. (140° , 145° C.) 5 y ,, xylene.
336°, 342°F. (168.9°, 172°C.) , , ,, cymene.
Commercially, however, that portion which distils over between
175° and 250°F. (79.5° and 121.1% C.), is designated and sold as
benzol or benzene.
(3.) Those volatile at a high temperature.—This constitutes the “dead
oil.” It is also called “yellow oil,” from its peculiar color, and “heavy
oil,” from its being heavier than, and therefore sinking in, water. The
last portions that distil over become nearly solid on cooling. Every
100 parts of tar yield about 25 per cent. of dead oil.
Dead oil contains carbolic acid, naphthaline, anthracene, aniline,
quinoline, etc.
DISTILLATION OF WooD. 501
Amongst the first products of the distillation of dead oil, is carbolic
acid (C6H60), the principal acid product of the oil. It comes over
chiefly between 300° and 400°F. (149° and 205°C.). Upon its pre-
sence depends the antiseptic properties of the dead oil, which is
largely used for preventing the decay of wood.
Amongst the last products of the distillation is anthracene (C14H10),
a body of great commercial value in the manufacture of artificial ali-
zarine. The first portion of the anthracene that distils over, is mixed
with naphthalene (CoHa), and the last part with chrysene (CaFIz). It
is purified in the first instance by re-distillation, the first and the
last portions being rejected. The intermediate portion is purified by
crystallising either from a solution in alcohol, or in coal oils boiling
between 212° and 248° F (100° and 120° C.).
(y.) Those not volatile at any temperature.—This constitutes the black
residue in the retort called pitch. It is used in the preparation of
Brunswick black, for asphalting, etc.
By the action of heat on horny matters, similar products to those
already described are formed, the ammonia (hartshorn) being pro-
duced in great quantity, owing to the richness of horn in nitrogen.
(2.) The Products of the Distillation of Wood (or other
non-nitrogenized substances.)
The following exhibits the difference in the chemical composition
of coal and wood:—
Per 100 parts. Carbon. Hydrogen. Nitrogen. Oxygen.
Bituminous coal . . . . 79.5 5' 5 1 - 9 13-1
Wood (dried oak) . . . . 51-6 5-7 0-2 42-5
We note therefore :– -
(1.) That in wood there is about one-third less carbon than in coal.
(2.) That in wood there is a mere trace of nitrogen (0.2 per cent.),
whilst in coal the quantity of nitrogen is considerable (1.9 per cent.)
(3.) That in wood there is more than three times as much oxygen as
there is in coal.
(4.) That the proportion of hydrogen in both are about the same.
From this we should expect in the destructive distillation of wood :—
(1.) That the gases evolved from wood would be less illuminating
than those from coal.
(2.) That there would be scarcely any nitrogenized products such as
ammonia, etc., produced ; but
(3.) That there would be a great excess of oxidized products, such
as water, carbonic acid and oxide, acetic acid, etc.
502 HANDBOOK OF MODERN CHEMISTRY.
The wood contained in an iron cage, is placed in a retort and
heated. Wood charcoal remains in the retort, and the products of
the distillation are as follows:—
Wood Tar.
Solids.
Paraffin . . . . . . CnH2n+2 Pyrene . . . . . . CisB to
Naphthaline . . . . Ciołł's Chrysene Cisłł12
Cedriret . . . . . . Resin
Pittacal
Liquids.
Toluene . . . . . . C. He Pyroligneous or )
Xylene. . . . . . . . CaFI to acetic acid C.H 10,
Cymene . . . . . . Cin His Wood naphtha . . CHAO
|Kreasote . . . . . . C., H30 Acetate of methyl. . CHA.C.H.0,
Picamar . . . . . . Formate of methyl CHA.CHO,
Kapnomor . . . . . . Clo Hú0 Acetone . . . . . . CŞII:0
Eupione . . . . . . C3H1, Water
Gases.
Marsh gas . . . . . . . . . . . . . . . . CH,
Carbonic oxide . . . . . . . . . . . . . . CO
Carbonic acid . . . . . . . . . . . . . . CO2
The distillate consists of water, tar, and naphtha.
The crude naphtha yields acetone (C3H6O), pyroligneous acid
(C.H.O.), and wood naphtha or methylic alcohol (CH4O), this latter
product being rectified by distillation below 212°F. (100° C.).
Paraffin distils over from the last portion of the tar. It may be
obtained in larger quantity by the distillation of “peat” or “Boghead
cannel.”
II. Action of Acids on Organic Matters.
(1.) Sulphuric acid—This acts on organic bodies in different
ways, as follows:– -
(a.) It may combine with the organic body. Eacamples:—Organic
bases become sulphates. Alcohol (C2H6O) becomes sulphovinic acid
or acid-ethylic-sulphate (C.H., HSO4). Benzoic acid (C7H6O.) be-
comes sulpho-benzoic acid (C, HGO2, SO3). Benzol (C6H5) becomes
sulphobenzolic acid (C6H6.S03). Glycerine (CsII20s) becomes sulpho-
glyceric acid (C,Eſg03, SO3). .
(6.) It may decompose the organic body. Examples:—Oxalic acid
(C,EI204 = CO2 + CO + H2O); formic acid (CH2O. = CO + H2O), etc.
(y.) It may abstract the elements of water from the organic body.
JExamples:–Thus sugar is carbonized by it. Alcohol (C2H6O) becomes
ether (C.H.100).
(6.) It may introduce the elements of water into the organic body.
JEvamples:—Dextrine (C6H10O3) becomes glucose (C5H12O6).
(e.) It may dissolve the organic body and effect an alteration in its
ORGANIC BODIES. 503
color. Eacample : –Salicine is turned a bright red by the action of
the acid.
(2.) Nitric acid. With some organic bodies (as morphia) nitric acid
strikes a deep red colour. The strong acid effects in many cases
complete destruction of the substance on which it acts. For example,
sugar is broken up into water and carbonic acid. The chemical
effects of the dilute acid on organic bodies vary as follows:–
(a.) It may combine with the organic body. Ecamples:–With
basic bodies it forms salts. Ethylamine (C2H1N) becomes ethylamine
nitrate (C.H, N, HNOs)
(3.) It may effect the oxidation of the organic body. Eramples —
Sugar (C12H22O11) and starch (C5H10O3) form oxalic acid (C2H2O4);
gum (C12H22O11) forms mucic acid (C5H10Os).
(y.) It may form substitution products with the organic body.
Thus, nitryl (NO2) may be substituted for hydrogen, forming nitro-
compounds, which are generally explosive. Examples : —Benzene
(C.Hg) becomes nitro-benzene (C6H2(NO2)); cellulin (C6H10O3) be-
comes guncotton (C6H1(NO2)3O3); glycerine (C5H8O3) becomes nitro-
glycerine (CAH3(NO2)3O3).
(3.) The Haloid acids (HCl ; HBr ; HI).
(a) They may combine with the organic body, as in the case of the
alkaloids, the compound ammonias, and various unsaturated com-
pounds. Examples:–Ethylamine (C.H.N) becomes ethylammonic
chloride (C.H. N.HCl); turpentine (CoH16) becomes hydrochlorate of
dadyle, or artificial camphor (CoH)6.HCl). (The same change occurs
by the action of HCl on most essential oils.) Fumaric acid (C, H.O.)
becomes bromo-succinic acid (C,EI,04, HBr); ethylene (C2H4) becomes
mono-iodo-ethane (C.H., HI); hydrocyanic acid (HCN) becomes hy-
driodate of formylamine (HCN, HI).
(ſ3.) The substitution of the chlorine, bromine, or iodine of the
acid for the group (HO) may result. This happens more particularly
in the case of the alcohols and oxy-acids. Eramples :—Alcohol
(C.H3(HO)) becomes ethylic iodide (C2H5T); oxy-proprionic acid
(CH3(HO)0) becomes bromo-proprionic acid (C,EI, BrO2).
[In the case of hydriodic acid, it effects the immediate decomposition
of the iodine substitution compounds, the iodine being replaced by
hydrogen. Thus hydriodic acid is a powerful reducing agent, for it
first of all replaces HO by I, and then instantly replaces the I by H.]
(4.) Phosphoric acid.—The anhydride acts as a dehydrating agent.
Example —Glycerine (C5H8O3) becomes acrolein (CEI,0).
III. Action of the Fixed Alkaline Hydrates on Organic Bodies.
(1.) They may combine with the organic body, as, e.g., where salts
are formed with organic acids, etc. Eacamples : —Potassic acetate.
Camphor (CoH)60)+ KHO forms potassic campholate (CoHirk02).
504 IIANDBOOK OF MODERN CHEMISTRY.
(2.) They may act as oxidising agents, forming acids, with the dis-
engagement of hydrogen. Example:—Acetic acid is formed by the
action of potassic hydrate on alcohol:—
C.H.60 + RBIO KC2H5O2 + 2H2.
Alcohol + Potassic hydrate = Potassic acetate + Hydrogen.
=
If the body be a nitrogenised body, the nascent hydrogen combines
with the nitrogen to form ammonia.
(3.) On chlorine, or other haloid substitution products, alkalies at
times effect (a) the replacement of the halogen by the group (HO), or
(3) remove the halogen in part or wholly from the compound.
(a.) C.H.Cl + KHO = ECC1 +C2H3(HO).
Ethylic chloride + Potassic hydrate = Potassic chloride + Alcohol.
(6.) C.H. Br + KHO = KBr + H2O + C.EI.
Bromethylene + Potassic hydrate = Potassic bromide + Water + Acetylene.
(4.) The amides (that is, compounds of amidogen (NH2) and an acid
radical), are decomposed by the alkaline hydrates, their nitrogen being
evolved as ammonia, the metal (K or Na) forming a salt with the
corresponding acid. Eacample:—Acetamide (NH2,C,EI50) becomes
ammonia (NH3) and potassic acetate (KO, C.H2O).
IV. Action of Alkaline Carbonates on Organic Matter.
When an organic body containing nitrogen is fused with an alkaline
carbonate, carbonic oxide is evolved, and cyanogen, as a cyanide of
the metal, is formed. Thus—
IC,CO3 + C, 4- N2 = 2KCN + 3CO.
Potassic carbonate + Carbon —H Nitrogen = Potassic cyanide + Carbonic oxide.
W, Action of the Haloid Elements on Organic Bodies.
(1.) Chlorine.
(a.) It may combine with the organic body (forming additive com-
pounds). This happens in the case of certain non-saturated compounds.
Eramples:–Benzene (C6H6) becomes benzene hexachloride (C6H3Cl3).
(3.) It may in the presence of water, oxidize the organic body.
Ecample —Benzoic aldehyde (C7H6O) becomes benzoic acid (C, H60.).
(y.) It may effect the removal of hydrogen (as HCl) from the
organic body with the substitution of chlorine (forming substitution
products). This may be complete or partial, depending upon the
substance acted upon, the temperature, etc. Thus we have :— -
CoEIAO2 ...... Acetic acid CH4 ...... Methane
C.H.ClO. ... Chloracetic acid CH3Cl. ... Chloromethane
C.HCl2O. ... Trichloracetic acid CH2Cl2... Dichloromethane
CHCl3 ... Trichloromethane
CC1, ...... Tetrachloromethane
ORGANIC MATTER. 505
(3.) It may effect the removal of hydrogen (as HCl) from the organic
body, but without the substitution of chlorine for it. Example :-By
acting with chlorine on alcohol (C.H5O), we form aldehyde (C2H40)
(C2H6O + Cl2=C.H,0+2HCl). -
(2.) Bromine.—The action of bromine is in all respects similar to,
but less intense than, that of chlorine.
(3.) Iodine. —Like chlorine and bromine, but less intensely than
either, iodine forms (1) additive compounds (such as C2H4Ic) with non-
saturated bodies, and (2) also acts as an oxidizing agent. But unlike
chlorine and bromine it does not form substitution products by direct
combination, unless (1) the hydriodic acid formed, be immediately
decomposed by some such means as by the addition of mercuric oxide
to the mixture, whereby HgI2 is formed (HgC) + 2 HI = HgI2 +
H2O), or iodic acid when free iodine is produced (HIO3 + 5HI =
3I.--3H2O); or (2) by the double decomposition of other chlorine and
bromine compounds with potassic iodide. For example:–Todacetic acid
(C.H.I.O.) may be formed from bromacetic acid (C.H. BrO2), by the
action upon it of potassic iodide. The intense action of hydriodic
acid on iodo-derivatives, explains the difficulty of forming substitution
compounds by the direct action of iodine.
WI. Action of Nascent Oxygen on Organic Bodies.
The nascent oxygen for this purpose is commonly liberated by
the action of dilute sulphuric acid on potassic dichromate.
1. The oxygen may combine with the organic body. Example :-
Aldehyde (C2H40) becomes acetic acid (C2H4O2).
2. It may decompose the organic body, forming two or more
oxidized compounds.
3. It may simply remove hydrogen from the organic body.
Example:—Alcohol (C2H5O) becomes aldehyde (C2H40).
4. It may remove hydrogen from the body, the oxygen replacing
it in equivalent quantity. Eacample :-Alcohol (C.H.60) becomes
acetic acid (C2H4O2).
5. It may remove hydrogen, the oxygen replacing it by twice its
equivalent quantity. Eacample s—Naphthalene (CoHs) becomes
naphtho-quinone (CoH6O2).
6. If the oxidation be intense, then (as in combustion) the carbon
and hydrogen of the organic body may be broken up into water and
carbonic anhydride, the sulphur oxidized, and the nitrogen and haloid
elements set free.
The changes thus effected by the oxidation of organic bodies, are
remarkable, and of great interest. By the action of nascent
oxygen on salicine (viz., by distilling it with dilute sulphuric
acid and potassic bichromate) we obtain the artificial oil of the
spiraea, or meadow-sweet. Uric acid (C5H4N403) by oxidation
506 HANDBOOK OF MODERN CHEMISTRY.
becomes alloxan (C,EIGN2O), and alloxan by oxidation becomes
urea (CH4N2O). By the action of nascent oxygen on amylic alcohol
(fusel oil) (C5H12O), we form valerianic acid (C5H10O2), etc.
VII. Action of Nascent Hydrogen on Organic Bodies.
Free hydrogen has no action on organic bodies; nascent hydrogen
acts powerfully. Nascent hydrogen may be set free either by (1) the
action of water on sodium amalgam, or (2) by the action of dilute
sulphuric acid on zinc, or of hydrochloric acid on tin. -
1. The hydrogen may combine with the organic body. Eacample:—
Ethene oxide (C.H.,0) forms alcohol (C.H.60).
2. The hydrogen (2 atoms) may remove oxygen (1 atom) from the
organic body. Ea’ample :-Benzoic acid (C7H6O2) + H2 becomes ben-
zoic aldehyde (C7H6O) + H2O. -
3. The hydrogen may effect the removal of the haloid elements.
4. The hydrogen may remove oxygen and the haloid elements, and
be substituted for them in the compound (inverse substitution). This
may happen either (a) in equivalent quantities, or (ſ3) the hydrogen
substituted may be only one-half the equivalent of oxygen removed.
Thus—
Benzoic acid Benzylic alcohol.
(6.) C6H3(NO2) + 3H2 = 2EI2O + C6H3(NH2).
Nitrobenzene Aniline.
VIII. Action of Other Reagents on Organic Bodies.
1. Zincic chloride, hydric-potassic sulphate, sulphuric and phos-
phoric oxides, are dehydrating agents.
2. Phosphoric chloride (PCl5) either (a) removes hydrogen from
the organic body, an equivalent of chlorine being substituted in its
place; or (3), removes oxygen from a compound, replacing it by its
equivalent of chlorine; or (y), removes hydroxyl, 1 of HO being
replaced by 1 of chlorine.
3. Sulphurous acid is a powerful reducing agent. In the presence
of a third body, having a tendency to combine with hydrogen, it de-
composes water, and forms sulphuric acid by combining with the
oxygen, hydrogen being set free.
4. Chromic acid. This acts as a powerful oxidising agent on organic
bodies.
We may notice lastly—
IX. The Action of Light and Electricity on Organic Bodies.
(1.) The action of light.—The combination of chlorine with many
organic bodies, is as much influenced by light as the combination of
ORGANIC BoDIES. - 507
chlorine and hydrogen. Thus chlorine and benzene combine imme-
diately in bright sunlight, slowly in diffused light, but not at all in
the dark. The decomposition of hydrocyanic acid is greatly accele-
rated by light: hence the acid is preserved in blue bottles. Moreover,
in some cases the compound formed differs according to the intensity
of the light; thus a mixture of chlorine and mono-chloro-propylene
(C.H,Cl) forms di-chloro-propylene (C,EI,Cl) in the dark, but the
compound (C3H3Cl3) in bright sunlight.
A well known action of light is its power of forming the green
chlorophyll of leaves; but we note also a special action of sunlight
in elaborating organic compounds generally, in the organisms of
growing plants.
(2.) The action of the galvanic current. The organic body is often
decomposed, oxygen being formed at the positive pole, and hydrogen
at the negative (from the decomposition of the water), these bodies
acting powerfully in their nascent condition on the Organic compound.
Professor J. H. Gladstone and Mr. Tribe have published a series
of researches on the action of what they call the copper-zinc couple ;
that is, a very intimate mixture of powdered copper and zinc. By
means of the galvanic power generated by the action of this mixed
metallic powder, the preparation and the decomposition of many
organic compounds have been effected. For eacample—the preparation
of zinc ethyl (Zn(C.H.)2), ethyl hydride (C.H.S.H.), diamyl, zinc amyl
(Zn(C,EIm)2), amyl hydride (C,Eſm.H), methyl hydride (CHs.H), age-
tylene (C2H3), propylene (C3H6), propyl hydride (CsPIT.H); also the
discovery of zinc propyl (Zn(C5H7)a), zinc isopropyl, zinc propiodide
(ZnC, H.I), and the ethylo-haloid compounds (as ZnC. H.Br.); also
the isolation of diallyl, the conversion of nitrates into ammonia
(Thorpe), etc., etc. (See “Chemical News” for years 1873–1876.)
508 IHANDIBOOK OF MOIDERN CHIEMIISTRY.
CHAPTER XXI.
CYANOGEN AND ITS COMPOUNDS.
Cyanogen-Hydrocyanic Acid–Cyanides—Compounds of Cyanogen with the Haloids
and with Hydroxyl-Sulphocyanic Acid–Double Cyanogen Salts—The Nitro.
prussides-Prussian Blue—Reactions of Cyanogen Compounds.
CYANOGEN.
CN or Cy. Molecular weight, 52. Molecular volume, | . Specific
gravity, 1801. Fuses at — 29.2°F. (–34° C.). Boils at – 5-39
(—20.7°C.).
Derivation,-(kūavoc blue ; yewváto I produce.)
History.—Discovered by Gay Lussac (1815).
Natural History.—It is not found in nature in a free state. It
is met with in the gases issuing from blast furnaces, and is pro-
duced in small quantities during the distillation of pit coal.
Preparation.—(1.) By the action of heat on the cyanides of mer-
cury, silver, or gold (HgCN)2=Hg--(CN)2). [A brown amorphous,
insoluble, non-volatile substance (paracyanogen (CN),) is formed
simultaneously with cyanogen. At a heat of 1548° F (860° C.) para-
cyanogen is converted solely into gaseous cyanogen, without leaving
any residue, thus proving it to be an isomer of cyanogen.]
(2,) By the dry distillation of ammonic oxalate [(NHA). C.O.] or
of oxamide [C2O2(NH3)2].
(NH4)2C2O, = 4H2O + (CN)2.
Ammonic oxalate - Water + Cyanogen.
Properties.—(a.) Physical. A colorless gas, having the odour of
bitter almonds. It is intensely poisonous. Its specific gravity is
1-801, and its relative weight 26; 100 cubic inches weigh 55.714 grs.,
and 1 litre, 2.8296 grims. A pressure of four atmospheres at 45° F.
(7.2°C.) or a cold of—22°F. (–30°C.) condenses it to a colorless liquid,
which has a specific gravity of 0.87°, and freezes at-29.2°F.(–34°C.).
It withstands a very high temperature without decomposing. It is
soluble in water (4 vols. in 1 of water), and very soluble in alcohol.
(6.) Chemical. Cyanogen burns in air with a rose-red flame, gene-
rating CO2 and N. Exploded with oxygen (1 vol. of Cy and 2 vols.
of O) it yields N (1 vol.) and CO, (2 vols.). Its solutions (whether
aqueous or alcoholic) decompose rapidly, the primary products being
ammonic oxalate [(NH4), C.O.,], a brown insoluble matter (azulmic
acid), and traces of hydrocyanic (HCN) and cyanic acids (CNOH). As
secondary products, formed by the action of the cyanic acid on the water,
we obtain urea CO(NH2), and hydric ammonic carbonate NH, HCO3.
FIYDROCYANIC ACID. 509
The decomposition of the aqueous solution is much retarded by the
presence of a mineral acid. Cyanogen was the first well-recognised
“compound organic radical.” Chemically it behaves exactly like a
monad non-metallic element, or simple acid chlorous radical, such as
chlorine. Just as chlorine (Cl)' is univalent, the molecule being re-
presented by Cl2, so cyanogen (CN) is univalent, its molecule being
represented by (CN)2. As chlorine combines with metals to form
chlorides (as AgCl; Hg"Cl2), so cyanogen combines with metals
to form cyanides (Ag(CN); Hg"(CN)2). As chlorine replaces monad
elements, so cyanogen replaces monad elements. Cyanogen combines
with hydrogen to form hydrocyanic acid (HCN), as chlorine forms
hydrochloric acid (HCl).
The reactions of cyanogen with potassic hydrate again, are exactly
analogous to those of chlorine. Thus:–
(a.) 2KHO + Cla = KCl + KClO + H2O.
Potassic + Chlorine = Potassic + Potassic + Water.
hydrate chloride hypochlorite
(3) 2KHO + (CN). = K(CN) + K(CN)0 + H.O.
Potassic + Cyanogen = Potassic + Potassic + Water.
hydrate cyanide cyanate
Thus cyanogen supplies us with a typical illustration of “a com-
pound radical,”—that is, a group of elements, capable of acting exactly
as though it were an element. To express this quasi-elementary
character of cyanogen, we represent it by the symbol Cy.
Hydrocyanic Acid (Prussic Acid) (HCN or HCy).
Iſolecular weight, 27. Molecular Volume, | | | . Specific gravity of
liquid at 44.9° F (7-2°C.) O-7058. Fuses at 5° F (15° C.) Boils
at 79-7° F (26.5°C.).
History.-Discovered by Scheele (1782), who named it prussic acid.
Its composition was proved by Berthollet (1787).
Natural History. It is found in cherry-laurel water (aqua lauro-
cerasi), in bitter-almond water, and in water distilled in contact with
various plants belonging to the N.O. Rosaceae, and with the kernels of
many stone fruits. Its formation in these is no doubt due to the
ferment action of emulsin or synaptase on the amygdalin or some
body of a similar nature (see page 486). It exists, however, ready
formed in the juice of the bitter cassava.
Preparation,-(1.) By passing electric sparks through a mixture
of nitrogen and acetylene.
No + C.H., - 2EICN.
Nitrogen + Acetylene = Hydrocyanic acid.
(2.) Process of B.P. in preparing acidum hydrocyanicum dilutum.
By distilling potassic ferrocyanide with dilute sulphuric acid—
510 HANDBOOK OF MODERN CHEMISTRY.
2K. FeCyå + 3 H.S0, - 6HCN + K.Fe,Cys 4- 8K.S0,
Potassic + Sulphuric = Hydrocyanic + Ferrocyanide of + Potassic
ferrocyanide acid acid iron and potassium sulphate.
The B.P. solution is made to have a specific gravity of 0.997, and
to contain 2 per cent of anhydrous acid; in other words, 100 grains of
the dilute acid should yield 10 grains of AgCy when heated with
argentic nitrate.
(3.) By the action of acids on metallic cyanides (KCN + HCl–
HCN + KCl).
Preparation of Scheele's Acid.—Prussian blue and mercuric oxide
(HgC) are boiled in water, whereby Fe2O, is precipitated, and a solu-
tion of mercuric cyanide (HgCyg) formed. The clear filtrate is then
mixed with dilute sulphuric acid, and shaken up with iron filings
(HgCyc+Fe+H2SO4–2HCy+FeSO4+Hg). The solution contains
4 or 5 per cent. of anhydrous acid.
(4.) By heating together chloroform and ammonia. The process is
facilitated by the addition of an alcoholic solution of potassic hydrate.
CH.Cl3 + NHa = EICN + 3HC1.
Chloroform + Ammonia = Hydrocyanic acid + Hydrochloric acid.
(5.) Preparation of anhydrous acid.—By decomposing argentic cyanide
(gently heated) with sulphuretted hydrogen, or with gaseous hydro-
chloric acid.
2AgCN + H.S = AgaS + 2HCN.
Argentic + Sulphuretted = Argentic + IHydrocyanic
cyanide hydrogen sulphide acid.
Properties.—(a.) Physical. A colorless, highly volatile liquid,
having a bitter almond odor and a bitter taste. It freezes at 0°F.
(–19.8°C.), and boils at 79°F (26.1°C.), emitting a combustible vapor.
The anhydrous acid is so volatile that during its spontaneous evapora-
tion it freezes the rest of the acid. It mixes with water and alcohol
in all proportions. Its physiological action is intense, destroying life
rapidly. It is given in medicine internally, and, when very much
diluted with air, is occasionally used as an inhalation (vapor acidi
hydrocyanici (B.P.)). |
(3.) Chemical. Its acid properties are so feeble that it cannot even
displace carbonic acid from its compounds. Both the pure acid and
the aqueous solution decompose spontaneously (particularly when
exposed to the light), a brown substance called paracyanogen (CN),
being deposited, and ammonic oxalate and formate produced. A trace
of mineral acid, such as is certain to be present in the B.P. acid,
retards the decomposition. [It is worthy of note that when ammonic
formate is heated, it yields hydrocyanic acid and water (CNH4H0.
=CNH+2FI2O)]. It forms with the haloid acids crystalline bodies,
such as (HCN.HCl), etc., which are easily decomposed into formic
acid and ammonic salts (HCN.EICl-i-2H2O=CH2O. (formic acid) +
COMPOUNDS OF CYANOGEN. 511
NH,Cl). It forms metallic cyanides with metallic oxides and
hydrates, but when boiled with an excess of potash it evolves
ammonia.
The Cyanides, Chlorides, and Hydroxides of Cyanogen.
The following constitute the most important of these compounds —
I. Cyanides.

$– º g
cº cº; s $2 >
P-4 r—- --> g
= | ##| | ## ;
$E cº • P. § 3. c:3
3 "E. Sº - E ă,
JO -
Pi— = 2 Ö Q-
-:
ſ Deliquescent; soluble in
water and spirit; fusi-
ble. They are not
Potassic cyanide . . . . KCy 65 White changed by heat when
cubes J air is excluded, but in
\ the presence of air they
Sodic cyanide e = < * NaCy 49 do. become cyanates. Their
solutions, when boiled,
yield formates. Solu-
| tions alkaline.
Ammonic cyanide ... NH,Cy | 44 do. Very soluble ; the solution
easily decomposes.
Mercuric cyanide. . . . . HgCy, 252 do. Soluble in water and alco-
hol; solution not preci-
pitated by alkalies.
Argentic cyanide . . . . . AgCy | 134 do. Insoluble.
Zincic cyanide . . . . ZnCy, 91 do. Do.
Cobaltous cyanide ... CoCy, 111 do. Do.
Palladious cyanide . . PdCy, 158 Yellowish Do.
white
Auric cyanide . . . . AuCys 275 do. Insoluble, soluble in KCy.
Ferrous cyanide . . . . . FeCy, 108 Yellowish Soluble in KCy, forming
& red (KCyAFe"Cys).
Ferric cyanide . . . . . Fe,Cys - Only known in solution.
II. Haloid Salts.
Cyanic chloride (gaseous) . . * & s & ... CyCl.
2 3 (liquid) . . & ºt tº e . . Cy:Cls.
3 * (solid) . . * * * * * ... CyåCls.
Cyanic bromide . . e tº tº a * - ... Cybr.
2 3 tº ſº * e q : * & . . CyåBrs.
Cyanic iodide * { ſº tº * * * * ... CyI.
Cyanic sulphide .. tº # tº e ſº tº ... Cy;S.
III. Hydroxides, Etc.
ſ Potassic cyanate . . ... KCyO.
Cyanic acid. , ... CyOH Ammonic cyanate . . ... NH,Cy0.
. - l Urea . . * * * * ... CHAN,0.
ſ Argentic cyanurate ... AggCyå0s.
Cyanuric acid ... Cy,(), H, Argentic hydric cyanurate Ag, HCyå0s.
l Potassic hydric cyanurate.. KH,Cy;0s.
512 EIANDBOOK OF MOIDERN CEIEMISTRY.
Fulminuric acid ... Cy,0, H.,...Potassic hydric fulminurate K.HCy,0,.
Cyamelide . . ... CyAOAHA
Mercuric fulminate . . ... Hg"Cy,0,.
Fulminic acid ... Cy, H.O., (?) , Argentic fulminate . . ... Ag.,Cy20,.
Ammonic argentic fulminate NH, AgCy,0,.
Ammonic sulphocyanate.. NH,CyS.
Sulphocyanogen ... CNS or CyS or Scy ) Potassic sulphocyanate ... KCyS.
Sulphocyanic acid ... HCyS Plumbic sulphocyanate ... Pb(CyS),.
Mercuric sulphocyanate ... HgCy.S.
The Cyanides.
The cyanides are closely allied to the haloid salts.
Preparation of Metallic Cyanides.
1. By burning the metal in cyanogen gas, or in the vapor of hydro-
cyanic acid (KCy; NaCy).
Ammonic cyanide may be formed by mixing together the vapors
of ammonia and hydrocyanic acid.
2. By acting on metallic oxides or hydrates with hydrocyanic acid:
(a.) HgC) + 2 HCy = Hg"Cy2 + H2O
(3.) KHO + HCy = KCy + H2O.
3. By passing nitrogen over a red-hot mixture of a metallic car-
bonate and carbon –
R2CO3 + 4C + 2N 2KCN + 3CO.
Potassic + Carbon + Nitrogen = Potassic + Carbonic
carbonate cyanide oxide.
-
Thus cyanogen is formed in blast furnaces, the potassic carbonate being
supplied by the ash, and the C and N by the fuel. Ammonic cyanide
may be formed by passing ammonia gas over red-hot charcoal.
4. In the case of potassic cyanide it may be prepared either—
(a) By merely heating potassic ferrocyanide,-
K. Fe"Cyg = 4KCy + FeC., + No.
Hotassic ferro- = Potassic + Carbide of + Nitrogen.
cyanide cyanide iron
(3.) Or, by heating a mixture of potassic ferrocyanide and potassic
carbonate.
K.Fe"Cyd -- K.CO2 = 5ICCy + KCyO + Fe + CO2.
Potassic ferro- + Potassic = Potassic + Potassic + Iron + Carbonic
cyanide carbonate cyanide cyanate anhydride.
[Prepared in this way commercial potassic cyanide usually contains
both potassic cyanate and potassic carbonate.]
If mercuric sulphate be added to the potassic ferrocyanide, mer-
curic cyanide is formed.
5. By the action of a soluble cyanide, or of hydrocyanic acid, on
metallic salts. -
(a.) Thus potassic cyanide, with ammonic chloride, forms ammonic
CYANOGEN. 513
cyanide; with mercuric oxide, mercuric cyanide; with palladious
chloride, palladious cyanide, etc.
(ſ3.) Thus hydro-cyanic acid with zinc acetate, forms zincic cyanide,
etc.
Properties of the Cyanides.—They are all more or less of a white
color, and have a bitter-almond odor. In the case of potassic cyanide,
it evolves an odor of almonds (from the free hydro-cyanic acid
present) and ammonia (from the decomposition of the cyanate by
moisture).
2KCyO -- 4H2O R2COs + (NH4)2CO3.
Potassic cyanate + Water = Potassic carbonate + Ammonic carbonate.
All the cyanides are poisonous bodies.
The alkaline cyanides, when fused in the presence of air, become
cyanates. Acids decompose certain cyanides readily, such as potassic
cyanide (which is even decomposed by carbonic acid), whilst on
other cyanides, as aurous cyanide, they act with difficulty. Most
cyanides are soluble in solutions of the alkaline cyanides, forming
double cyanides. So rapid is this combination in some cases (as with
ferrous and ferric cyanides), that the simple cyanides can scarcely be
said to exist in a separate state.
IJses.—Potassic cyanide is the most important of the cyanides. It
is used (a) in electro-plating and gilding, from its property of dissolving
argentic cyanide, forming with it a compound which is easily decom-
posed with the battery; (3) in photography, from its property of dis-
solving silver, either as a chloride, bromide, iodide, or as the metal;
and (y) in the laboratory, as a reducing agent, from its property of
abstracting oxygen from bodies at a high temperature to form a
cyanate (SnO2+2RCy=Sn+2KCyO).
Cyanogen Chlorides, etc.
Three isomeric chlorides of cyanogen have been described. They
are all the products of the action of chlorine on hydrocyanic acid, or
on a metallic cyanide :-
Gaseous Cyanic Chloride (CyCl=61-5. Mol. Vol. TT ) is a
colorless pungent gas, capable of being liquefied by a pressure of
four atmospheres. It is soluble in water, alcohol and ether. On
being passed into a solution of ammonia in anhydrous ether, it forms
cyanamide CN2H2.
Liquid Cyanic Chloride (CyaCl2=123. Mol. Vol. III) is an
oily liquid, boiling at 59.9° F. (15-5° C.), and freezing at 23° F.
(–5°C.). Preserved in hermetically-sealed tubes for some time, it
assumes the solid modification.
Solid Cyanic Chloride (CyåCls=1845. Mol. Vol. Ti) is a
Crystalline colorless solid. It is soluble in alcohol and ether. It
L L
514 IIANDIBOOIC OF MODERN CHEMISTRY.
melts at 284°F. (140°C.), and at a higher temperature sublimes
unchanged.
This body yields, by distillation, cyanic acid (HCy0), and by the
action of water, its polymer cyanuric acid (H3Cy30s).
The Cyanic Bromides (CyBr and Cyg|Bra), and a solid crystalline
Cyanic Iodide (CyI), have been prepared. By the action of the
latter on sulpho-Cyanate of silver, a Cyanic Sulphide (Cygs) is
formed.
CoMPOUNDS OF CYANOGEN AND HYDRoxy L.
Cyanic acid # tº e iº º & tº a º tº e & CyOH.
Tyanuric acid ... & º ºs & © & * * * Cy30s H3.
Fulminuric acid tº 9 º' tº º º tº tº º Cy30, H3.
Cyamelide s & © * CynO, Hn.
Cyanic Acid (CyOH or CN(OH)=43) and the Cyanates.
(a.) Preparation of the acid.—By the distillation of dry cyanuric
acid (Cy30s H3) into an ice-cold receiver.
(ſ3.) Preparation of the cyanates (M'CNO).-(1.) By the direct oxida-
tion of the cyanides (KCy--PbO-Pb-i-KCNO).
(2.) By the action of cyanogen gas upon potassic hydrate ((CN)2 +
2KHO=KCN + KCNO + H2O). The acid cannot be prepared by the
addition of acids to the salts, inasmuch as it forms, by combination
(a) with water, ammonic carbonate, and (3) with ammonia, urea, or
ammonic cyanate. Thus—
(a.) Cy(OH)+2H2O=NH, HCO3 (ammonic carbonate);
(ſ3.) Cy(OH)--NH3=CH4N2O (urea).
Properties.—Cyanic acid is a colorless, pungent, acid liquid. It
changes rapidly at 32°F. (0°C.) into cyamelide. It is monobasic.
Ammonic Cyanate (NH,CyO); urea (CH,N.0).
Preparation.—(1.) When cyanic acid vapor is mixed with an excess
of ammonia, ammonic cyanate is formed. After a short time by
exposure to air, or immediately at 212°F. (100° C.), the salt under-
goes a molecular change, and becomes urea. (Wöhler.)
(2.) Ammonic cyanate and urea may also be prepared by mixing
potassic cyanate and ammonic sulphate in water, evaporating to dry-
ness, and dissolving out the urea from the residue with alcohol.
2KCyO + (NHA). SO = K.SO, + 2NH,Cy 0.
Totassic + Ammonic F. Potassic + Ammonic
cyanate sulphate sulphate cyanate.
TJrea is a weak base, and constitutes the chief nitrogenised com-
pound of urine. It may be obtained as a nitrate [(CN.H.Q.) HNO3] by
adding nitric acid to concentrated urine. The aqueous solution, when
mixed with Oxalic acid, forms an insoluble oxalate of urea
[(CN.H.O)C.H.O.].
It is decomposed by heat, giving off ammonia, the residue constituting
cyanuric acid.
CYANOG15N. 515
In contact with decomposing matter, urea combines with water and
becomes ammonic carbonate. Hence the presence of the latter in
decomposed urine.
CN.EI,0 + 2B.O (NH)2CO3.
Urea + Water - Ammonic carbonate.
=
A compound where the oxygen of the urea has been replaced by
sulphur, forming what is called sulphur-urea (CN.H.S), has been ob-
tained.
Cyanur ic Acid (Cy3O3H3 or C3N4(OH)3).
Preparation.—(1.) By the action of heat on urea.
(2.) By the action of water on solid cyanic chloride (Cy;C1,4-3H2O
=3|HCl·HCys EI,0s). As water replaces the Cl of cyanic chloride by
the group HO, so phosphorus pentachloride replaces the group HO of
cyanuric acid by Cl, (CANA(OH)3 + 3PC];=C,N3Cl3+3POCl3+3HCl)].
Properties.—It forms colorless efflorescent crystals, which are not
soluble in cold water, but are soluble in boiling (1 in 24). The acid
is very stable, and is dissolved, but not decomposed, by strong sul-
phuric or by nitric acid. In this respect it contrasts remarkably with
its isomer cyanic acid.
It is a tribasic acid, and forms three classes of salts: viz., M's Cy303
(as Ag:CysOs), M.HCyå0s (as Age HCy30), and M'H. CysO3 (as
RH2Cy30s).
Fulminuric Acid (Cy30s Hº Ol' CN3(OH)2).
Preparation.— By the action of a soluble chloride on mercuric ful-
minate.
3Hg"Cy20. --8ICC1-i-H2O = 4KCl–F2HgCl2 + Hg"O+2K.HCysOs
\———' \—y———”
Mercuric Potassic
fulminate. r fulminurate.
Fulminuric acid, unlike cyanuric acid (both of which have the same
composition), is monobasic.
Cyamelide (Cy,O.H., or Cy,(HO),—A white, solid, amorphous
body, formed spontaneously from cyanic acid. It is insoluble either in
dilute acids, in alcohol, in ether, or in water. By dry distillation it
yields cyanic acid.
The relationship of these bodies requires notice :-
1. Cyanic acid may be prepared by heat from cyanuric acid.
2. Ammonic cyanate forms urea.
3. Urea by heat forms cyanuric acid.
4. Cyanic acid changes spontaneously to cyamelide.
5. Cyamelide by dry distillation yields cyanic acid.
Fulminic Acid. This acid has never been isolated. Its probable
composition is H2Cy202. Thus it is polymeric both with cyanic and
with cyanuric acids. It is a bibasic acid.
The fulminates are highly explosive bodies. They are formed by
dissolving the metal in nitric acid and adding alcohol.
516 k HANDBOOK OF MODERN CHEMISTRY.
Fulminate of Mercury (Hg"Cy202) has a specific gravity of 4:4,
and is decomposed either by a temperature of 360°F. (1822°C.), or by
being touched with sulphuric or nitric acid, carbonic oxide, nitrogen,
and the free metal being produced. Thus:–
Hg"Cy20. = Hg + 2CO + N2.
Fulminate of Silver has the composition Ag:Cy202, and is even
more easily decomposed than mercuric fulminate.
Double Fulminates have also been prepared, as, e. g., NH4Ag
CycC., and AgICCy202.
Sulphocyanic Acid (HCNS, or HCyS). This is the sulphur ana-
logue of cyanic acid.
Preparation.—By decomposing lead sulphocyanate suspended in
water, with sulphuretted hydrogen.
Properties.—As prepared above, it is a colorless acid solution, from
which the acid may be obtained as a solid crystalline body by cold.
It is decomposed by boiling, and also by exposure to air. The acid
is monobasic, and forms salts called sulphocyanates.
Ammonic Sulphocyanate (NH,CyS) is prepared by neutralizing
the acid with ammonia, or by digesting hydrocyanic acid with yellow
ammonic sulphide. By its distillation at a high temperature a body
called Melam (C6H5N1) is formed. Melam, by the action of potassic
hydrate and heat, forms Mellamine (C,EIGN6).
Potassic Sulphocyanate (KCyS) is prepared either (1) by fusing
together potassic cyanide and sulphur, or (2) by fusing together three
parts of potassic ferrocyanide, one part of potassic carbonate, and two
parts of sulphur, in a covered crucible. The mass is then lixiviated,
and the salt crystallised from the solution —
R. Fe"Cyg -- S6 = 4KCyS + Fe"(CyS).
By the action of chlorine on a solution of potassic sulphocyanate,
a yellow insoluble precipitate is formed of persulphocyanogen (Cys HSS),
which when heated forms a body called mellone (C6Hs), an organic
radical, which with hydrogen forms an acid called hydro-mellonic acid
(H3C9H13). The salts are called mellonides, as the potassic mellonides
(K3C9H13; K2HC9His and KH2C6Hs). The tripotassic mellonide
yields insoluble precipitates with salts of silver, mercury, lead, etc.,
viz., argentic mellonide (Ag3C, His); mercuric mellonide (Hg (CoHº).);
plumbic mellonide (Pbs(CoEIs)..).
Plumbic Sulphocyanate (Pb(CyS).) is prepared by acting on
potassic sulphocyanate with lead acetate.
Mercuric Sulphocyanate (Hg"(CyS)2) constitutes the toy known
as Pharaoh’s Serpents.
These bodies are represented as containing the compound radical
sulphocyanogen (CyS or Scy).
The selenio-cyanates correspond to the sulphocyanates, and have the
formula (M'CNSe).
DOL BILE CYANIDES. 517
Double Salts, etc., of Cyanogen.
Formula.
Ferrocyanogen Fe"Cyc
Ferrocyanic acid H,Fe"Cys
Potassic ferrocyanide K, Fe"Cys
Cuptic ferrocyanide Cu”,Fe"Cys
Plumbic ferrocyanide * g tº tº º Pb,Fe"Cys
Feltic ferrocyanide (Prussian blue) * † & e 'Fe", Fe",0yrs
Potassic ferrous ferrocyanide (Everitt's white salt) FeF,Fe"Cys
Potassic nickelous cyanide. . K.Ni"Cy, =2KCy, NiCy,
Ferricyanogen Fe"Cy,
Ferricyanic acid H,Fe"Cys
l’otassic ferricyanide R. Fe"Cys
Plumbic ferricyanide º & * * Pººya
Ferrous ferricyanide (Turnbull's blue) Fe", Fe",Cyl,
Potassic ferrous ferricyanide Fe"KFe"Cys
Hydro-nitro-prussic acid H.(NO)Fe"Cy.
Sodic nitro-prusside Na,(NO)Fe"Cy;
Double Cyanides.
These consist of compounds of an alkaline cyanide or a cyanide of
an alkaline earth, with a cyanide of another metal.
Preparation.— By dissolving a cyanide of a heavy metal in an alka-
line cyanide.
Properties.—The double cyanides may be divided into two classes:–
(a.) The unstable double cyanides, which are very poisonous, and are
decomposed by a dilute acid (as HCl), hydrocyanic acid being liberated
from the alkaline cyanide, either with the precipitation of the metallic
cyanide, or with the conversion of both metals into chlorides. Thus :-
K.Ni"Cy, + 2 HCl = NiCy2 + 2KCl + 2 HCy.
Potassic nickelous + Hydrochloric = Nickelous + Potassic + Hydrocyanic
cyunide acid cyanide chloride acid.
(B.) The stable double cyanides, which are not poisonous. They are
not decomposed, like the above, by a dilute acid, but one of the metals
unites with hydrogen to form an acid. Thus:—
R. Fe"Cys + 4HC1 = H,FeCys -- 4KCl.
Ferrocyanide of + Hydrochloric = Hydroferrocyanic + Potassic
potassium acid acid chloride.
The ferrocyanides and ferricyanides are of importance. The pure
cyanides of iron, owing to their strong tendency to form double salts
have never been prepared. -
Ferrocyanogen and Ferricyanogen.—These groups, neither of
which have been isolated, constitute two compound radicals contain-
ing iron, differing from one another only in this, that in ferrocyan-
ogen the iron is bivalent, whilst in ferricyanogen it is trivalent. Thus:–
518 HANDBOOK OF MODERN CHIEMISTRY.
Ferrocyanogen.—Fe"Cyg forms potassic ferrocyanide (K, Fe"Cyg).
Ferricyanogen.—Fe"Cy5 ,, potassic ferricyanide (KaRe"Cyg, or
K6(Fe...)"Cyg).
It will be further noticed that a ferrocyanide differs only from a ferri-
cyanide by one atom of a monad metal (such as K'); hence (a) oridi-
zing agents (as Cl and HNO3) convert ferrocyanides into ferricyanides,
whilst (ſ3) reducing agents (i. e., agents capable of undergoing oxida-
tion or of giving up hydrogen) convert ferricyanides into ferrocyanides.
To express the radical ferrocyanogen briefly, the formula (Fey) is
frequently used.
Analogous to ferricyanogen we have compound radicals, where
the iron is displaced by other metals, as cobalticyanogen (CoCy5),
platinocyanogen (PtCya), etc. These bodies are distinguished by
forming acids with hydrogen, from which salts may be prepared by
the displacement of hydrogen.
Ferrocyanic Acid (H,Fe"Cyg).
Preparation.—(1.) By decomposing plumbic (or cupric) ferro-
cyanide, suspended in Water, with sulphuretted hydrogen.
(2.) By decomposing a strong solution of potassic ferrocyanide
with hydrochloric acid.
R. FeCy5 + 4HCl = H, Fe"Cys -- 4KCl.
Potassic ferro- + Hydrochloric = Hydroferrocyanic + Potassic
cyanide acid acid chloride.
Properties.—A white, crystalline, soluble substance, decomposed by
heat into hydrocyanic acid and ferrous cyanide (H4Fe(Syö–4HCy+
FeCyc), the ferrous cyanide forming Prussian blue by exposure to
air (9PeCyc+O3='Fe", Fe"3Cyås--Fe2O3). The acid is tetrabasic, and
forms salts called ferrocyanides (M'. Fe"Cyg).
Potassic Ferrocyanide.— Yellow prussiate of potash (KAFe"Cyg, or
4KCy, Fe"Cya, or KAPey, or K. Fe(CN)6).
Preparation.—(1.) By the action on potassic cyanide, either (a) of
iron filings, the mixture being freely exposed to the air, or (3) of
ferrous hydrate.
(a.) 6KCy + Fe -- H.O + O = K, Fe"Cy3+ 2KHO.
Potassic + Iron + Water + Oxygen = Potassic -- Potassic
cyanide ferrocyanide hydrate.
(6.) 6KCy + FeH.O. = K, Fe"Cys -- 2KHO.
Potassic + Ferrous F Potassic ferro- + Potassic
cyanide hydrate cyanide hydrate.
(2.) By digesting potassic cyanide, either (a) with ferrous sulphide,
or (ſ3) with a soluble ferrous salt.
(a.) Fe''S + 6KCy = K, Fe"Cys -- K.S.
Ferrous —H· Potassic F. Potassic ferro- + Potassic
sulphide cyanide - cyanide sulphide.
(3.) FeSO, + 6|KCy = K. Fe"Cy5 + K.SO4.
Ferrous -H Potassic F Potassic ferro- + Potassic
sulphate cyanide cyanide sulphate.
DOUBLE CYANIDES. 519
(3.) The ordinary process of manufacturing “yellow prussiate” is
as follows:—Nitrogenised animal matters, such as horns, parings of
hides, blood, etc., are fused with crude potassic carbonate and scraps
of old iron, in covered iron vessels. Thus—(a.) A potassic cyanide is
formed—
ICACOs + C, + N. — ECCN + 3CO.
Potassic + Carbon + Nitrogen = Potassic + Carbonic
carbonate cyanide oxide.
(3.) And also a ferrous sulphide, from the combination of the iron
with the sulphur derived partly from the animal matter, and partly
from the K2SO4 present in the crude potassic carbonate.
The fused mass is now treated with boiling water, when the ferrous
sulphide re-acts (as in process 2 (a)) on the potassic cyanide, forming
sulphide and ferrocyanide of potassium, the separation of the latter
being easily effected by solution and crystallisation (FeS + 6RCy=
K. FeCyc+ K.S). Sometimes, to avoid the formation of potassic
sulphide, pure potassic carbonate is used, and the cyanides formed
afterwards digested with ferrous carbonate:—
IFeCOs + 6|KCy = RAFe"Cys + IC,CO3.
Ferrous + Totassic - Potassic + Potassic
carbonate cyanide ferrocyanide carbonate.
Properties.—It forms large, tough, yellow crystals (K, FeCy5+
3H2O), soluble in both cold and hot water (1 in 4 at 60°F.; 1 in 2 at
212°F), and insoluble in alcohol. It is not poisonous.
At a moderate heat the yellow salt becomes white and anhydrous.
IIeated intensely in air, it forms potassic cyanate ; but heated without
air it forms potassic cyanide, carbide of iron, etc.
With dilute sulphuric acid, it yields hydrocyanic acid, but with strong
sulphuric acid, the salt is decomposed (KAFe"Cyc+6H2SO4+ 6H2O=
6CO+FeSO4+2IC..SO,--3 (NH4)2SO)]. By the action of hydrochloric
acid, hydroferrocyanic acid is precipitated (HAFeCy5).
IFused with alkaline carbonates, it forms potassic cyanide.
With neutral or acid solutions of many metallic salts, it gives
characteristic precipitates. With ferrous salts, it forms a light blue
potassio-ferrous ferrocyanide (Fe"K.Fe"Cyg); with ferrie salts, ferric
ferrocyanide or Prussian blue ('Fe"; Fe"3Cyls); with cupric salts, a
red cupric ferrocyanide (Cu". Fe"Cyg); with lead salts, a plumbic
ferrocyanide (Pb2FeCyg), etc.
The precipitate with cobalt, is yellowish green ; with uranium,
brown; and with zinc, cadmium, nickel, manganese, tin, lead, bismuth,
antimony, silver, and mercury, white. Except the precipitates with zinc
and cadmium, they are all insoluble in dilute hydrochloric acid.
Uses.—It is largely used in the manufacture of Prussian blue (see
page 521), in the preparation of hydrocyanic acid (see page 509),
etc.
520 EIANDIBOOK OF MODERN CHEMISTRY.
Ferricyanic Acid (HAFeCyg).
Preparation.—By decomposing plumbie ferricyanide (Pb,Fe".Cylº),
suspended in water, with sulphuric acid.
Properties.—A red unstable liquid. By heat, it forms hydrocyanic
acid and a hydrated ferric cyanide (Fe2Cyg,3H2O).
Potassic Ferricyanide,-Red prussiate of potash (KAFe"Cyc, or
3RCy, Fe"Cy3, or K6(Fe2)YiCylo).
Preparation. By the action of an oxidizing agent (such as nitric
acid, chlorine, etc.,) on potassic ferrocyanide :-
2(K, Fe"Cyg) + Cl3 = 2(KAFe"Cyg) + 2KC1.
Potassic + Chlorine -: Potassic + Potassic
ferrocyanide ferricyanide chloride.
The chlorine withdraws one-fourth of the potassium from the ferro-
cyanide. The chlorine must not be used in eaccess, otherwise the salt
will be decomposed.
Properties. A red crystalline salt, permanent in the air, and
soluble in water (1 in 4 at 60°F.)
It is decomposed by reducing agents.
Its re-actions are important :
1. It forms insoluble precipitates of characteristic color with many
metallic salts in neutral or in feebly acid solutions; e.g., an orange pre-
cipitate with zinc or silver; a yellow, with cadmium ; a green, with
nickel and copper; a reddish brown, with cobalt ; a brown, with man-
ganese; a white, with stannous salts, etc.
Excepting those of zinc and tin, the ferricyanides of the above
metals are insoluble in dilute hydrochloric acid.
2. (a.) With a ferric or persalt of iron (that is, where the iron is
really a hexad, although apparently trivalent, as in (Fe2)"Cl6, it gives
no precipitate, but merely turns the solution a reddish brown color.
(3.) With a ferrous or protosalt of iron (that is, where the iron is
bivalent, as in Fe"Cl2) it gives a deep blue precipitate of ferrous
ferricyanide, Fe", Fe".Cy12-i-Aq, which, when dried, constitutes “Turn-
bull's blue.” -
[Non-E.-Potassic ferrocyanide forms a blue precipitate (Prussian
blue) with ferric salts, but not with ferrous salts, potassic ferricyanide
constituting the test for iron as a ferrous salt, in which case a blue
precipitate is formed. To distinguish Prussian blue (ferric ferro-
cyanide, 'Fe", Fe",Cyia) from Turnbull's blue (ferrous ferricyanide,
Fe", Fe". Cylo), add potassic hydrate :-with Prussian blue we obtain
potassic ferrocyanide, and ferric or red owide of iron (Fe2O3); whilst
with Turnbull’s blue we obtain potassic ferrocyanide and magnetic
or black owide of iron (Fe3O4).]
3. The ferricyanide is used in dyeing, a fabric being colored blue
when boiled in a solution of the salt acidulated with acetic acid.
Mixed with potassic hydrate it forms, as an oxidizing agent, a
discharge for indigo. Thus :—
T)OTBLE CYANIDES. 521
2(R, Fe"Cyg) + 2KHO = 2(K, Fe"Cyg) + O + H2O.
Potassic ferri- + Potassic = Potassic ferro- + Oxygen + Water.
cyanide hydrate cyanide
The Nitro-prussides.—Preparation.—By the action of nitric acid
on the ferro- or ferri-cyanides.
Hydro-nitroprussic acid, H2(NO)Fe"Cys, has been prepared in a crys-
talline form.
The sodic nitroprusside (Na2(NO)Fe"Cy3+2aq) is the only salt of
importance. -
Preparation.—Potassic ferrocyanide is boiled with dilute nitric acid
until a ferrous salt added to the solution gives a slate-colored precipi-
tate. It is then boiled with an excess of sodic carbonate, and the
solution filtered and crystallized.
Properties.—It is a brilliant red crystalline (rhombic) body. The
soluble nitroprussides produce a purple color with a mere trace of an
alkaline sulphide. -
Constitution.—The nitroprussides may be regarded as containing a
radical similar to ferrocyanogen (Fe"Cyg), where one of the monatomic
radical (NO) has replaced one of Cy.—(Fe"(NO)Cys). This radical is
diatomic, inasmuch as Cyc of the group remains unsaturated.
Ferric Ferrocyanide (Prussian Blue), Fe", Fe",Cyls or Fer
Cyla or 3 Fe"Cya,2'Fe". Cys, or 2CRed)"Cyg,3Fe"Cy2+ 18H2O).
History.—It was discovered about 1700. Its true nature was not
at first understood. Macquer (1724) discovered that it was decom-
posed by an alkali, a residue being formed of red oxide of iron.
Hence he supposed it must be a compound of oxide of iron with an
acid, but which acid had a greater affinity for an alkali than it had
for oxide of iron. This view was supported by the fact that when
a salt of iron was added to the solution, prussian blue was re-formed.
Scheele, in 1782, prepared the acid which he called prussic acid. Gay
Lussac, in 1815, called prussian blue prussiate of iron.
Preparation.—(1.) By the action of potassic ferrocyanide on ferric
salts.
3K, Fe"Cyg -- 2Fe2Cl6 = Fe", Fe",Cyls + 12KCl.
Potassic ferro- + Ferric chloride = Ferric ferro- + Potassic
cyanide cyanide chloride.
[This precipitate forms what is commercially known as soluble
prussian blue, the precipitate being soluble in pure water.]
(2.) By the action of a mixture of ferrous and ferric salts on
potassic cyanide. (This constitutes the principle of Scheele's test for
HCN. (See page 522.)
3 Fe"Cl2 +2'Fe",Cls + 18FCCy = 18.RCl + 'Fe", Fe",Cyls.
Ferrous + Ferric + Potassic = Potassic -i- Prussian
chloride chloride cyanide chloride blue.
(3.) By the action of oxidizing agents, such as air, nitric acid,
522 TIANIDIBOOIC OF MOIDERN C [IFMISTRY.
chlorine, etc., on the light blue precipitate of potassic ferrous ferro-
cyanide (Everitt’s white salt = Feka, FeCyg) produced when ferrous
salts are precipitated with potassic ferrocyanide.
(a.) K.Pe"Cyd -- FeSO, E= Feſ. FeCyg + K.S.O.
Potassic ferro- + Ferrous = Potassic ferrous + Potassic
cyanide sulphate ferrocyanide Sulphate.
(3) 6(Feka, Fe"Cyg) + 3O2 =3(K, Fe"Cyg)+ Fe2O,--'Fe", Fe",0ys
Potassic +Oxygen = Potassic + Ferric + Prussian
ferrous ferrocyanide ferrocyanide oxide blue.
[This process is ordinarily employed in the manufacture of
prussian blue. The prussian blue made in this way, however, is not
so pure as that prepared by process 1, the pigment being always
more or less mixed with potassic-ferrous-ferricyanide (Fe"K, Fe"Cys),
which has also a blue color, and which, it will be seen, differs only
from the potassic-ferrous-ferrocyanide by the loss of one potassium
atom.]
Properties.—Prussian blue is a hard, blue, and brittle substance,
without taste or odor. It is largely used as a pigment, but its
color is not of a very permanent nature. That prepared by process 1
is soluble in pure water; that by process 3 is insoluble. Heated in
air, it burns freely, leaving a residue of Fe2O3. Heated without air,
it gives off water, ammonic cyanide and ammonic carbonate, a carbide
of iron remaining as a residue.
It is insoluble in dilute acids, except in a solution of oxalic acid,
this solution forming blue ink; strong sulphuric acid turns it white,
the color being restored on dilution with water. It is decomposed by
strong nitric and hydrochloric acids. Alkalies and alkaline carbonates
destroy the color, dissolving out a ferrocyanide, and leaving ferric
oxide.
'Fe", Fe",Cyla-- 12 RHO= 3K, Fe"Cyg -- 2Fe2O3 + 6H2O.
Prussian + Potassic = Potassic ferro- + Ferric oxide + Water
blue hydrate cyanide
[Thus the calico printer in forming a pattern on a fabrig dyed with
prussian blue, first discharges the color with an alkali, and them dis-
solves the ferric oxide formed with a dilute acid.]
(1.) Tests for hydrocyanic acid and the cyanides.
(a.) The odor of prussic acid. º
(3.) Argentic Nitrate; gives with the acid a white precipitate of
argentic cyanide (AgCy), insoluble in nitric acid, and soluble in
alkaline cyanides; almost insoluble in ammonia. By this means, and
also by its not being readily blackened on exposure, AgCy may be
known from AgCl.
The argentic cyanide when heated evolves cyanogen, which burns
with a rose-red flame, reduced silver only remaining in the tube.
(y.) (Scheele's Test.) Add to the acid a few drops of a solution of
FLYI)]&OCYANIC ACID. - 523
potassic hydrate. Thus a potassic cyanide is formed (HCN+KHO=
KCN + H2O). Add to the KCy solution, a mixture of a ferrous and
ferric salt (such as ferrous chloride and ferric chloride). The ferrous
salt converts the cyanogen into ferro-cyanogen (FeCyg), which com-
bines with the iron of the ferric salt to form prussian blue (18ECy--
3FeCl2 +2Fe2Cl6=18]{Cl-i-FezCya). Now add dilute sulphuric acid,
to re-dissolve any excess of the ferrous and ferric hydrates precipitated
by the excess of potassic hydrate, the result being that pure prussian
blue will be precipitated.
In dilute solutions the reaction is slow.
[Thus in hydrocyanic acid poisoning, a mixture of solutions of sul-
phate of iron, perchloride of iron, and potassic hydrate, constitutes
the best antidote.]
(6.) Mercurous Nitrate; a grey precipitate of metallic mercury,
mercuric cyanide remaining in solution.
(e.) Place some hydrocyanic acid, or a mixture of a cyanide and
hydrochloric acid in a watch-glass. Invert over this a second watch-
glass, moistened with a few drops of yellow ammonic sulphide, in
such manner that the sulphide may be freely exposed to the vapor
of the acid. Heat very gently to dryness. Thus an ammonic sulpho-
cyanate (NH,CNS) is formed :-
(NH4)2S + S. -- 2HCy = 2NH,CyS + H.S.
\— ~~-—”
Yellow ammonic + Hydrocyanic = Ammonic sulpho- + Sulphuretted
sulphide acid cyanate hydrogen.
This residue, when touched with a ferric chloride solution, yields the
blood-red color of ferric sulphocyanate.
JEstimation of Hydrocyanic Acid.—1. Argentic nitrate is added to
a known quantity of the solution, and the argentic cyanide formed
collected and weighed.
100 grs. of AgCN=19.4 grs. of CN, or
=48-57 grs. of KCN.
2. Supersaturate a hydrocyanic acid solution with potash, and add
a few drops of a solution of common salt. Add to this a nitrate of
silver solution of known strength. Immediately that a permanent
precipitate of AgCl occurs, it proves that all the HCN present in the
solution has been converted into the soluble double salt KCyAgCy,
the combination of the chlorine with the silver not occurring until
this is complete. (Every 170 of AgNO3 corresponds to 26 of cyanogen,
and to 65.1 of KCy).
(2.) Tests for the Ferrocyanides :
Ferric salts; a blue ppt. of Prussian blue ('Fe", Fe"3Cys).
Cupric salts : a red ppt. of cupric ferrocyanide (Cu". Fe" Cyg).
524 HANDBOOK OF MODERN CHEMISTRY.
(3.) Tests for the Ferricyanides : '
Ferric salts; no ppt., but merely a reddish-brown solution formed.
Ferrous salts; a blue ppt. of ferrous ferricyanide (Fe's Fe", Cyg).
(4.) Tests for the Sulphocyanates (Sulphocyanides):
Ferric salts give a blood-red coloration from the formation of
ferric sulphocyanate.
(5.) Tests for the Nitroprussides :
Alkaline sulphides give a purple color.
525
CEIAPTER XXII.
TEIE HYDROCARBONS.
SERIES OF HYDRocARBONs.—The Paraffins—Chloroform—The Olefines—Acetylene-
Turpenes—Benzenes—Naphthalene —Anthracene —Formation of Alizarene.
SUPPLEMENT.-Paraffin and Petroleum—T urpentine–Volatile Oils—Camphors—
Resins—Gum Resins—Oleo-Resins—Balsams—India Rubber—Gutta Percha.
THE HYDR00ARBONS.
It will assist us if, before considering the hydrocarbons in detail,
we note the following facts : —
1. Carbon is a tetrad element. When combined, therefore, with four
monad atoms (as in CH4), it is regarded as fully “saturated.”
2. Although, however, the carbon in CH4 is fully saturated, and is
therefore incapable of further combination, nevertheless it can ex-
change one or more unit weights of its hydrogen for an equivalent
quantity of some other element. Thus CH4 can form CH3C1 or
CH2Cl2. These substitution compounds with the halogens are called
haloid derivatives. Again, it can exchange its hydrogen for a monad
group, such as (CN)' (NO2)" (NH2)', etc., and thus form other deri-
vatives, as CH3(CN)', etc.
3. Again, carbon has the property of uniting with itself (duplication).
Whenever this occurs its atom-fixing power is increased by at most
two monad units; thus—
1C can unite with 4 unit weights of hydrogen, etc., to form = CH,
2C 3 * ,, 6 3 y y y 5 y = C, Hs
3C 5 y 5 y 8 32 3 y 33 - Cs Bis
This fact has been already represented graphically (see page 366).
A series where the members or terms of the series, as they are
called, increase by a regular increment of CH2, is called an homologous
series. All the members of the series described above are fully
Saturated.
4. If a saturated hydrocarbon, as CHA, be deprived of a molecule of
hydrogen (H2) a molecule is left (CH3), which is “not saturated,”
and gives rise to a new homologous series, all the members of which
are also non-saturated molecules; as follows:—
CH2—C.EIA-CSFI6—C4Hs, etc.
These non-saturated hydrocarbons, however, are able to unite with
other elements or compound radicals to form saturated compounds.
526 HANDIBOOIK OF MODERN CHEMISTRY.
5. By an isologous series, we imply a series in which the successive
terms differ by Hz; thus the series
Ethane ... tº º º * & e gº tº º ... C. H6
Ethene (Ethelene) Q & e tº º tº ... CºEIA
Ethine (Acetylene) * g is tº £ tº ... C.FIg, etc.
constitute an isologous series.
6. Hydrocarbons of even equivalence (such as those with the for-
mula CAH2n+2, as CH4) may exist separately, whilst hydrocarbons
of unequal equivalence (as CH3 methyl) are incapable of existing in
the free state, unless perhaps as double molecules, i.e. | §-CH,
3
7. A hydrocarbon containing an even number of hydrogen atoms
has been regarded as a hydride of a radical, containing an uneven
number of hydrogen atoms. Thus methane (CHA) may be regarded
as a hydride of methyl (CH3.H), ethane (C.Hg) as a hydride of ethyl
(C2H5.H), etc. The groups CH3, C.H.3, etc., are called either “hy-
drocarbon radicals,” or, for reasons to be seen directly, “alcohol
radicals.”
It must, however, be remembered that there is no reason to believe
that one of the hydrogens of the body CH1, plays a different part in
the compound to the other three. Experiment, indeed, is opposed to
such a view.
8. (a.) An alcohol is a hydrocarbon in which one or more atoms of
hydrogen have been replaced by one or more of the group (OH).
An alcohol may be regarded as the organic analogue of a metallic
hydrate, such as Na (OH). Thus
Methane CH, forms methylic alcohol CH3(OH);
Ethane C2H6 , , ethylic alcohol CºEI5(OH); etc.
(3.) A thio-alcohol or mercaptan is, in like manner, the organic
analogue of a metallic sulphydrate, as Na (SH); thus
Methylic sulphydrate CH3(SH); Ethylic sulphydrate C.H.4 (SH).
9. (a.) An owygen ether is a compound of hydrocarbon radicals and
oxygen. It may, therefore, be regarded as an alcoholic oacide or anhy-
dride. It will be remarked that the relationship of Na(OH) to
Na2O is an analogous relationship to that existing between an alcohol
and an ether. Thus— -
Sodic hydrate Na (OH) and Sodic oride Na2O correspond to
Ethylic alcohol C.H.4 (OH) and Ethylic ether (C2H5).O.
(3.) In a sulphur (thio-ether) or selenium ether, the analogues
of metallic sulphides or selenides, the O is replaced by S or by Se; as,
e.g., (C2H5)2S.
10. An aldehyde is a hydrocarbon where the hydrogen is replaced
by the group (COH)'. Thus:–
CH.H methane yields CH3(COH) acetic aldehyde.
PTYIDPOCARIBONS.
527
It may be remarked here that an aldehyde is produced by the
oxidation of an alcohol, and an acid by the oxidation of an aldehyde.
Thus an aldehyde stands midway between an alcohol and an acid.
Thus : —
Ethylic alcohol
C.B.O
Acetic aldehyde
— C2H4O2.
— Acetic acid.
11. A ketone is an aldehyde where the H of the group COH in the
aldehyde, is replaced by a monad hydrocarbon group. Thus:—
the group carboxyl (CO.OH)'. Thus:–
CH, ; CH3(COOH) —
Methane ; Acetic acid
CH3(COH) —
Aldehyde
CH2(CO(CHA).
— Dimethyl ketone.
The ketones differ from the aldehydes in the products of their
oxidation.
12. An acid is a hydrocarbon where the hydrogen is replaced by
C. He
— Benzene
; C6H3(COOH).
; Benzoic acid.
The acids may be regarded, therefore, as oxidized alcohols and
aldehydes.
Series of Hydrocarbons.
We have to consider the following series of hydrocarbons :—

SERIES.
Formula of Series.
Examples.
II.
III.
IV.
V.
WI.
VII.
VIII.
. Marsh gas (paraffins) . .
Olefines
Acetylene
Terpenes
Benzenes
(Aromatic series.)
Cinnamene
Naphthalene .
IX.
X
. Anthracene
XI.
XII.
XIII
. Chrysene
XIV.
XW.
CaFIgn + 2
CnH2n
CnH2n-2
CnH2n-.
CnH2n-6
CnH2n-s
* In
n
| Methane CH,
| Ethane C.Hs,
| Ethylene C, H,
| Propylene C, Hs,
| Acetylene C.H.,
| Allylene C, H,
Quintone C, Els
Decone CiołIns
\ Benzene CeBIs
| Toluene C, H,
| Cinnamene CSFI's
| Allylbenzene Caſſio
Acetenylbenzene CHs
Naphthalene Cho Hs
Diphenyl Cls. His
Anthracene C1, Huo
Stilbene C, H,
Diacetenyl-benzene Cls Hio
Chrysene Cls His
Tetraphenylethylene Cºs Hºo
Respecting these series we would note generally that—
1. The 2nd and 3rd series (viz., the olefine and acetylene series)
may be obtained from the 1st series (the paraffins) by similar opera-
Further we note that the paraffins do not form additive
tions.
528 HANDBOOK OF MODERN CHEMISTRY.
compounds with the haloids, but that the 2nd and 3rd series do,
whereby they are rendered compounds of a similar constitution to the
paraffins. Thus : —
ſ a substitution
C2H2 forms C2H2Cl4 l derivative Of ſ C2H6
Acetylene Tetrachlorethane Ethane.
2. The paraffins are in all respects a singularly inert class of
bodies.
3. The 1st, 2nd, and 3rd series do not form nitro-derivatives or
sulphonic acids.
4. The “terpenes" (Series IV.) are a very stable group. They
have a peculiar action on polarized light, and combine readily with
the haloids, but they yield neither nitro derivatives nor sulphonic
acids.
5. The benzenes (Series W.), or aromatic series as they have been
called, and with them Series VIII. and X., form additive compounds
with difficulty, but substitution derivatives with ease, these latter being
stable bodies, and not decomposed in some cases even by fusion with
potassic hydrate. The benzenes form nitro-compounds and sul-
phonic acids by their direct union with nitric and sulphuric acids, by
which they may be distinguished from all the preceding, but not from
the succeeding series.
6. The naphthalene, anthracene, chrysene and pyrene series of
hydrocarbons, form by oxidation “quinones,” that is, bodies where
two units of hydrogen are replaced by two units of oxygen.
Marsh Gas Series, or Paraffins.
SERIES I.-Formula CaF2n+2.
Boiling point. Sp. Gr. at
NAME. |Formula F C deg. Cent. Remarks.
Methane CH, See page 228.
Ethane C2H6 Ethylic hydride C.H.H.
Propane C3He o o
Tetrane C.H., | 33-8 1 '600 at 0° | Diethyl (C.H.),
Pentane C.H., 100-4: 38° •628 at 17°
Hexane C.H. 1580 | 70° • 669 at 16°
Hºptºne ... ºff. . . . . . . .
CU8lD.6) C.H. 55.2° $ ). A Q *726 at 15 * . Îl, , )., .
º, (ii. 298.4° 148° • 728 at 13° Dibutyl (C.H.),
Decane C.H. 334.4° | 168° • 739 at 13°
Undecane ... C, H., 363'2" | 184 •765 at 16°
Dodecane . . . C. H. 395'6" | 202 •774 at 17°
Tridecane . . . C. H. 424'4" | 218. •792 at 20°
Tetradecane || C. H. 464-0 || 240 -----
Pentadecane | C. H. 505'6" | 262. •825 at 16° & o TT / ) 1 O ſº \
Hexdecane. . . C.H. 532'4" | 278° Solid–melts at 69.8°F. (21°C.)
The above table represents the gravities and boiling points of
MARSH GAs. 529
the normal primary paraffins. Several isomeric modifications of many
of these bodies have been prepared, but not of the first three mem-
bers of the series, viz., methane, ethane or propane. These isomers
are prepared differently, have different gravities and boiling points, and
exhibit different reactions. It is customary and convenient to express
these varieties by different formulae, although such expressions must be
regarded as merely theoretical, and not in any sense representations
of actual molecular construction.
Thus the first three terms of the series have no isomers, and however
prepared, exhibit the same chemical and physical properties. They
may be represented thus:—
CH,
CH,
CH, CH2
CH,
CH:
Methane. Ethane. Propane.
These, indeed, are the only ways in which it is possible to group
the carbon atoms of these bodies. The fourth term C, Hio is derived
from the third term by the replacement of one hydrogen atom by the
group CH3. But this displacement of hydrogen may occur in one
of two places ; i.e., either in one of the end CH3 groups, or in the
centre CH2 group; that is in one case, none of the carbon atoms may be
united with more than two carbon atoms, whilst in the second case
one of the carbon atoms may be directly combined with three carbon
atoms. Thus it may be represented as—
(1.) (CH3CH.C.H.CHA), or as (2.) (CH3CH(CH3). CH3).
We may express these two forms graphically thus—
H H H H H H H
| |
H–C– 6–4–3– n-º-º-º-H
| | | | | |
H H H H H H
H–C–H
|
H
No. 1. No. 2.
Or again we may have such isomeric compounds as the following:—
CH, CH, CH, CH,(OH) = Normal butylic alcohol.
CH(CHA). CH3(OH) = Iso-primary do.
C(CH2)(C.H.) H.OH = Secondary do.
C(CH3)3(OH) = Tertiary do.

It has been shown that all these various isomers (and it is evident
that the number of isomers will increase with the advance of the
series) may be represented under four heads:-
IM M
530 HANDBOOK OF MODERN CHEMISTRY.
(1.) Where each carbon atom is at most associated with two carbon
atoms (No. 1 as figured on last page).
(2.) Where one carbon atom is associated with three carbon atoms (No.
2 as figured on last page).
(3.) Where such group (i.e., of one carbon atom being associated with
three carbon atoms) occurs twice in a molecule, as e. g.—
CH, CH,
| |
H–C C EI
| |
CH, CH,
No. 3.
(4.) Where one carbon atom is associated with four other carbon atoms,
as e. g., in-
CH,
|
CH.H.C–C–CH2.C.H.,
CH,
No. 4.
Similarly it must be noted that various isomers of the derivatives
of the paraffins also result from the displacement taking place in
different groups. Thus—
CH3.C.H.C.H.I = propyliodide (a-iodopropane).
CH3.CHI.CHs = iso-propyliodide (3-iodopropane).
Preparation of the Paraffins,—(General.)—1. From the alcohols
of the C, H2n+10B. Series. These are first (a) converted into mono-
chlorinated, etc., paraffins by the action of a haloid acid, and after-
wards (3) submitted to the action of nascent hydrogen. These re-
actions will be noted in the preparation of ethane;
t
(a.) C.H.3(OH) + HCl = (C.Hs)C1 + H2O.
Ethylic alcohol + Hydrochloric acid = Ethylic chloride + Water.
(3.) (C2H5)Cl. -- He = C.H.S + HCl.
Bthylic chloride + Hydrogen = Ethane + Hydrochloric acid.
2. By the action on the alcoholic iodides, either (a), of zinc and
water, or (3), of zinc alone and heat, in closed vessels.
(a.) 20:HgI + Zn2 + H2O = ZnH2O2+ ZnT3 + 2C.H6.
Ethylic + Zinc + Water = Zincic + Zincic + Ethane.
iodide hydrate iodide
(ſ3.) 2C2H5T + Zn = ZnT3 + Cº.LIlo.
Ethylic iodide + Zinc = Zincic iodide + Tetrane.
MARSH GA8, 531
*
3. From the acetic series of acids by electrolysis.
+ sºms:
- r ~\— Y 2–’—
2C2H4O2 - C2H6 + 2CO, + H2.
Acetic acid = Ethane + Carbonic anhydride + Hydrogen.
4. From the acids (a) of the acetic series, and (3) of the succinic series,
by the action of alkalies on their alkaline salts.
(a.) KC.H.O., + KHO = K2CO3 + CH4.
Potassic + Potassic – Potassic + Methane.
acetate hydrate carbonate .
(6.) K.CaFII30, + 2ECHO - 2K2COs + C6H14.
Potassic + Potassic = Potassic + Hexane.
suberate hydrate carbonate
General Properties.—(a.) Physical. The viscidity of the paraffins
increases with their molecular weight, the members of the series be-
coming gradually less volatile and of higher gravity. Thus the first
three terms are gaseous, those next in order are liquid, whilst the
final terms are solid.
(ſ3.) Chemical. Chlorine, and bromine to a less extent, act directly
on the paraffins under the influence of sunlight, to form substitution
products, which may be partial or complete. Iodine forms no such
compounds directly, but it forms them indirectly. Thus it forms
iodoform (CHIs) by its action, in the presence of potassic hydrate, on
various Organic substances, such as sugar, alcohol, etc.
When chlorine acts on the normal primary paraffins, it forms simul-
taneously two isomeric derivatives, differing in their boiling points
and in their specific gravities, and convertible respectively into a
normal primary and a normal secondary monohydric alcohol. One
or two illustrations will suffice :-

Boiling pt. of Derivative. Specific Gravity,
(a.) (3.) at 8 C.
• F. 9 C. 9 F. ° C. (a.) (8.)
CH,Cl . . . . . .
C.H.C. . . . . . . 54-5 | 12:5 920 at 0°
C.H.Cl . . . . . . 115-7 || 46-5 || 102-2 || 39 915 874 at 10°
C, H,Cl . . . . . . 171.5 77.5 | 158-0 || 70 907 895 at 0°
C.H. Cl. . . . . . . 223-7 || 106.5 231-8 111 901 SS6 at 0°
With nitric acid the higher paraffins form directly nitro-compounds,
whilst on the lower terms of the series, nitric acid has no such action,
although nitro-compounds may be produced by indirect means.
Some of the more important substitution derivatives of the
paraffins are stated in the following table:—
532
HANDBOOK OF MODERN CHEMISTRY.

Name. Formula.
Methylic chloride.. CH,Cl
(Monochloromethane) -
Methylene chloride CH,Cl,
(Dichloromethane)
Chloroform . . . . . . CHCl,
(Trichloromethane) .
Carbonic Tetrachloride. CC1,
(Tetrachloromethane)
Iodoform * * * CHI,
(Triiodomethane)
Nitro-methane CH,(NO.)
Nitro-ethane. . C.H.(NO.)
Cyano-ethane or Ethyl || C.H.(CN)
cyanide
Cyanomethane or Me- CH,(CN)
thyl cyanide
Preparation and Properties.
Preparation.--(1.) By the action of Cl on CH, in
diffused light. t
(2.) By the action of HCl gas on methylic alcohol.
Properties.—A colorless gas, condensing at —4°F.
(—20° C.).
Preparation.—By the action of C1 on CH,Cl in
Sunshine.
Properties.—A colorless liquid; specific gravity,
1:36; boils at 107.6° F. (42°C.).
See below.
Preparation.—(1.) By the action of chlorine on
chloroform in sunlight.
(2.) By the action of Cl on warm CS2.
Properties.—A colorless liquid; specific gravity,
1:6; boils at 172.4° F. (78° C.).
By the action of nascent hydrogen it may be suc-
cessively reduced to CH1.
Preparation.—By the action of iodine on alcohol,
etc., in the presence of potassic hydrate.
Properties.—A yellow crystalline body, soluble
in alcohol and in ether. It forms cyanoform,
2CH(CN), when heated with mercuric cyanide.
Preparation.—By the action of argentic nitrate on
methylic iodide (CH, I-H AgNO3=AgI+CHA
NO.).
rºa. An oily liquid; boils at 210-2° F.
(99° C.). Forms with NaHO the derivative
CH,Na(NO.).
Preparation.— By the action of argentic nitrate on
ethylic iodide.
Properties.—A colorless liquid; boils at 235-4° F.
(113° C.). By the action of nascent hydrogen,
forms ethylamine.
When methyl or ethyl iodide is heated with ar-
gentic cyanide, two isomeric ethyl or methyl
liquid compounds are formed:—
Ethyl compounds (1.) boils at 1913° F (88.5° C.);
no odor.
37 (2) boils at 174.2°F. (79° C.);
intolerable odor.
Methyl compounds (1.) boils at 170-6°F (77°C.);
not acted on by acids.
3 y (2) boils at 131° F. (55° C);
decomposed by acids.
Trichloromethane (Chloroform).
Terchloride of formyle; methenyl
chloride; dichlorinated methylic chloride (CHCl3).
Molecular weight, 119°5.
Specific gravity, l'48.
Boils at 141.8° F.
(61.0°C.). Vapor density (air=1) 4:20.
Preparation.—(1.) By the action of chlorine on methane.
(2). (Commercial method.) By distilling together 1 part of alcohol
(wood spirit being sometimes employed), 6 parts of chloride of lime,
and 24 parts of water.
The distillate consists of water and chloroform,
OLEFINES. - 533
which, on standing, separates into two layers, the water being above,
and the chloroform below. The exact reaction is doubtful. Pro-
bably (a) chloral is formed in the first stage, and (3) in the next stage
is decomposed by the calcic hydrate; thus—
(a.) C, H2(OH) + 4Cl. = 5HCl + CC1,COEI.
Alcohol + Chlorine = Hydrochloric acid + Chloral.
(3.) 2001,COH+ CaFI.O. = Ca"(CHO.), + 2CHCl2.
Chloral + Calcic hydrate = Calcic formate + Chloroform.
The chloroform is afterwards purified from certain oils that distil over
along with it, by being shaken up with oil of vitriol, on which the
chloroform floats. It is then drawn off from the acid and again
distilled.
Properties.—(a.) Physical. A colorless liquid, having a fragant odor
and a sweet taste ; specific gravity, 1:48. It is insoluble in water.
(6.) Chemical. Chloroform burns with difficulty with a greenish
flame. Sulphuric acid has no action upon it; boiled with nitric acid
it forms chloropicrin (nitrotrichloromethane) [C(NO2)Cls], a colorless
liquid, having a specific gravity of 1-6, and boiling at 233.6° F.
(112°C.). Boiled with a solution of potassic hydrate it forms potassic
chloride and formate (CHCl3+4KHO=3KCI+CHO(OK)+2H2O).
When heated with potassium amalgam, acetylene (C2H3) is set free.
Distilled in a current of chlorine, it forms CC13,
Uses.—As an anaesthetic. For dissolving caoutchouc, and for ex-
tracting the alkaloids from organic matters.
(See SUPPLEMENTARY CHAPTER.)
The Olefines.
SERIES II.-Formula CAH2n.
The following hydrocarbons of this series have been obtained :-

Melting point. Boiling point.
|Formula
• F. °C. °F. °C.
Ethylene (ethene). . . C.H., \ See page 229.
Propylene (propene) CaFIs —0°4 —18
Butylene (quartene) CAHs 33-8 l
Amylene (quintene) CsPilo 95 35 A colorless liquid.
Hexylene (sextene) CSEIts 149 65
Heptylene (Septene) C.His 204.8 96
Octylene (octene) ... CsPils 248 120
Nonylene (nonene) CºHts 284 140
Diamylene (decene) Ciołlso 320 160
Triamylene ... Cistiao 482 250
Cetene (sexdecene) | ChełIsa 527 275
Tetramylene . CºoHºo 752 400
Cerotene. . . . C.H., (134°6 57 (?)
Melene .. C.Hºo 143-6 || 62 707 375 (?)
534 HANDBOOK OF MODERN CHEMISTRY.
Preparation of the Olefines (General.)—1. From the alcohols of
series C. Han-e OH. By abstracting the elements of water by dehy-
drating reagents, such as Sulphuric acid. Thus:–
C.H.OH - C.H., + H.O.
Ethylic alcohol - Ethylene + Water.
2. From the paraffins. (a.) By the action of lime or potassic hy-
drate on their mono-haloid derivatives. Thus:—
C, Hoſ -- KHO = C, Ha -- KI + H2O.
Iodotetrane + Potassic = Butylene + Potassic + Water.
hydrate iodide
(6.) By the action of sodium on a mixture of a mon-iodo-paraffin
and a mon-iodo-olefine.
(y.) By the decomposition of a mon-iodo-paraffin. At the moment
that the monad radical is set free, its transformation, by the action of
zinc or sodium, into the dyad radical and the hydride of the monad
radical, may be accomplished. This is seen in the formation of
ethylene :-
Ethylic + Zinc = Ethylene + Zincic + Ethylic
iodide iodide hydride.
(3.) By the action of a mon-iodo-paraffin on a sodium compound of
the same radical. Thus:–
C.H.I + C.H5Na = C.H., + NaI + C.H.S.H.
Ethylic + Sodium = Ethylene + Sodic + Ethylic
iodide ethyl iodide hydride.
3. From other simpler hydrocarbons by direct synthesis. Thus :—
(a.) C2H2 + H2 - C2H4.
Acetylene + Hydrogen - Ethylene.
Methane + Carbonic oxide = Propylene + Water.
4. From acids of the C, Han (CO.OH), series, by electrolysis.
Properties (General.)–(a.) Physical. The lower members of this
series are gaseous; the higher are solid; the intermediate ones are
liquid.
(ſ3.) Chemical. The olefines are dyad radicals. Thus they unite
with two atoms of the haloids (as C.H.Br.), or with one of oxygen (as
C2H40). They unite directly with the haloids, forming compounds
which are decomposed by an alcoholic solution of potassic hydrate.
Thus:—
C.H.Cl2 + KHO = KCl + H2O + C2H3Cl.
Ethylene + Potassic = Potassic + Water + Chlor-
dichloride hydrate chloride ethylene.
The compound C.H.Cl may be made to combine with Cl, to form
the compound C.H.Cls. When this is decomposed with alcoholic potash,
OLEFINES. 535
it forms the compound C.H.Cl2. These operations may be repeated
until CaCl, is formed, which body will also combine with Cl2 to form
the solid “per substituted ” paraffin, C2Cl6.
By the action of alcoholic potash on a monochlorinated (or mono-
brominated) olefine, a hydrocarbon of the series C.E.2a-2 is formed.
Thus : —
C.H. Br + KHO ICBr + H2O + Cº.RIg,
Bromethylene + Potassic = Potassic + Water + Acetylene.
hydrate bromide
With strong sulphuric acid, certain of the olefines form ethereal
salts, or, as they are called, acid ethers of sulphuric acid (as
C.H., + H2SO4=C2H5.HSO4). These, when heated with water, are
decomposed into sulphuric acid and the mon-atomic alcohol cor-
responding to the olefine (thus C.H.S.HSO4+ H2O=PH2SO,--C2H3
(OEI)). With fuming sulphuric acid, such olefines form sulpho-acids
(not acid ethereal salts), which sulpho-acids are not decomposed
by water.
A paraffin cannot be formed directly from an olefine by the action
of nascent hydrogen; nevertheless, such a change may be effected
indirectly. Thus by heating ethylene iodide (C. EIAI.) in closed tubes
for some hours with water, ethane (C2H6) is formed ; this conversion
being due to the hydrogen, set free from the decomposition of one
portion of the ethylene iodide (a), acting on a second and undecom-
posed portion (3). Thus:– -
(a.) C.H.I., + 4H2O = 6He + 2CO2 + Ig.
Ethylene + , Water = Hydrogen + Carbonic + Iodine.
iodide anhydride
(3.) C.H.I. + EI2 = C.EI6 + Io.
Ethylene iodide —- Hydrogen - Ethane + Iodine.
The olefines form monochlorinated monohydric alcohols with hypo-
chlorous acid (a), which, by the action of nascent hydrogen may be
converted into the corresponding alcohols (3). Thus—
(a.) C.H., + C10H = C, H,Cl(OH).
(B.) C.H,Cl(OH) + H2 = C.H3(OH) + HCl.
Lastly, the olefines may exist either as saturated hydrocarbons or
as dyad radicals, the difference depending on the linking of the
carbon particles. Thus we may represent ethylene, either as
EI EI H. H.
| | |
C==C OI’ –––
| | | |
EI H. EI H
Saturated Ol' &S a dyad radical.
Acetylene Series.
SERIES III.--Formula CAHsu e.
This includes the following bodies, isomeric modifications of most
of which are known :—
536 HANDBOOK OF MODERN CHEMISTRY.
Boiling point.
NAME. F la. -
OTDOlúlia, F. C.
Acetylene (ethine) C.H.,
Allylene (propine) C3H4
Crotonylene (quartine) CAHs 64-4* 18.0°
Valerylene (quintine) C;Hs 113.0° 45' 0°
Diallyl (sextine) CoPſ to 136.4 ° 58.0°
Rutylene (decine) C.H. 302.0° i30°
Preparation of the Acetylene Series (General).-1. From the
olefines.—By acting on a mono haloid derivative, either with alcoholic
potash, or with sodic ethylate, at a temperature of 302°F. (150° C.)
(a.) C.H. Br + KHO = KBr + H2O + C.H.
(6.) C.H. Br + C.H. NaO = NaBr + C2H3(OH) + C.Hz.
2. From the acids of the maleic series [C, H2n-2(COOH)2], by
electrolysis:— *
C.H.O. = C, EI2 + 2CO2 + Hz.
Fumaric acid = Acetylene + Carbonic anhydride + Hydrogen.
Properties.—(a.) Physical—Acetylene and allylene are gases; the
rest are liquids.
**
(6.) Chemical.—The acetylene series may either exist in a free state,
or they may act as divalent or quadrivalent radicals, thus—
H EI
H–C+=C–H ; C==C; H–C–C–H
Saturated. Divalent radical. Quadrivalent radical.
Thus C.H., can combine with the haloids to form C.H. Brz or
C2H4Br2.
Turpene Series.
SERIES IV.-Formula CAEIgn 4.
Of this series two terms only have been prepared synthetically.


Boiling point.
Formula.
OTInllia, F. C.
Prepared by the action of
potassic hydrate on
Quintone (valylene). . C. He 140° 60° valerylene dibromide
Decone & e º º C10H16 320° 160° (C, HaBr) and rutylene
dibromide (CoHis Br) re-
spectively.
(See SUPPLEMENTARY CHAPTER.)
BENZENES.
587
The Aromatic Series—The Benzenes.
SERIES W.—Formula C.H...-a,
This includes:—

Boiling point.
Formula.
F.o C.9
C.H. Benzene C6H6 176.9 80.5 An isomer is known called
Dipropargyl.
C, H, Toluene (methylbenzene). Cs Hs. CHA 230-0 || 110 -
Xylene (ethylbenzene) CoEſs(C.Hs) 275-0 || 135 | Xylene of coal tar oil is
Pāraxylene Dimethyl CeBI,(CH3), 276-8 136 principally metaxylene.
C.H.10 Metaxylene lmethyl- Cs H., (CH3), 280 - 4 || 138 By oxidation it yields
Orthoxylene benzenes CeBI,(CH3), 285-8 || 14 I metatoluic acid.
Propylbenzene . . CeBIs (CAH,) (a.) 314-6 157 | Cumene (mesitylene of coal
Isopropylbenzene CeBis(CaFI.) (3.) 303-8 ; lij 1 tar oil) may be obtained
C.H., Ethelmethylbenzene ...] C.H. (CH,)(C.H.) | 320-0 | 160 by heating acetone with
9+12 +. y * 6+4 3/ \ – 2-5 * t - -
Mesitylene }". 96H3(CH3)3. 3.25°4 | 163 sulphuric acid:—
Pseudocumene benzenes CSH3(CH3)3 330-8 | 166 3C, H,0=C,EIla+3H2O.
Isobutylbenzene . . . . CFIs (C, Ho) (3.) 320-0 | 160 Cymene has been obtained
Propylmethylbenzene ..] CSPI,(CH2)(C, H,) (a.) 354-2 || 179 synthetically in all its
c. II. Isopropylmethylbenzene .. Q.H.QHA)(C.H.) (3)|348.8 17% forms except modifica-
*** | Diethylbenzene . . . . CsPI,(C2H5), 354-2 || 179 tion (a.).
Ethyldimethylbenzene CSPIs(C.Hs)(CH3)2 363-2 184
Tetramethylbenzene CŞH3(CH3), 374-0 | 190
Isoamylbenzene . . . . CSH s(CSHil) (3.) 379° 4 || 193
(IIHis Isopropyldimethylbenzene Cs Ha(CHs. 39;H) (6.) 370-4 188
fiéthymethylbenzene "...|C.H. (CHjö. H. "|352.4 its
(JI, Isoamylmethylbenzene ...|C.H.(CH)(C.H.) (3)|415.4 213
"Ji, Isoamyldimethylbenzene...|CSEI,(CH3)2(C.Hil) (3.) 451.4 || 233


General Preparation of the Benzenes.-(1.) The benzenes may
be obtained from coal tar.
(2.) By the action of sodium on a mixture of a moniodated paraffin
with a brominated derivative either of benzene, or of an homologous
hydrocarbon :-
C.H2n+[I+C, Hen–7 Br-H Nae-C, H2A-7.C.H2n+1+NaI+NaBr.
Properties (General).--This group, most of the members of which
may be obtained from coal tar naphtha, and may also be prepared syn-
thetically, is called the aromatic group, on account of the fragrant odor
of many of the series. As a class, the benzenes are very stable bodies,
and are remarkable for the numerous isomers and metamers that the
various terms afford, toluene standing almost alone in the series in
having no isomers.
538 HANDBOOIC OF MODERN OEIEMISTRY.
The aromatic series act as Saturated molecules, forming substitution
rather than additive compounds, differing in this respect from the
former groups we have considered, the tendency of which was rather
to form additive than substitution compounds.
The constitution of these hydrocarbons is important. They all
contain a group of 6 carbon atoms; 24 (6 × 4), therefore, is the total
combining or atom-fixing power of the 6 atoms. But 18 of this 24 power
is occupied by the combination of the carbon atoms with each other,
leaving only a power of 6 to be filled up to form a fully saturated
molecule. Thus C6H6 may be regarded as a fully saturated hydro-
carbon. This is shown in Fig. 1:- -
TH EI EI H . CH, CH,
| | | | | |
C=C C–C C=C
/ N / N /
E[–C C–H H–C C—CEI, H–C C—CH,
N / N / N /
C–C C–C C–C
| | | | | |
H EI H. H. EI EI
Fig. 1. Fig. 2. Fig. 3.
It will be seen how other bodies may be derived from this com-
pound by the substitution of more or less complicated molecules in the
place of the hydrogen, as in Fig. 2, which represents toluene, or, as
in Fig. 3, which represents mesitylene (cumene).
The table on page 537 exhibits some of the numerous isomers of this
series. We shall note isomeric compounds made up of the same groups,
as e.g., 3 dimethyl benzenes, C6H4(CH3)2, as well as isomeric com-
pounds made up of different groups, such as ethylbenzene (C6H5)(C2H5)
and dimethylbenzene (C6H1)(CH3)2. The nature of these hydrocarbons
is to be specially inferred by their behaviour on oridation, as when
treated with dilute nitric or chromic acids. The following facts on this
point must be noted : —
(1.) Benzene forms no oxidation products that contain 6 carbon
atoms. It may be burnt and form H2O and CO2. It may also be
made to form benzoic acid (C7H6O2) or phthalic acid (CeB6O4).
(2.) All the derivatives of benzene formed by the replacement of
one atom of hydrogen by the group CnH2n + 1, such as methylbenzene
C6H3(CHA), propylbenzene, C6H3(C5H7), butylbenzene, C6H3(CHo), amyl-
benzene, C6H3(C5H11), etc., yield, by oxidation, one and the same acid,
viz., benzoic acid (C, H5O2).
(3.) The derivatives formed by the replacement of H. by two groups
of the formula CAPT2n+1, such as dimethylbenzene, C6H4(CH3)2 or
diethylbenzene, (C6H4(C2H5)2, produce by oxidation, in the first in-
stance an acid of the benzoic acid series, whilst they all finally yield
the same acid, viz., terephthalic acid, C6H4(COOH)2.
BENZENES. 539
(4.) The derivatives formed by the replacement of Ha by 3 groups
of the formula C, E, 11, such as trimethylbenzene, C6H3(CH3)3, etc.,
yield on oxidation as their final product mesitic acid, C6H3(COOH)3.
The molecular constitution of these bodies may be further in-
ferred by their synthetical formation. Thus methylbenzene or toluene
C6H3(CH3)=(C, Hs) is obtained by the action of sodium on a mix-
ture of methylic iodide and bromobenzene ; ethylbenzene or aylene,
C6H3(CH3)=(C,EIlo) is obtained by the action of sodium on a
mixture of ethylic iodide and bromobenzene ; whilst dimethylbenzene,
C6H (CH3)2=(CeBIto), an isomer of xylene, is formed by the action
of sodium on iodomethane and dibromobenzene.
Chlorine and bromine form substitution and additive compounds
with benzene in the presence of iodine. The iodine acts in such cases
as the carrier of chlorine, that is, the chloride of iodine forms moniodo-
benzene with the benzene, and this, by the action of a further
portion of iodine chloride, is converted into chlorobenzene. Thus—
(a.) C6H6 + CII - C6H5T + EICl.
Benzene + Iodine chloride = Iodobenzene + Hydrochloric acid.
Iodobenzene + Iodine chloride = Chlorobenzene + Iodine.
Iodobenzenes may be formed by the action of iodine on benzene in
the presence of iodic acid. The iodic acid decomposes the hydriodic acid
as soon as formed. If iodic acid was not added, the hydriodic acid
would decompose the iodo derivative, by withdrawing iodine from it
and replacing it by hydrogen. The following equations will explain
this:—
(1.) Without iodic acid; C6H51+HI-C6H6+I2.
(2.) With iodic acid; C6H3L-1-5EII+HIO =C5H5T-i-3H20+3.I.,
On toluene in the cold, chlorine forms the stable compound chloro-
toluene (C7H7Cl), which is unacted upon, either by nascent hydrogen
or by fusion with alkalies. On boiling toluene, chlorine forms benzylic
chloride (C7H7Ol), a body having the same composition as chlorotol-
uene, but differing from it, in that nascent hydrogen changes it to
toluene, and alkalies readily decompose it. On boiling toluene, however,
&n the presence of iodine, the stable body chlorotoluene is formed, which
as we have said, is singularly unamenable to the action of ordinary
reagents.
With strong nitric acid the benzenes form nitro derivatives [CH6
+HNO3=H2O+C6H3(NO2)]. With sulphuric acid they form sul-
phonic acids [CSH6+ H2SO4–II,0+C6H3(HSOs)]; and with hydri-
odic acid, aided by a continuous heat of 536° F (280°C.) they are
Converted into the corresponding paraffins.
Benzene,—Bengol; bicarburet of hydrogen; phenylic hydride (C6H6).
[Molecular weight, 78. Molecular volume, ITI. Boils at 176.9°F.
(80.5° C).] -*.
Preparation.—(1.) By the action of heat on acetylene (3C.H.-
C6H6).
540 HANDBOOK OF MODERN CHEMISTRY.
(2.) By the distillation (a) of benzoic acid with lime, or (3) by the
action of heat only on benzoic acid :—
(a.) C6H3(CO.OH)+Caf1202– CaCOs + H2O + CGH6.
Benzoic acid + Lime = Calcic Carbonate + Water + Benzene,
(6.) C6H3(COOH) = CO2 + C6H6.
Benzoic acid - Carbonic anhydride + Benzene.
Its preparation from that portion of the coal tar boiling below
180°F. (82.2°C.), has been already referred to (page 500).
Properties.—(a.) Physical. A colorless, inflammable liquid of high
refracting power, having an ethereal odor and a burning taste. Its
Sp. Gr. at 0°C. is 0-899. It boils at 176.9°F. (80.5°C.), and solidifies
at 41.9°F. (5-5°C.) to a white crystalline solid. It is insoluble in
water, but is soluble in alcohol and in ether, and is a solvent for iodine,
sulphur, phosphorus, fats, resins, etc. When its vapor is passed
through a porcelain tube heated to bright redness, it is decomposed
into the gases hydrogen and acetylene (C2H4), into the liquids diphenyl
(C18H16) and chrysene (CaFIIs), and into an orange-colored solid
called benzerythrene. •
(6.) Chemical. With the haloids, benzene forms both additive and
substitution compounds. As illustrations of the additive compounds
that it forms, we have benzene headachloride (C6H6Cl6) and benzene heava-
bromide (C6H6Brg), both of which are solid bodies, formed by the action
of sunlight on a mixture of chlorine and benzene. As illustrations of
substitution compounds, we have monochlorobenzene, C6H3Cl, and also
the compounds C6H4Cle, C6H3Cl3, etc.
Some of the benzene derivatives are stated in the following
table :-
Boiling point. Melting point.
Formula.
• F. ° C. • F. • C.
Monochlorobenzene . C.H.Cl 276.8 136 —40 —40
Dichlorobenzene CeBIACl, 339.8 171 |+127.4 +53
Trichlorobenzene . CeBIACls 402.8 206 62-6 17
Tetrachlorobenzene . . . . . . . CaFI.Cl, 464 - 0 240 2S2-2 139
Pentachlorobenzene . . . . . . CºFIUls 521-6 272 185:0 S5
E[exachlorobenzene . . . . CoCl6 618-8 326 4.38.8 226
Monobromobenzene . . C.H. Br 302-0 150
Dibromobenzene CoII, Br, 4 17.2 214
Tribromobenzene C6H4Bra 527.0 275 1 11 - 2 44
Tetrabromobenzene . . . . . . . CoPI, Br,
The iodobenzenes are similar to
the above.
Nitrobenzene . . . . . . . . . C6H5NO2
(Artificial oil of almonds.)
Dinitrobenzene . . . . . . . . . CaFIA(NO2),
The chlor-benzenes are formed by passing chlorine into a solution
of iodine in benzene, the iodine acting as a carrier of the chlorine to
the benzene, f
BENZENES, 541
The benzene haloid derivatives are very stable bodies. Unlike
the paraffin derivatives, they are unaffected by nascent hydrogen, or
even by fusion with potassic hydrate. With hypochlorous acid, ben-
zene forms the additive compound C6H6(ClOH)3, which, by the action
of water, forms a non-fermentable body called “phenose,” having the
same composition as grape-sugar. When this body is dissolved
in fuming nitric acid, and water added to the solution, nitrobenzene
(C6H5NO2), or artificial essence of bitter almonds, separates, which,
by the action of reducing agents, yields aniline.
Toluene,—Methylbenzene (C7Ha=C6H5, CH3. [Molecular weight, 92.
Boils at 230°F. (110°C.). Not solid at —4°F. (–20°C.). Specific
gravity, 0-881 at 41°F. (5° C.).]
Preparation.—(1) From coal tar oil. (See page 497.) It is con-
tained in that portion boiling between 212° and 248° F. (100° and
120° C.). -
(2.) By the action of sodium on a mixture of bromobenzene and
methyl iodide. Thus:–
C6H. Br + CHAI + Naa = NaBr + NaI + C3H3.CHs.
Bromobenzene + Methyl + Sodium = Sodic + Sodic + Toluene.
iodide bromide iodide
(3.) By the action of methane in a nascent state on benzene.
Properties.—A limpid liquid. Sp. Gr. 0-881 at 5° C. Boils at
230°F. (110°C.). Chemically, it behaves very like benzene, yielding
benzoic acid when treated with oxidising agents. -
Two isomeric derivatives are formed in almost every case by the
action of reagents on toluene.
SERIES WI.-Formula CAH2n-s Series.
This includes:—
Boiling point.

• F. ° C.
4.Y
Cinnamene. . . . . CaFIs 293 145 | Preparation.—(1.) By passing the vapors
(Styrolene) of benzene and acetylene, or (2.) of
benzene and ethylene, through a red-
hot tube. (3.) By heating acetylene
(4C, H2-C's Hs). (4.) It is present in,
and may be obtained from, liquid
storax.
Properties.—A colorless liquid. It does
not solidify at —4° F. (–20° C.)
Heated in closed tubes to 39.2° F.
(200° C.) it is converted into a white
solid metacinnamene, which yields, on
distillation, liquid cinnamene,
Allylbenzene . . . CoPſio || 338 170 | Preparation.— By the action of nascent
hydrogen on cinnamic alcohol.
Phenylbutylene. . . CloBI, Preparation.—By the action of sodium on
a mixture of benzylic chloride and
allylic iodide.
542 HANDBOOK OF MODERN CEIEMISTRY.
SERIES VII.-Formula C.H2n-10 Series.
This includes,
Acetenylbenzene (CeBIs) a colorless liquid boiling at 282-29 F.
(189°C.). It is prepared by the action of an alcoholic solution of
potassic hydrate on cinnamene dibromide (C.B.,Br, +2KHO=C.B.,
+2KBr-F2H2O). Like acetylene it precipitates many metallic
solutions.
The Naphthalene Series,
SERIES VIII.-Formula C.H. ix.
This includes ... —
Boiling point.
o F. o C.
Naphthalene. ... .. C10Hs 4 13.6 212
Methylnaphthalene.. * - Clo Hio = Clo H., (CIIA) 447-8 231
Ethyl naphthalene . . tº e C12 Hº-Cio H+(CH3) 483-8 251
Naphthalene (CoHg).
Occurrence and Preparation.—(1) Naphthalene is a bye-product
in the preparation of coal gas. In distilling coal tar, the latter
portion of the distillate contains a large quantity of naphthalene.
It is produced whenever organic matter is distilled at a high tem-
perature out of contact with air, or whenever the vapours of benzene,
cinnamene, chrysene or anthracene are passed through a red-hot
tube. --
(2.) By passing the vapour of dibromophenylbutylene over red-hot
lime (CoHigPro-Cio Ha-i-H2+2HBr). -
Properties.—(a). Physical.—A white solid body, crystallizing in
brilliant scales. It has a faint narcissus-like odour. It melts at
176° F (80°C.) and boils at 413.6°F. (212°C.) Its vapor density
is 4,528. It is insoluble in cold water—slightly soluble in boiling
water—very soluble in alcohol, in ether, in acetic acid, and in the
volatile oils.
(6.) Chemical.—It burns in air with a red smoky flame. It forms
with chlorine and with bromine both additive and substitution com-
pounds, such as CoPIgCl, and CoEI, Cl, etc. By oxidation it yields
dinaphthyl, C20H14, and phthalic acid CaFI604. It is soluble in strong
sulphuric acid, forming two isomeric naphthalene-sulphonic acids,
CoEI,(HSO3) both of which form soluble baric salts. Nitric acid
f
ANTHRACENES. 543
converts it, first, into a crystalline solid nitronaphthalene CoH1NO2, and
finally into tetramitronaphthalene CoHA(NO3)4. With a solution of
chromic anhydride in acetic acid, it forms naphtho-quinone CoEI6O2.
SERIES IX. — Formula C, H2n-14 Series.
This includes:—
Melting point. Boiling Point."
• F. ° C. ° F. ° C.
ſ Preparation.—By passing
benzene through a red-hot
tube (2C6H3–CI, Ho-HBL).
By oxidation it forms benzoic
acid. It sublimes at 140°F.
(60° C.). It is contained in
C.H., | Diphenyl. . . . . . 140-0 | 60-0 |464-0 |240-0 || coal-tar, and distils over in
- (C6Hs,CGH; that portion that boils be-
tween 518° and 572°F. (270°
and 300° C.). By oxidation
it forms naphthalic acid,
which, when distilled with
U lime, yields naphthalene.
Acenaphthene. . . . . 203-0 | 95.0 |514.4 268-0
Preparation. — By the
action of heat on a mixture
of benzylic chloride and
Diphenyl methane .. benzene (CSHs-HC, H,Cl=
C.H., (Benzylbenzene) || 797 26-5 |501.8 |261-0 || HCl·HC, H, )." [The 'pre-
(C6Hs, CH,CSEIs) sence of a little zinc and
copper facilitate the action.]
By oxidation it yields benzo-
phenome (C.H.C.O.C.H.).
Ditolyl (a) 249'S 121-0 Preparation. — By the
» (8) . . . . liquid action of sodium on benzylic
C.H. (QHA.C.H.C.H.C.H.) chloride. It is insoluble in
***14 | Dibenzyl . . . . . . . 125-6 52-0 || 543.2 284-0 water, but is soluble in
(C6Hs.C.H.C.H.C.H.) alcohol and ether.
Benzyltoluene . . liquid 534-2 || 277-0
Benzyl ethylbenzene liquid 561.2 294-0
CisłIts | Benzyl metaxylene . liquid 563-0 || 295.0
Benzyl paraxylene. . liquid 561.2 | 294-0
Excepting acenaphthene, all these bodies act as saturated mole-
cules and form substitution but not additive compounds.
The Anthracene Series.
SERIES X. —Formula C, Han is.
This includes —

Melting point. Boiling point.
• F. • C. • F. • C.
Anthracene . . . . . . . . CuHuo 415-4 213 680 360
Dimethylanthracene . . . . Cisłſis
\{}
544 w º HANDBOOK OF MODERN CHEMISTRY.
Anthracene (Paranaphthalene.) (HLH1) Molecular weight 178.
Specific gravity 1-147. Melts at 415.4° F (213° C); boils at 680° F.
(360° C.)
Preparation.—(1.) It is obtained commercially from the semi-
Solid portion of the coal tar distillate, which comes over at from 644°
to 752° F (340° to 400° C.) It is important to note that when
distilled at ...the lower temperature, the anthracene is mixed with
naphthalene, but that when distilled at the higher temperature it is
mixed with chrysene and pyrene, these latter being the final products
of the distillation of coal tar. Inasmuch, however, as anthracene is a
valuable commercial product used in the preparation of artificial
alizarine, and that alizarine cannot be produced either from naphtha-
lene or from chrysene, the exact relation of anthracene to these
bodies becomes important. -
(2.) By passing benzene, mixed either with (a) ethylene, (3)
with cinnamene, or (y) with naphthalene vapor, through a red hot
, tube:—
Benzene + Ethylene = Hydrogen + Anthracene
(3.) C6H6 + Cafia - 2H2 + Cºlio.
Benzene + Cinnamene = Hydrogen + Anthracene.
(y.) 3C6H6 + Cloſis 3H2 + 2C14H10.
–
Benzene + Naphthalene Hydrogen + Anthracene.
(3.) By the action of heat on a mixture of (a) ethylene and diphenyl
or (3.) of ethylene and chrysene —
(a.) C2H4 + C19Ho
Ethylene + Diphenyl
(6.) C.H., + ClaRue
Ethylene + Chrysene
4. (4.) By the action of heat on toluene, xylene, or cumene.
(5.) By the action of heat on benzylic chloride:—
4C, H,Cl = C, Hio + ClaRIA + 4HCl,
Benzylic chloride = Anthracene + Benzyltoluene + Hydrochloric acid.
(6.) By the action of heat on a mixture of alizarine and zinc dust.
Probably some of the alizarine is decomposed and hydrogen set free.
The action may be formulated thus:–
C.H.0, H- . He -- 4Zn = Cl, Hio + 4ZnO.
Alizarine + Hydrogen + Zinc = Anthracene + Zincic oxide.
Properties.—(a.) Physical. A colorless solid, crystallizing in four
or six-sided plates. Specific gravity, 1.147. It sublimes at 212°F.
(100° C.); melts at 415.4° F (213° C), and boils at 680° F. (360° C).
[Naphthalene melts at 176° F (80°C.), and boils at 418.6° (212° C.)]
Anthracene is insoluble in water, almost insoluble in cold alcohol (in
which naphthalene issoluble), somewhat soluble in carbonic disulphide
and in boiling alcohol; soluble in ether, in benzene, and in the volatile
2H2 +- * > ClaRIlo.
Hydrogen + Anthracene.
C6H6 + C4H10.
Benzene + Anthracene.
–
–
ANTHRACENE. 545
oils (such as turpentine). Sunlight in time effects its physical trans-
formation into paranthracene, a body that melts at 471-2°F. (244°C.),
but which may be reconverted by fusion into common anthracene.
(6.) Chemical.-With nascent hydrogen, it forms a dihydride,
C14H10, H2. With the haloids it forms both substitution and additive
products (as C4Hs Brø.Br.).
Its reaction with oxidizing bodies is of great importance, inasmuch
as by this means artificial alizarin, a body identical with the red
coloring matter of madder, and a product of great commercial value,
is prepared. The equations representing the reactions that occur in its
preparation may be thus stated:—
(1.) (a.) Heated with nitric acid, or with potassic bichromate and
sulphuric acid, anthracene forms anthraquinone. Thus:—
2C14H10 + 30, = 2EC, Ha(O2)"] + 2 H2O.
Anthracene + Oxygen -: Anthra-quinone + Water.
In anthraquinone it will be noted that (O2), like (Hg2) in mercurous
compounds, plays the part of a dyad radical.
[N.B. This body is called anthraquinone because it bears the same
relationship to anthracene that quinone bears to benzene. Thus:–
C6H6 — C6H (O.)"; C14H10 — C14Ha(O2)".
Benzene - Quinone ; Anthracene — Anthraquinone.
(3.) When anthraquinone is heated with bromine it forms dibrom-
anthra-quinone. Thus : —
C14H8O2 + 2Brz C1, EIGBr2O3 + 2 HBr.
Anthra-quinone + Bromine = Dibrom-anthra- + Hydrobromic
quinone acid.
(y.) When dibrom-anthra-quinone is heated to 350° F. (176.1° C.)
with potassic hydrate, it forms the potassic derivative of dioxy-anthra-
quinone (or alizarin). Thus :—
C14H6BreO2 + 4KHO - C14H8O.(KO). + 2ECBT +- 2H2O.
Dibrom-anthra- + Potassic = Potassic alizarate + Potassic + Water.
quinone hydrate bromide
(6.) When an acid is added to a solution of the fused mass con-
taining potassic alizarate, crude alizarin, C1, HaO, or C14H6(OH)2(O.)",
is thrown down as a yellow precipitate, which when carefully sub-
limed produces a red sublimate of fine alizarin.
Alizarin may also be prepared as follows:–
(2.) (a.) By the action of chlorine on anthracene, dichlor-anthracene
is formed. Thus:–
C14H10 + 2Cl2 -: C14H9Cls + 2HC1.
Anthracene + Chlorine = Dichlor-anthracene + Hydrochloric acid,
(6.) When this dichlor-anthracene is heated with sulphuric acid it
forms dichlor-anthracene-disulphonic acid [C1, H3Cl3(HSOs).]. Thus:–
C14H9Cls + 2H2SO4 = Cl, EIGCl3(HSO3)2 + 2 H2O.
Dichlor-anthracene + Sulphuric acid = Dichlor-anthracene + Water.
disulphonic acid
N N
546 * HANDBOOK OF MODERN CHEMISTRY.
(y.) By acting on this product with oxidizing agents, or by heating
it with strong sulphuric acid, it forms anthraquinone-disulphonic acid
C.H.O.(HSO). Thus ... —
C14H6Cl2(HSOs). + O2 F C14H8O2(HSO4)2 + Cl2.
Dichloranthracene disul- + Oxygen = Anthra-quinone- + Chlorine.
phonic acid disulphonic acid
(6.) When this is heated with potassic hydrate it forms potassic
alizarate, which is then treated with an acid in the manner already
described.
C14H8O2(HSOs),-- 6KHO = C, HGO.(KO). -- 2K.S0s -- 4H.O.
Anthra-quinone- + Potassic = Potassic alizarate + Potassic -- Water.
disulphonic acid hydrate sulphite
Alizarin is soluble in alkaline solutions, and in solutions of the
alkaline carbonates, forming deep purple liquids, from which alizarin
may be precipitated by an acid.
Coal tar oil contains several bodies that are isomers of anthracene.
For example, phenanthrene a solid, melting at 212°F. (100° C.), and
boiling at 644°F. (340°C.); tolane, a solid, melting at 140°F.
(60°C.); and a third body melting at 476.6° F (247° C.).
NoTE.—We may here note, that, starting from benzene, we have a
complete series of hydrocarbons, where the successive terms differ by
CaLig. Thus : —

Fusing point. Boiling point.
Formula.
o F. o C, o F, o C.
Benzene . . . . . . . . . . CoPIs 41 '9 5' 5 176.9 80 - 5
Naphthalene . . . . . . . . Cioffs 176-0 80-0 || 413. 6 212-0
Anthracene . . . . . . . . C14H10 415' 4 || 213-0 | 680-0 || 360 °0
Chrysene . . . . . . . . . . Claſſis 478.4 248-0 || |
The relationship of these bodies is remarkable. They all form
Quinones, that is, bodies where H., is replaced by (O.)" directly (in all
cases except that of benzene) as products of their oxidation (see page
528). These quinones are neutral bodies, and furnish hydro-quinones
(the dioxy-derivatives of the several hydrocarbons), by the action of
nascent hydrogen. Thus:–
C6H6 — CGH1(O2)" — C6H1(OH)2.
Benzene -- Quinone * Hydroquinone.
SERIES XI.—Formula CAEIzu-16 Series.
This includes only stilbene or toluyene (C1, H12). This hydrocarbon
is a crystalline solid, prepared by the action of heat on dibenzyl
BIYDROCARBONS. 547
(C.H.4–C., Hig-H H.). It melts at 212°F. (100° C.), and boils at
557.6° F (292°C.). It forms both substitution and additive products.
By the action of potassic hydrate on the dibromide C14H12Brz,
tolane (C14H10) is formed.
SERIES XII.-Formula CAH2n-22 Series.
This includes—

Fusing point.
o F. o C.
Diacetenylbenzene 287-6 Present in coal tar oil.
C15H10 | P ‘6 || 142-0 | (N.B.-These bodies contain 95 per
- yrene
Clo Bis(CSH.) - cent. of carbon.)
Obtained, with other products, by
passing benzene through red-hot
Diphenylbenzene • () 9(); , tubes. It yields an oxidation
CisBi. C6H3(C6H5)2 401-0 | 205-0 first phenylbenzoic acid & H.C.#.
(CO, H), and finally terephthalic
acid CSPI,(CO2H)2.
Preparation.—By the action of heat
Triphenylbenzene • K • K in closed tubes on a mixture of
Cu,FIIs CH(C6H5)3 198: 5 92.5 benzylene chloride, and mercuric
phenyl.
SERIES XIII.-Formula C, Hen—24 Series.
Chrysene (CsII2). This, the only known member of the series, is
found together with pyrene (C16H10) as the final product of the dis-
tillation of coal tar. It crystallizes in fine yellow scales, which melt
at from 473° to 478.4°F. (245° to 248°C.). It is insoluble in alcohol,
and nearly insoluble in ether, but is soluble in boiling turpentine, from
which it is deposited as the liquid cools. By oxidation it forms
chrysoquinone (ClaRioCs).
SERIES XV.-Formula CAH2n-22 Series.
This includes tetraphenylethylene (Cº(C5H5),=C.6Boo), a crystalline
body which melts at 428°F. (220° C.), and is prepared by the action
of heat on a mixture of finely divided silver and diphenylketone, this
latter body being a product of the action of phosphorus pentachloride
on benzophenone. Thus—
2[(C6H5)3CCl2] + 2Age = Cº(C6H5), + 4AgCl.
Diphenylketone + Silver = Tetraphenylethylene + Argentic chloride.
548 IIANDBOOK OF MODERN cIIEMISTRY.
SUPPLEMENT TO CHAPTER ON THE
HYDRO CARBONS.
ADDENDUM TO THE PARAFFINS.
Petroleum—Paraffins.
The paraffins, it will be noted, vary greatly in their physical con-
ditions. The higher terms are solid, and are employed in the manu-
facture of candles, etc. Following these are a series of buttery
compounds, used for lubricating purposes. Then follow compounds
which are liquid and are used for burning in lamps; and finally, cer-
tain liquids volatile below 100°F. (37.8°C.) (petroleum spirit), that
are used as solvents in the arts.
In American petroleum and in the mineral oils of a like nature found
in or near the coal formation, and formed by the gradual decomposition
of vegetable matter beneath the earth’s surface, we have an admixture
of numerous hydrocarbons of this group of paraffins. In order to
prepare the oil for illuminating purposes, it is necessary that all the
hydrocarbons volatile at a temperature above 100°F. (37.8°C.), (that
is, all the hydrocarbons containing less than six carbon atoms), should
be distilled off, otherwise the oil would be dangerous. The distillate
constitutes what is called “Petroleum spirit,” and is used as a solvent
for caoutchouc and resinous bodies, whilst the liquid remaining in the
retort is safe for burning in lamps.
Paraffin oil, which is also a mixture of the paraffin hydrocarbons, is
obtained by the destructive distillation of such bodies as boghead
cannel, peat, etc. The most volatile portions are used for illuminating
purposes, and the least volatile (mixed with fatty oils, such as rape,
cotton, etc.) are employed for lubricating machinery.
Paraffin.
If petroleum (Rangoon tar or rock oil), or paraffin oil be subjected
to an intense cold, the separation of a solid body, called paraffin, takes
place. This substance exists ready formed in such minerals as Ozo-
kerit, mineral wax, etc. It is a compound of several hydrocarbons
of the CPI, group, and is largely used for candles, etc. The following
is an outline of its preparation :-
The crude tar resulting from the destructive distillation of boghead
cannel, etc., is distilled. The distillate is first shaken up with a
sodic hydrate solution, in order to remove all acid bodies. It is
afterwards treated with sulphuric acid, to remove all basic substances
such as naphthalene, etc. The residue of these operations, after
being well washed, is distilled, and the solid distillate collected.
TUIRIPENES. 549.
Any liquid oils present in the mass are now extracted, first by a
centrifugal apparatus, then by pressure in the cold, and finally by
pressure at or about 105° F (40-5°C.), so as to remove all hydro-
carbons melting below this temperature. The residue is again
treated with sulphuric acid, whereby all hydrocarbons other than
paraffins, are charred. The paraffin collects on the surface of the
acid, and is then removed. After being washed, it is melted in oils
of low boiling-point, the solution decolorised by filtration through
animal charcoal, and finally the volatile oils removed by distillation
from the pure paraffin.
Properties.—(a.) Physical. A white waxy solid, without taste or
smell. Its fusing-point varies, according to its source, from 104°F.
(40°C.) to 140°F. (60°C.), the latter being the temperature at which
the paraffin obtained from ozokerit melts. It boils at about 698°F.
(370°C.). A continuous heat under pressure converts it into liquid
hydrocarbons (Thorpe and Young). It is insoluble in water, slightly
soluble in alcohol, very soluble in ether and in the fixed and
volatile oils.
(3.) Chemical.—Paraffin is remarkable, as its preparation given
above would indicate, for its resistance to most chemical reagents
(parum affinis). When, however, it is heated continuously for several
days with sulphuric acid and potassic dichromate, cerotic acid is
formed (C27H54O2), and when similarly treated with nitric acid, a
mixture results of solid and liquid fatty acids. When melted paraffin
is acted on with chlorine, it is gradually attacked, and gives off
hydrochloric acid.
ADDENDUM TO THE “TURPENES.”
Oil of Turpentine and its Allies.—The Turpenes,
The name turpentine is given to an oleo-resinous juice exuding from
certain varieties of pines. Common English turpentine is obtained from
the Scotch fir, the Pinus Australis and Pinus Toeda; Venice turpentine
from the larch ; French turpentine from the Pinus maritima, etc.
“Turpentine’’ is a solution of rosin in spirits of turpentine. When
distilled, the residue in the retort, amounting to from 75 to 90 per
cent., constitutes rosin, and the distillate, varying in quantity from 10
to 25 per cent., constitutes turps, or spirits of turpentine. In the case
of the Boston turpentine, the distillate constitutes “camphine.”
Properties of spirits of turpentine.—(a.) Physical. A colorless, mobile,
peculiar smelling liquid. Sp. Gr. 0.864. It boils at 320°F. (160°C.).
It is not very soluble in water, but is very soluble in alcohol, carbonic
disulphide, and in ether, and is itself a solvent for iodine, sulphur,
phosphorus, resinous and fatty matters, caoutchouc, etc. It is a
powerful refractor of light.
550 EIANDBOOK OF MODERN CHEMISTRY.
(3.) Chemical. When French spirits of turpentine is neutralised with
an alkaline carbonate and distilled, it yields “terebenthene” (CoHig),
a liquid boiling at 321.8°F. (161° C.), and having a Sp. Gr. of 0-864.
It turns the plane of polarisation to the left. English spirits of turpen-
time similarly treated, yields “austraterebenthene,” a liquid having a
similar gravity and boiling-point to terebenthene, but turning the
plane of polarisation to the right.
(1.) Both bodies (i.e., terebenthene or austraterebentheme) when
heated to 482°F. (250° C.), form two levo-rotatory oils, which
may be separated by distillation; viz., austrapyrolene, boiling at
352.4°F. (178°C.), and metaterebentheme (C26H52), boiling at 680° F.
(360° C.).
(2.) By the action of air, turpentine becomes oxidised and forms a
product of a resinous nature.
(3.) Spirits of turpentine, though insoluble in water, forms three
hydrates: viz., (a) a crystalline hydrate, Cloſing,3EI2O, soluble in
water, fusing at 217°F. (102.8°C.); (3) a second crystalline hydrate,
Clo H16,2H2O, subliming at 480°F. (248.9°C.) formed by the action
of heat on the former hydrate ; and (y) a liquid hydrate called
terpinole, (CoH16), H2O, having an odor of hyacinths, and obtained by
distilling either of the former hydrates with sulphuric acid.
(4.) Chlorine and bromine are so rapidly absorbed by turpentine, that
inflammation frequently results, EIBr and HCl being formed, and
carbon set free. Distilled with water and chloride of lime, chloroform
is formed. With iodine, combustion does not usually occur. The
solution of iodine in turpentine is green, and, as the heat increases
during the progress of the chemical action, hydrochloric acid is evolved.
(5.) By the action of gaseous boric fluoride, or when the spirits of
turpentine is digested with a little oil of vitriol in the cold, it yields
two liquids, both of which are without action on a polarised ray; viz.,
terebene (CoH16), a liquid boiling at 320°F. (160°C.), having the odor
of thyme, and colophene or diterebene (C26H38), a liquid boiling at
600°F. (315-5°C.), and having a Sp. Gr. of 0-940 (vapor density 4:76).
This latter liquid appears colorless by directly transmitted light, and
blue by obliquely transmitted light.
(6.) Common nitric acid forms, with turpentine, acid products. The
action of the fuming acid upon it is sufficiently energetic to cause
combustion.
The following volatile or essential oils have the same composition
as common spirits of turpentine (CoH16), viz., oils of lemon,
orange, bergamot, lime, citron, neroli (?), caraway, camomile,
coriander, elemi, gomart, hop, juniper, laurel, parsley, savin,
thyme, valerian, wintergreen, cloves, etc. The oils of copaiba
and cubebs (C26H42) are also polymeric with spirits of turpen-
tine.
All these bodies form resinoid substances by exposure to air.
ESSENTIAL OR vol.ATILE OTLs. - 551
They also form crystalline hydrates and artificial camphors, by the
action of hydrochloric acid.
It will be convenient here to consider a few bodies, the exact
relationship of Some of which it is not easy to define.
I. Essential or Wolatile Oils.
These hydrocarbons are found for the most part in the vegetable
kingdom and in all parts of the plant : sometimes in the seed, as in
the mustard; sometimes in the rind of the fruit, as in the Orange ;
sometimes in the flower, as in the rose; sometimes in the leaves, as in
the myrtle. A few only are found in the bodies of animals, such as
e.g., the oil of ants.
Preparation of the Wolatile Oils.-(a.) By pressure. Examples—
Oils of lemon, bergamot, laurel, etc.
(3.) By distillation with water. This is the common method of
extracting the majority of these oils.
(y.) By fermentation and distillation. This is illustrated in the
preparation of the oils of bitter almond and mustard, where, after the
seed has been crushed and mixed with water, the action of some
nitrogenized body on certain compounds in the seed, develops the oil
which is afterwards extracted by distillation.
(6.) By destructive distillation. Examples—The volatile oils from
peat, wood, coal, bones, etc.
(e.) By solution in a fired oil destitute of odor (such as poppy oil).
Eacamples—Oils of geranium, jessamine, violet, heliotrope, etc.
(...) By chemical action. Example—Oil of spiraea, from salicine.
Properties.-(a.) Physical. At ordinary temperatures these oils
are usually liquid. Oil of aniseed, however, is a solid. Their color
is mostly yellow when first prepared, but they rapidly darken by
exposure to air from the absorption of oxygen, becoming finally a
resinoid mass. Their odor is powerful. Their boiling point is
usually above 212°F. (100°C.). They produce on paper a greasy stain
which is transient, and dissipated by heat. Their specific gravities
vary, but they are usually lighter than water.
(ſ3.) Chemical. They are all combustible bodies, slightly soluble in
water, the solution forming the officinal medicated waters. They
are freely soluble in spirit (forming essences), from which solutions
they are precipitated by water. They are soluble in fatty oils. By
the action of cold they separate into a solid crystalline compound
(Camphor or stearoptene) and a liquid oil (eloeoptene). They are
destroyed by the action of acids. They are insoluble in potash, and
are not saponified by alkalies.
552.
HANDBOOK OF MODERN CHEMISTRY.
Essential Oils.
ISOMERS AND PolyMERs of TURPENTINE,


Specific Gravity. Boiling Pt. Direction
Oils of - of Source. Remarks.
Liquid. Vapor. o F. o C. Rotation.
Turpentine ... 0.864 || 4-812 320 160'0 left Coniferous
- trees
Bergamot ... ... 0-869 361 | 182'8 right See Oil of lemon.
Borneene * * * * 4' 60 320 | 160- 0 left
Birch . . . . . . . 0-847 5 °38 313 || 156*1
Camomile . . . 347 175'0 Anthemidis Contains, the hydrocarbon Cao Hie, and
flores an oxidized body, C, o H, e Oa.
Caraway 0.938 5' 17 343 172:8 right Contains carvene (Clo Hae) and carvoi
(Clo H.O).
Cloves . . . . . 0-918 289 142.8
Elemi . . . . . 0-849 345 || 173'9 left,
Hop. w e º 'º right
Juniper . . . . . 0-86 320 160'ſ) left,
Lemon . . . . . 0-851 4-87 343 172-8 right Contains, in common with many others,
hesperidene (Clo Hig), and certain oxi-
dized hydrocarbons.
Orange . . . . . 0-83 4-64 || 356 180-0 | right See Lemon.
Parsley 320 160-0
Pepper .. O'864 4'73 333 167.2
Savine tº º 320 | 160-0
Tolu . . . . . 0°837 320 160-0
Thyme . . . . 4-76 329 || || 65'0 Il OIn 6
Capivi . . . 0°878 500 | 260-0 | left } C, . H
Cubebs . . . . . 0-929 490 || 2:54:5 left 1.5 +* 24,
Attur of Roses.. 592 || 311'1 Contains a solid hydrocarbon, Ce Hie, and
an oxidized product to which the scent
is due.
Bitter Almond.. Amygdala
{\Oſlº, I'ºl,
Dill . . . . Fructus | Contains anethene (Clo Hag), and an oil,
an ethi no H 140.
Aniseed . . . . Pompenella | Contains a solid hydrocarbon, Cao Has.
anisum
Horseradish Composition, C, H,CNS,
Neroli.. See Oil of lemons.
Cardamoms Ditto. It also contains a camphor,
Cao H163H2O.
Cajeput Contains cajwpwtol (Cao Hia.HaO).
Ciunamon.. I'0.50
Fennel
Peppermint Contains menthème (Cao Hia).
Sassafras . . 1'094
Mustard l"O15 t
II. Camphors.
Camphors are oxidized hydrocarbons, and are closely related to the
essential oils.
Common camphor (CoH16O) is obtained from the wood of the
Laurus Camphora, or camphor laurel, by boiling it in water, and
oondensing the camphor as it passes over, on straw placed at the head
of the still. It is afterwards purified by sublimation. An oil distils over
during the action, called liquid camphor or oil of camphor (C10H16);0,
which by exposure to air oxidizes and deposits common camphor.
Properties.—(a.) Physical. A white crystalline (octahedra) solid,
volatile at ordinary temperatures. It has a specific gravity of
0.996. It fuses at 347° F. (175°C.) and boils at 399°F. (203.9°C.).
It rotates a ray of light to the right (+47:4). It is very slightly
IRESINS. 553
soluble in water (1 in 2,000 parts, or 40 grains per gallon), but is
freely soluble in alcohol, in ether, and in strong acetic acid.
(6.) Chemical. Camphor burns with a smoky flame. When distilled
it yields the colorless compound camphoric oride (CoH1,0s). Distilled
with P.S. or with phosphoric anhydride, it forms cymene (CoH14), and
when similarly treated with PCl3, it forms cymene and hydro-chloric
acid. With nitric acid it forms camphoric acid (CoH16O4), a dextro-
rotatory body. It is acted on by bromine, forming Ciołł16Br2O ; other
compounds are also formed by it with bromine, such as monobromcamphor
(CoH.BrO). Chlorine is without action upon it. Heated in sealed
tubes with an alcoholic solution of caustic soda, it is resolved into
camphol (CoHisO) and camphic acid (C10H16O2).
Borneo camphor (CoH16O) is an exudation from the Dryabalanops
camphora. It crystallizes in prisms. By distillation it yields a vola-
tile oil called borneene (CoH16), which is often sold in the market as
camphor oil, or liquid camphor.
By oxidation with nitric acid, Borneo camphor forms common cam-
phor; whilst, by the action of metallic sodium on a solution of com-
mon camphor in toluene, it may be converted into Borneo camphor.
Common camphor rotates a ray of light to the right. The camphor
contained in the oil of feverfew rotates it to the left. The camphor in the
essential oils of the N. O. Labiatae are optically inactive. The cam-
phoric acids respectively formed from these camphors by the action
upon them of nitric acid, have similar optical effects to the camphors
themselves, but if the right and the left rotatory acids be mixed toge-
ther in equal proportions, the acid formed is found to be without
action on the polarized ray.
III. Resins.
Resins are bodies which exude from plants, dissolved in the essential
oil peculiar to the plant. They are for the most part oxidized tere-
benes, and are produced in the plant by the oxidation of their essential
oils.
Preparation.— (1.) By simple exudation. Example—Copal.
(2.) By distilling the oil from the resin in which it is dissolved.
Example—Common rosin.
(3.) By destructive distillation. Examples—Guiacum, pitch.
Properties.—(a.) Physical.—The resins are solid transparent bodies,
sometimes crystallizable. They have no well-marked odor. They
are easily fused, but they are not volatile. They are decomposed
when heated in closed vessels. They are insoluble in water, but are
soluble in spirit. They are electrical insulators, and yield, by friction,
negative electricity.
(3.) Chemical.—The resins are combustible, and burn with a white
flame. Many of them are acid to litmus (as, e.g., sandarach and
554 HANDBOOK OF MODERN CHEMISTRY.
guiacum), and yield a lather when acted on with an alkaline lye.
This mixture, however, differs from a soap solution in not being pre-
cipitated on the addition of common salt.
The resins generally are compounds of more than one resin; their
exact proximate constitution is not, in the majority of cases, well
understood.
Varieties of Resins.
Resins.
Source.
Brown . .
White . .
Common rosin
(colophony)
Amber - - e e
Arnicin (C20H200.)
Cannabin . . e tº
Capsicum resin
Castorin . . • *
Copal e O e ‘e
Dammar resin . . * -
Dragon's blood (C20H2004)
Ergotin . . tº e + ºr
Guiacum resin
Jalap resin e tº
Koussin (Cai Hasſ) to)
Lac tº ſº
The residue of American turpentine (pinus abies).
(Galipot). The residue of Bordeaux turpentiné (pinus
maritima).
A fossil resin.
The active principle of arnica root (arnica radix).
Indian hemp (cannabis indica).
Obtained from the fruit of the capsicum.
Castor is the dried preputial follicles and secretions of the
beaver.
An exuded resin from certain extinct trees (hymenaea
Verrucosa P). It is found beneath the ground.
An exudation from the fruit of a palm (calamus draco).
An active constituent of ergot.
From the wood of guiacum officinale.
From the jalap tubercles. It is insoluble in turpentine.
From kousso.
An exudation on certain trees (as the ficus indica) pro-
duced by the puncture of an insect (coccus).
From the stem of the mastic or lentisk tree (pistachia
lentiscus).
From the dried bark of the Daphne mezereum.
From the stem of the spruce fir (abies excelsa).
From podophyllum root.
Mastich ..
Mezereon resin
Burgundy pitch
Podophyllum resin
Pyrethrin . . tº º From pellitory root.
Rhubarb resin From rhubarb.
Rottlerin . . From kamala.
Sandarach .. From the juniperus communis.
f
1. Common rosin (colophony) is the residue of the distillation of
turpentine. The quantity obtained varies from 75 to 90 per cent. of
the turpentine employed. It is a mixture of two acid bodies, viz., a
crystallizable acid called abietic acid (C,EIS,05), and an amorphous
acid called pinic acid (CoofſsoC)2). -
2. Lac is an exudation from certain trees, occasioned by the punc-
ture of an insect. “Stick lac * is the crude state in which the resin
is collected. “Seed lac” is the resinous residue left after boiling the
crude lac with a solution of sodic carbonate, in order to extract from it a
red-coloring matter (lac-dye) used by the dyer. “Shellac" is the fused
“seed-lac.” This resin is largely used for hats, sealing-wax, and var-
nishes. “Indian ink” consists of a mixture of shellac (100 grs.),
borax (20 grs.), lampblack and water (4 ozs.). “Lacquer” is an
alcoholic solution of shellac, Sandarach, and Wenice turpentine.
RESINS. 555
3. Amber is a fossil resin found accompanying lignite. It is soluble
in alcohol (1 part in 8), and in ether (1 in 10). It is more soluble in
these liquids after it has been fused than before. When acted on
with nitric acid or digested with alkalies, it yields succinic acid.
4. Copal differs from other resins by its comparatively slight solu-
bility in alcohol and in essential oils. When melted, however, it
mixes with oils, and is thus made into varnish.
5. Guiacum resin is the exudation from the wood of the guiacum
officinale. It is soluble in alcohol. Oxidizing agents, under the influ-
ence of certain organic substances, produce a blue, green, and brown
color with the alcoholic solution.
Uses of Resins.—For varnishes. For stiffening purposes; for
yellow soap, and for sealing-wax.
In the manufacture of varnishes, the powdered resin (copal, mastic,
sandarach, lac, elemi and anime being those most frequently used) is
mixed with some powdered glass, so as to prevent its becoming
lumpy. The solvents principally employed are turpentine, methylated
alcohol and wood spirit; in the case of copal, mastic and sandarach,
certain liquids such as acetone, a little turpentine or some fixed oil,
(such as linseed or poppy) are commonly added to prevent the varnish
cracking when dry (oil warnishes). Spirit varnishes dry rapidly;
oil warnishes dry slowly, but are more durable.
IV. Gum Resins.
Definition.—Mixtures of a resin or of an oleo-resin and gum.
Gum resins form an emulsion when rubbed up with water, i.e., the
particles of resin are held in suspension by the solution of gum.
The gum resins are soluble in dilute alcohol and in weak alkalies.
They form a numerous class, amongst which may be mentioned
ammoniacum, assafoetida, aloes, euphorbium, galbanum, gamboge,
myrrh, Olibanum or Arabian frankincense, and scammony.
W. Oleo-Resins.
Definition.—A mixture of a resin and a volatile oil.
This class includes copaiva, the turpentines, common frankincense,
(Pinus Toeda), Canada balsam (the turpentine from the Balm of
Gilead fir), Sumbul root, etc. -
WI. Balsams.
Definition.—A resin, or an oleo-resin, containing benzoic or
cinnamic acid. (Ilſemo. Balsam of Copaiba and Canada balsam are not
true balsams, as they neither contain cinnamic nor benzoic acid).
This class includes benzoin (styrax benzoin), balsam of Peru
(myroxylon Pereira), balsam of tolu (myroxylon toluifera), storax
(liquidambar orientale), etc.
556 HANDBOOK OF MODERN CHEMISTRY.
India Rubber—Caoutchouc.
Natural History.—A milky juice, solidifying on exposure to air.
It is obtained from many tropical plants, such as the Ficus elastica,
etc.
Constitution.—A mixture of several isomers and polymers of tur-
pentine oil.
Preparation.—The juice, which is perfectly white and liquid when
first obtained, flows from incisions made in the tree, and is then dried
on clay moulds.
Properties of the solid caoutchouc.—An elastic solid. Specific
gravity 0.93. It melts at 250° F (120.9°C.) When heated slightly
beyond its melting-point, it forms a liquid which does not solidify on
cooling. At a higher temperature it is decomposed into two liquids,
viz., isoprene (C5Ha), boiling at 98.6° F (37° C.), and caoutchine,
boiling at 339.8°F. (171°C.), and in both of which liquids caoutchouc
is soluble. It is insoluble in alcohol or in water, but is softened by
boiling water. It is soluble in ether, in naphtha, and in the volatile
oils, and remains unchanged as the solvent evaporates. Neither
alkalies, dilute acids, nor indeed chemical reagents generally, have
any action upon it. It combines with about 2 to 3 per cent. of
sulphur when melted in contact with it, forming “Vulcanized India
I&ubber,” which is a more elastic body than rubber, but is insoluble in
naphtha or in turpentine, and is incapable like rubber, of cohering
to other surfaces with which it may be brought into contact,
Uses :—
1. For general cleansing purposes.
2. For waterproofing.
3. For vulcanized India rubber. Most specimens of vulcanized
rubber contain more than 2 per cent. of sulphur. Under such cir-
cumstances the rubber after a short time becomes inelastic and brittle,
owing to the oxidation of the free sulphur.
4. For ebonite (vulcanite). This is prepared by mixing caoutchouc
with about half its weight of sulphur, and afterwards hardening the
mixture by heat and pressure. It takes a high polish.
5. Marine glue is a solution of Caoutchouc mixed with a little shellac,
in coal tar naphtha.
Gutta Percha.
Natural History.—A milky juice exuding from the Isonandra
percha, and solidifying by exposure to air.
Composition—Similar to that of caoutchouc.
Properties.—An inelastic solid; specific gravity 0.98. It is in-
soluble in water, alcohol, acids or alkalies, but is soluble in ether,
volatile oils, chloroform, carbonic disulphide, naphtha, etc. It
softens at 212°F. (100° C.) and decomposes at 400°F. (204.4° C.)
It may be vulcanized like caoutchouc.
557
CHAPTER XXIII.
TELE ALCOHOLS.
Relation of Alcohols to other Bodies—Series of Alcohols—General preparation and
properties of the members of the various Series—Mercaptans.
SUPPLEMENTARY CHAPTER : Sugar — Glucosides — Starches — Gums — Reaction of
various Alcohols and allied Bodies.
The alcohols are saturated derivatives of the hydrocarbons, one or
more atoms of the hydrogen of the hydrocarbon being replaced by a
semi-molecule of hydroxyl (OH); in other words, the alcohols are
compounds of hydroxyl and alcohol radicals.
(a.) If 1 hydrogen atom only of the hydrocarbon be replaced by
1 of the group (OH), a monohydric alcohol is formed. Thus C3H1(OH),
a derivative of CAHs, constitutes monohydric propylic alcohol.
(6.) If 2 or more hydrogen atoms be replaced by 2 or more of the
group (OH), a dihydric (or trihydric, etc.) alcohol is formed. Thus
C3H3(OH)3 constitutes the trihydric alcohol glycerine.
The exact relationships of the alcohols must be noted.
Relation of the alcohols to the haloid ethers.-If the group or groups
of (OH) in the alcohol, be replaced (partly or wholly) by chlorine, (as
e.g., by the action upon the alcohol either of a haloid acid, or of a com-
pound of phosphorus with a haloid), a haloid ether is formed. Thus
propylic alcohol, C3H1(OH), forms propane chloride, C3H1(Cl).
If this haloid ether be treated with potassic or sodic hydrate, the
alcohol will be reformed ; thus:–
C3H7(Cl) + ROH C.H. (OH) + ICC1.
Propane + Potassic = Propylic + Potassic
chloride hydrate alcohol chloride.
Relation of the alcohols to the oacy-ethers.-If the group or groups of
(OH) in the alcohol be replaced by potassoxyl (OK) or methyloxyl
(OCH3), etc., an oacygen ether is formed. Thus—
Ethylic alcohol (C2H3(OH) forms C.H. (OK), potassic ethylate :
5 y ,, C.H3(OCH3), methylic ethylate, etc.
Relation of the alcohols to the compound ethers (ethereal salts).-If the
hydrogen of the hydroxyl (OH) in the alcohol, be replaced by an acid
radical, an ethereal salt is formed. Thus—
Methylie alcohol, CH3(OH), forms CH3(OC.H.,0), methylic acetate.
Constitution.—An alcohol may be regarded as formed on the water
type, where one atom of hydrogen is replaced by a compound radical.
Thus—
º O = C.H.3(OH) º
* - C.H. (OH)
H Ethylic alcohol;
O = Propylic alcohol.
558
HANDBOOK OF MOI).ERN CHEMISTRY.
$
The alcohols may be arranged in the following groups:—
SERIES.
Formula.
Examples.
A.—MonoHYDRIC ALCOHOLS—
I. Ethylic series ..
II. Vinylic series
III.
IV.
W. Benzylic series. .
VI. Cinnamic series
VII.
B.—DIHYDRIC ALCOHOLS—
I. Glycols
II. Orcins * @ &
C.—TRIHYDRIC ALCOHOLS—
I. Glyceric series . .
II. Pyrogallic series
D.—TETRAHYDRIC ALCOHOLS-
E.—HEXHYDRIC ALCOHOLS—
Il-º-º-20-13
CnH2n(OH)2
Culian-s(OH),
CnH2n-1(OH),
CnH2n-2(OH)3
CnH2n-2(OH),
CnH2n-4(OH)6
Methylic alcohol, CH,(OH).
Vinylic alcohol C, H2(OH).
Propargylic alcohol Č.H. (Ó EI).
Phenol C.H.(OH).
Cinnamic alcohol C,EI,(OH).
Glycol C.H.,(OH),
Orcin CeBI,(CH4)(OH)2.
Glycerin C.H.(OH),
Pyrogallol &#,(off),
Erythrite C.H. (OH).
Mannite CsII2(OH)6.
A.—MONOHYDRIC ALCOHOLS.
Ethylic Series.
SERIES I.-Formula C, Han 11(OH).
This includes—

Specific G Boiling Pt. V
Alcohols. Formula. Pº I”, Dºğ. Source.
o F.
1. Methylic (wood
naphtha) . . . . . CH3(OH) 0.798 at 20 | 1510 | 66-1 || 1:12 || Destructive distillation of wood.
2. Ethylic (spirits of
wine) . . . . . . . C., H2(OH) 0.7938 at 15 173-0 || 78.3 | 1.61 | Fermentation of sugar.
3. Propylic . . C., Hy(OH) ()'R205 at 0 | 206'0 96*6 || 2:02 Ditto of grape husks.
4. Butylic . . . . . . C., Ho (OH) Ú-8032 at 18 233-0 || 111°7 2'59 Ditto of beet rout.
5. Amylic (fusel oil ;
pentylic) . . . . . . C.H. (OH) || 0-8111 269.8 || 132-1 || 3:15 IDitto of potatoes.
6. Hexylic (caproic). Co Haa (OH) || 0-819 at 23 309-0 || 1539 || 3:53 Dilto of grape husks.
7. OEnanthic(heptylic) || C. His (OH) 343'0 || 172-8 Distillation of castor oil with
HO.
8. Caprylic (octylic).. Cs Haz (OH) || 0-87.17 at 16 || 356-0 | 180-0 || 4'50 | Fermentation of grape husks.
9. Nonylic . . . . . . . . Co Hio (OH) 392:0 | 200-0
10. Rutic (decatylic) . . . Cao Ha (OH) 414'0 212°2 Oil of rue.
11. Lauric . . . . . . . . . C., a HasſOH) Whale oil.
12. Cetylic (ethal) Cae Haa(OH) Spermaceti ; fuses at 122°F.
13. Cerylic (cerotene). , | Can H35(QFI) Chinese wax ; fuses at 174° F.
14. Melissic (melissine) || Cao Ha 1(OH) Beeswax ; fuses at 1859 F.
Isomeric forms.--All these alcohols (excepting
isomeric modifications.
have numerous
the two first terms)
They are distinguished
partly by their different physical properties, such as by their different
boiling-points, but more especially by their behaviour on oxidation.
To Kolbe we are indebted for a systematic arrangement of these iso-
MONOHYDRIC. ALCOHOLS. 559
merides. To methylic alcohol (CH3OH) he has given the name
carbinol, whilst all the succeeding alcohols he terms carbinols, regarding
them as derivatives of the first term (methylic alcohol), and formed by
the replacement of hydrogen by monad radicals of the form C, H2n + , :
(a.) If, judging by its preparation and by its mode of formation,
the alcohol be formed by the replacement of 1 unit of hydrogen of the
carbinol by the compound group (C,EI2n + 1), the alcohol is then called
a primary alcohol. Thus, (CH3.OH) being carbinol—
CH,(CHA)0II is the primary alcohol methyl carbinol (ethylic alcohol).
CH,(C.H.) OH 5 y } } ethyl carbinol (propylic alcohol).
(3.) If two units of hydrogen of the carbinol be replaced by 2 of the
group (C, H2n+1), the alcohol is then called a secondary alcohol. Thus—
CH(CH2)(CH.)0FI is the secondary alcohol dimethyl carbinol (propylic alcohol).
CH(C.H.)(CH.)0H 5 3 5 y ethylmethyl carbinol (butylic alcohol).
(y.) If three units of hydrogen of the carbinol be replaced by three
of the group (CAH2n+1), the alcohol is then called a tertiary alcohol.
Thus—
C(CH2)(CH,)(CH.)0H is the tertiary alcohol trimethyl carbinol (butylic alcohol).
C(C.H.)(CHA)(CH3)0H , 3 y ethyldimethyl carbinol (amylic alcohol).
It will therefore be understood that an alcohol is regarded as
primary, secondary, or tertiary, according as the carbon atom in com-
bination with the hydroxyl group, is also directly combined with 1, 2,
or 3 other carbon atoms. It will further be evident why no isomeric
modifications of methylic or ethylic alcohol are possible.
The following list includes the principal secondary alcohols : —
Boiling point.
Formula. 9 p
• F. o C.
Dimethyl carbinol . . . . . . . . CH(CH),0H 185 85-0
Ethyl methyl carbinol . . . . . . . CH(CH2)(C.H.)0H 207 97.2
Methyl-isopropyl carbinol . . . . CH.CH(CH3)3OH 226 107-8
Methyl propyl carbinol. . . . . . . CH(CH2)(C, H,)0H 24 S 120-0
Methylbutyl carbinol . . . . . . . CH(CH2)(C.H.)0H 277 136 - 1
Methyl pentyl carbinol . . . . . . . CH(CHS)(Cs Hil)0BI 320 160-0
Methyl hexyl carbinol . . . . . . CH(CH2)(CSH13)OH 35S 1 SI - I
Methyl nonyl carbinol . . . . . . . CH(CH2)(C,EIlo) OH 445 225-5
The following tertiary alcohols are known :-

Boiling point.
Formula. *===
o F. o C.
Trimethyl carbinol. . . . §§ H 179
Dimethyl ethyl carbinol C(CHS),(C,EIs)0H 212
Dimethyl isopropyl carbinol . . C(CH2)2(CH3)2CH.0H 234
Dimethyl propyi carbinol . . . . C(CH.). (C.H.)0H 239
Methyl diethyl carbinol. . C(CH2)(C, Hs),0H 248
Triethyl carbinol . . . . Gö. H.),6H 284
Diethyl propyl carbinol.. C(C,EIs),(C,EI)0H
560 HANDBOOK OF MODERN CHEMISTRY.
It will be convenient here to note the different effects of oxidizing
agents on these three classes of alcohols:—
(a.) Primary alcohols.-These yield, by oxidation, three products;
viz., (1) an aldehyde; (2) a monobasic acid; and (3) an ethereal salt, the
relative quantities of each of these products being dependent on many
causes, such as the temperature, the alcohol, the oxidising agent, and
the quantity of water present. Thus:–
(1.) CH2CH2(OH) + O = CH3COH + H2O.
Ethylic alcohol + Oxygen = Acetic aldehyde + Water.
(2.) CH,COH + O = CH3COOH.
Acetic aldehyde + Oxygen = Acetic acid.
(3) CH,COOH + C, H2(OH) = CH3COO(C.H.) + H.O.
Acetic acid + Ethylic alcohol = Ethylic acetate + Water.
Thus a primary alcohol yields on oacidation, an aldehyde, an acid con-
taining the same number of carbon atoms as the alcohol oacidised, and an
ethereal salt.
(6.) Secondary alcohols.-These yield no aldehyde on oxidation, but
(1) a ketone, which, by the prolonged action of the oxidising agent,
becomes (2) an acid, but which acid contains a less number of carbon
atoms than the alcohol oacidised. g
(y.) Tertiary alcohols.-These yield no ketone, and no aldehyde on
oxidation, but one or more acids of the acetic series. Possibly a ketone
may be formed, but it has never yet been discovered.
Preparation (General Methods) of the Normal Primary Alcohols.
(1.) From the paraffins (C, H2n+2).—This is illustrated in the pre-
paration of methylic alcohol from methane (CH4), as follows:—
(a.) A monochlorinated derivative of the paraffin is first formed, by
the action of chlorine on the paraffin. Thus:–
CH, -i- Cl3 = HCI + CH,Cl.
Methane + Chlorine = Hydrochloric acid + Methyl chloride.
(6.) By the action of argentic acetate on this chlorinated derivative,
an ethereal salt is formed. Thus, e.g. : —
CH3Cl + AgC2H3O2 = AgCl + CH3(C2H4O2).
Methyl + Argentic = Argentic + Methylic
chloride acetate chloride acetate.
(y.) By the action of potassic hydrate on this ethereal salt, potassic
acetate and methylic alcohol are formed.
CH,(C.H.O.) + KHO = CH3(OH) + KC.H.O.
Methylic + Potassic = Methylic + Potassic
acetate hydrate alcohol acetate.
[Conversely it may be noted that the alcohol may be converted into
its corresponding paraffin by first forming from it a chlorine deriva-
tive, and then acting on the chlorine derivative with nascent hydrogen
(see page 530).] -
(2.) From the olefines (C,EIan).-This may be effected by two
MONoHYDRIC ALCOHOLs. 561
methods, which may be illustrated in the formation of ethylic alcohol
from ethylene (C2H4):—
(A.) (First process.) (a.) The olefine is first acted on with sulphuric
acid, whereby an acid ether of sulphuric acid is formed. Thus:–
C.H., + H.SO, - C.H.S.HSO4.
Ethylene –H Sulphuric == (Sulpho-vinic acid) or
acid hydric ethylic sulphate.
(3.) This ethereal salt is now distilled with water, when the alcohol
and sulphuric acid are formed. Thus:—
Sulpho-winic + Water - Ethylic + Sulphuric
acid alcohol acid.
(B.) (Second process.) (a.) By the action of hypochlorous acid
on the olefine, a monochlorinated monohydric alcohol is formed.
Thus :-
C2H4 + EICIO = C.H,Cl(OH).
Ethylene + Hypochlorous = Chlorinated ethylic
acid alcohol.
(6.) When this is acted on with nascent hydrogen, the alcohol and
hydrochloric acid are formed,
C.H.Cl(OH) + H2 =C.H. (OH)+ HCl.
Chlorinated ethylic + Hydrogen = Ethylic + Hydrochloric
alcohol alcohol acid.
[Conversely, by the abstraction of the elements of water, the olefine
may be prepared from the alcohol. Thus:–
C.H3(OH) — H2O = C2H4. |
Ethylic alcohol — Water = Acetylene.
(3.) From the normal primary (a) aldehydes, or from the (3) anhydrides
of the acetic series.—By the action of nascent hydrogen in each case:—
(a.) H(COH) + H. = CH3(OH); CH3(COEI) + H2 = C, H2(OH).
Formic + Hy- = Methylic Acetic + Hy- = Ethylic
aldehyde drogen alcohol; aldehyde drogen alcohol.
[By the action of nascent hydrogen on the isoprimary aldehydes of
the acetic series, isoprimary alcohols are formed.]
(3.) §o + 4H2 = 2ſC.H3(OH)] + OH2.
Acetic + Hydrogen = Ethylic + Water.
anhydride alcohol
(4.) One alcohol may be prepared from the alcohol immediately pre-
ceding it in the series.—Thus formic aldehyde yields methylic alcohol,
and methylic alcohol may be made to yield ethylic alcohol. Thus:–
(a.) Iodomethane (CH3I) is first formed by the action of hydriodic
acid on methylic alcohol.
(3) Cyanomethane (CH3(CN)) is then formed by the action of
potassic cyanide on iodomethane.
- O O
562 HANDBOOK OF MODERN CHEMISTRY.
(y.) Sodic acetate (NaC., H3O2) is formed by digesting cyanomethane
with sodic hydrate.
(6.) Acetic aldehyde (CH3COH) is formed by distilling sodic acetate
with potassic formate.
(e.) Ethylic alcohol (C2H3(OH)) is formed by the action of nascent
hydrogen on acetic aldehyde.
Similarly normal primary propylic alcohol may be prepared from
ethylic alcohol, etc.
Normal secondary alcohols are prepared (a) by the action of nascent
hydrogen on the normal primary ketones, and (3) from the normal
primary paraffins.
Tertiary alcohols may be prepared by the action of water on the
product formed by the action of the zinc organo-metallic compounds
on the acid chlorides of the form C, H2n+1COCl.
General Properties.—(a.) Physical. — All the alcohols of the
ethylic series are colorless, and possess a more or less powerful odor.
The first nine are colorless liquids. The first two (methylic and
ethylic alcohol) are mobile liquids, and are soluble in water in all
proportions, but the third (propylic alcohol) has not unlimited solu-
bility. From this point the liquids get thicker, their boiling
points higher, and their solubility in water less. Thus butylic alcohol
is not very soluble, amylic alcohol is very sparingly soluble, and
hexylic alcohol is insoluble in water. Caprylic alcohol leaves a
greasy stain when dropped on paper. From nonylic alcohol down-
wards, the members of the series are solid.
One molecule in each case yields two molecules of vapor.
(6.) Chemical. With phosphorus pentasulphide, the ethylic series
form mercaptans or sulphydrates (5(C2H3(OH))+P.Sg=5(C2H5(SH))
(ethylie sulphydrate) + P.O;); with oxyacids they form ethereal salts
(C.H3(OH) + HNO3 = (C.H.S)NOs (ethylic nitrate) + H2O); with
haloid acids or with compounds of phosphorus and the haloids, they form
monohaloid derivatives of the corresponding paraffins (CH3(OH) +
HI = CHAI (iodomethane) + H2O); with the alkaline metals, hydrogen
is evolved, and a metallic derivative formed (2(C.H3(OH)) + Naz =
2(C.H. (ONa))+H.), which metallic derivative is decomposed by
water, with the formation of a metallic hydrate and the alcohol
(C.H.(ONa) + H2O = C, H2(OH) + NaHO). Their reactions with
oacidizing agents have been described (p. 560), whilst with dehydrating
agents the corresponding olefine is formed by the abstraction of water
(C.H.(OH) – H.0 = C.H., + H2O).
(1.) Methylic Alcohol. (CH3OH) or Me(OH). [Molecular
weight 32. Molecular volume | | | . Specific gravity, 0.798. Boils at
151.7° F (66.5° C.) 100 c.i. of the vapor weigh 24.684 grs., and
1 litre 1,433 grins.]
Synonyms.--Carbinol; Wood or Pyroxylic spirit; Hydroxymethane;
Pyroligneous ether.
METHYLIC ALCOHOL. - 563
A
Preparation.—1. From the paraffin methane (General Methods, 1).
2. From formic aldehyde (General Methods, 3 (a).
3. By the action of potassic hydrate on the oil of the Gaultheria
procumbens (wintergreen; methylic salicylate).
[This oil was the first vegetable product prepared artificially.
Thus:—By the action of potassic hydrate on salicin, salicylic acid
is formed, and this, when distilled with wood spirit and sulphuric
acid yields the artificial oil.]
CºH,(OH),CO.CH, + KHO = C5H,(OH).CO.K -- CH3(OH).
Methylic salicylate + Potassic = Potassic salicylate + Methylic
hydrate alcohol.
4. By the action of heat on the nitrite of methylamine —
(a.) Methylamine is formed by the action of nascent hydrogen on
hydrocyanic acid ; thus —
EICN + 2H2 - CHs.H.N.
Hydrocyanic acid + Hydrogen -: Methylamine.
(3). By boiling the solution of nitrite of methylamine, nitrogen,
water, and methylic alcohol are formed ; thus—
Nitrite of methylamine = Nitrogen + Water + Methylic alcohol.
5. Commercial process. It is prepared from the watery liquid, or crude
wood vinegar as it is called, produced by the destructive distillation of
wood, and which contains 1 part of naphtha and 20 parts of acetic acid.
This watery liquid is first of all distilled, the portion that distils
over at a temperature below 212°F. (100° C.), being collected sepa-
rately. This contains methylic alcohol, acetone, acetate of methyl,
and certain oily substances to which its odor is largely due. To this
distillate slaked lime is added, and the clear liquor (that is, the liquid
drawn from the centre, by which means the lime which sinks and the oil
that floats are avoided) is several times redistilled. This distillate is
now saturated with calcic chloride, whereby a crystalline compound
(CaCl2,4CH2O), containing four molecules of methylic alcohol and one
molecule of calcic chloride, is formed. This solid residue is now heated
below 212°F. (100° C.), (beyond which temperature it would be de-
composed), to drive off any acetone or methylic acetate present.
Water is now added to the dried residue to decompose it, and the
alcohol distilled off. Finally the methylic alcohol is purified by
rectification, and rendered anhydrous by distillation after digestion
with powdered quicklime.
The purest methylic alcohol is prepared by the action of water on
methylic oxalate.
Properties.—(a.) Physical. When pure, methylic alcohol is a thin
colorless liquid, having a taste and odor very like ethylic alcohol. The
crude alcohol has an offensive odor and a burning taste. Specific
564 - HANDBOOK OF MODERN CHEMISTRY.
gravity 0.798 at 20° C. Boiling point 151-7° F (66.5°C.). It mixes
with water (condensation resulting) in all proportions, and it is (like
ethylic alcohol) a solvent of resins, volatile oils, etc.
(3.) Chemical.—It unites with certain salts in the capacity of water of
crystallization (e.g. CaCl2.2CH3.OH). It unites with the alkaline metals,
forming methylates, hydrogen being evolved (2CHs.OH + K. =
2CH3.O.K -- H3); it also dissolves caustic soda, potash, baryta, etc.
(BaO,2OH.O). Distilled with chloride of lime and water it forms
chloroform (see Chloroform); by ocidation, as by exposure to air on
platinum black, it yields formic acid (CH3(HO) + O. = H20 +
CH.O.). -
It burns in lamps yielding a pale-colored flame, which deposits
Ino SOOt.
Uses.—In the arts it is employed as a solvent of resins for var-
nishes, and for burning in lamps as a heating power only. Also for
mixing with pure alcohol to form methylated spirit (= ethylic alcohol
90 parts—methylic alcohol 10 parts. Specific gravity 0.83).
(2.) Ethylic Alcohol (C2H3(OH) or Et (OH). [Molecular weight
------
46. Molecular volume | | | . Specific gravity 0.7938 at 15° C. Boiling
point 173° F (78.4° C.).]
Synonyms.-Alcohol; Vinic alcohol ; Spirits of wine; Methyl carbinol,
CH3(CH2OH); Hydroxyl ethene.
Preparation.—(1.) From the olefine ethylene, C.H.4 (see General
Methods 2). -
[Note. Ethylene may be prepared by the direct union of carbon
and hydrogen.]
(2.) By the fermentation of grape sugar.
Properties.—A colorless liquid having an agreeable taste and odor.
It burns with a non-luminous smokeless flame, requiring three times
its own volume of oxygen for complete combustion. When imper-
fectly burnt, an acrid volatile compound is formed. Anhydrous
alcohol boils at 173° F (78.8° C.) at standard pressure. By dilution
the boiling point becomes gradually higher.
It has never been frozen.
Action of water on alcohol.—Alcohol is very hygroscopic, and mixes
with water in all proportions, heat and contraction of volume result-
ing from their admixture.
To determine the amount of alcohol present in any mixture, a given
quantity must be distilled until all the alcohol has passed over. The
distillate is then to be weighed, and its specific gravity taken, the
percentage of alcohol being determined by table (Table VII.).
Proof spirit (that is the weakest spirit that will fire gunpowder
when moistened with it and ignited), has a gravity of 0.92 and con-
tains in every 100 parts by weight—
Water tº º º tº dº wº tº º & 50-76.
Alcohol tº º º tº ºf e tº e º 49.24.
ETIIYLIC ALCOHOL. 565
A weaker spirit does not fire gunpowder, and is termed “under
proof,” a stronger spirit being spoken of as “over proof.” -
By distillation, a weak spirit may be made to yield a 90 per
cent. alcohol (that is, a spirit containing 90 per cent. of alcohol), but
distillation will not effect the separation of the last 10 per cent. of
water. A further separation of 5 per cent. of water (that is, the
formation of a 95 per cent. alcohol) may be effected by enclosing the
alcohol in a bladder, through which the water exudes more rapidly
than the alcohol. An alcohol of 89 per cent. may be obtained by
dissolving dry potassic carbonate in the alcohol to saturation. The
solution separates into two layers, the upper consisting of spirit
of 89 per cent., and the lower of water, containing potassic carbo-
nate in solution. Absolute alcohol (100 per cent.) is prepared by
digesting the alcohol with quick lime for three or four days, and dis-
tilling. It is very hygroscopic.
Commercial rectified spirit contains 13 or 14 per cent. of water. Sp. Gr. 0-835.
25 proof 25 49-5 5 y 5 y Sp. Gr. 0.9198.
Alcohol dissolves numerous salts, but no salts are soluble in alcohol
that are insoluble in water. It dissolves most deliquescent salts, and
but few efflorescent salts. With some it forms definite crystalline
compounds, called alcoholates, i. e., salts containing alcohol in the
place of water of crystallization, as, e.g., ZnCl2,202 HSO, etc. These
bodies are decomposed by water. It also dissolves the alkaline
metals, hydrogen being evolved forming C.HsKO and C.H5NaO;
also the elementary gases O, H, and N ; also the gaseous hydrocarbons;
also certain organic bodies, such as the alkaloids, resins, essential
oils, etc.
When the vapor of alcohol is passed through a red-hot tube, it yields
marsh gas, carbonic oxide and hydrogen (C2H60=CH4+ H8+ CO),
other bodies, such as C.H6, C6H6, etc., being also formed.
Action of chlorine.—By the action of chlorine on absolute alcohol, con-
tinued until hydrochloric acid ceases to be evolved, ethylic acetate
and chloral hydrate (trichloraldehyde) are formed :-
2C2H5.0EI + 4Cl3 = CCls.CPI(OH)2 + C.H.Cl + 4HCl.
Ethylic + Chlorine = Chloral hydrate + Ethylic + Hydro-
alcohol chloride chloric acid.
By the action of chlorine on dilute alcohol, aldehyde but no chloral is
formed.
By the action of chlorine on alcohol in the presence of alkalies (or by
the action on the alcohol of chloride of lime), chloroform and carbonic
anhydride are formed. Thus—
C.H3(OH)+ 5Cl2 + H2O = CO2 + 7.HCl + CHCla.
Ethylic + Chlorine + Water = Carbonic + Hydrochloric + Chloroform.
alcohol anhydride acid
Numerous intermediate products may also be formed.
566 HANDBOOK OF MODERN CHEMISTRY.
By owidation alcohol (C.H.80) is converted into aldehyde (C.H.,0),
and finally, into acetic acid (C, H,02).
Sulphuric acid combines with dilute alcohol to form ethyl-sulphuric
acid (C2H5)PISO4. When sulphuric anhydride acts on anhydrous
alcohol, a white substance called ethionic oxide is formed (C2H4S2O6),
which, when dissolved in water, forms ethionic acid (C2H5S207).
When alcohol is allowed to act on fused potassic hydrate, hydrogen
is evolved and potassic acetate is formed. Thus—
KHO + C.H2(OH) = KC.H.O., + 2 H2.
Potassic hydrate + Alcohol = Potassic acetate + Hydrogen.
(3) Propylic Alcohol, C.H. (OH)—This alcohol exists in two
isomeric modifications, viz., a normal primary propylic alcohol, termed
ethyl carbinol, and a secondary isopropylic alcohol, called dimethyl carbinol.
These may be figured as follows—
Normal propylic alcohol Isopropylic alcohol
(primary). - (secondary).
=C.H.S.C.H.OH =CH(CHA).OH
H H
| |
C2H5—C—OH CH3–C–OH
|
EI CHs
(a). Normal propylic alcohol, or ethyl carbinol, may be prepared from
ethyl alcohol (see General Methods, 4, page 561). -
Properties.—An oily liquid, yielding propionic acid by oxidation.
(3.) Isopropylic alcohol, or dimethyl carbinol, may be prepared
from acetone (CH3)2CO" by the action upon it of nascent hydrogen.
Thus—
(CEIA),CO + H2 CH(CH),(OH).
Acetone + Hydrogen F Isopropylic alcohol.
Properties.—A colorless liquid; Sp. Gr. 0-791°F. at 15° C.; boils
at 185° F. (85°C.). It does not freeze at — 4°F. (–20° C.). It has
no action on a polarized ray of light. It forms hydrates of remark-
able stability. It yields, by oxidation, first (a), acetone; and finally
(3), acetic acid.
(a.) CH(CH)2(OH) + O = CO(CHA). -- H.O.
Isopropylic alcohol + Oxygen +. Acetone + Water.
(6.) CO(CH.). -- 20, - CH3CO2H + CO2 + H2O.
Acetone + Oxygen = Acetic + Carbonic + Water.
acid anhydride
(4.) Butylic Alcohol, C.H. (OH)—There are four isomeric modi-
fications of this alcohol. Thus—
(a.) CHA.C.H.CH2CH2(OH), propyl carbinol, or normal primary
WINY LIC SERIES. 367
butylic alcohol, may be prepared from butylic aldehyde by the action
of nascent hydrogen. It boils at 240.8°F. (116°C.).
On oridation it yields normal butyric acid—
C, H,(OH) + O. = C,B,CO(OH) + H2O.
Butylic alcohol + Oxygen = Normal butyric acid + Water.
(6.) CEI(CH3)2CH2(OH) isopropyl carbinol, or iso-primary butylic
alcohol, is found in the fusel oil formed when beet sugar molasses is
fermented. It boils at 228.2°F. (109°C.).
On oacidation it yields iso-butyric acid.
C.H. (OH) + O2 = CH(CH3)2CO(OH).
Butylic alcohol + Oxygen - Isobutyric acid.
(y.) C(CH2)(C2H4)H(OH). Methyl ethyl carbinol, or secondary
butylic alcohol, is prepared by the action of moist argentic oxide on
methyl-ethyl-iodo-methane, formed by distilling erythrite (C4H6(OH)4),
a saccharine substance, with fuming hydriodic acid. Thus—
C(CH2)(C2H4)HI + AgHO = AgI + C(CH2)(C2H5)PI(OH).
Methyl ethyl iodo- + Argentic = Argentic + Secondary butylic
methane hydrate iodide alcohol.
It is a colorless oily liquid, having a Sp. Gr. of 0-85° at 32°
F. (0°C.).
On oridation it yields, first, methylethylketone, and finally, acetic acid.
(6.) C(CH3)3OH.-Trimethylcarbinol, or tertiary butylic alcohol, is pre-
pared by the action of water on the product formed by the action of
acetic chloride on zincic methide. It boils at 180°5° F. (82.5°C.).
On oacidation it yields isobutyric, acetic and formic acids; also ace-
tone, isobutylene, carbonic anhydride, and water.
(5.) Amylic Alcohol (C5H11(OH)).--There may be as many as
eight isomeric modifications of this alcohol, five of which are known.
The ordinary amylic alcohol, or iso-amylic alcohol (isobutyl carbi-
mol), is the fusel oil of the distiller. It is said to be a mixture of
two different alcohols, one rotating a ray of polarized light to the
left, and boiling at 262.4°F. (128°C.), the other without polar action,
and boiling at 266°F. (130° C.). Amylic alcohol is an oily liquid,
having a Sp. Gr. 0-811 1. It imparts a transient greasy stain to paper.
On oxidation both the varieties named above, yield valeric acid.
C, H,(CH.)OH + O. = C, H,CO(OH) + H.O.
Amylic alcohol —H. Oxygen - Valeric acid + Water.
Vinylic Series.
SERIES II.-Formula C, Hen 10H.
The relationship between the vinylic series and the olefines, is
identical to that subsisting between the ethylic series of alcohols and
the paraffins. Thus:–
(a.) Paraffin; Methane CH, and CH3(OH) methylie alcohol.
(3.) Olefine; Ethylene C.H., and C.H. (OH) vinylic alcohol.
568 HANDBOOK OF MODERN CHEMISTRY.
This series includes—
1. Vinylic alcohol . . . . c.H.OH)
2. Allylic alcohol . . . . . . G.H.(OH)
(1.) Winylic Alcohol (C2H3(OH)).-It is prepared (a) by first com-
bining acetylene with sulphuric acid, and (3) afterwards distilling the
product with water.
(a.) C.H2 + H2SO, 2- (C.H.)HSO4.
Acetylene + Sulphuric acid - Sulphovinylic acid.
(3) (C2H3)]HSO, + H2O = H2SO, + C.H. (OH).
Sulphovinylic acid + Water = Sulphuric acid + Vinylic alcohol.
It is a pungent liquid, isomeric with aldehyde and ethylenic oxide.
(2.) Allylic Alcohol (CAH3(OH)). [Specific gravity at 32°F. (0°C.)
0-8709. Boiling point, 204.8°F (96°C.).]
Preparation.—It may be formed from glycerin, as follows:–
(1.) (a.) Allylic iodide (C3H51) is first formed by the action of phos-
phorus iodide on glycerin—
2(CAH3(OH)3)-1- P.I., = 2C3H3T + 2 H3PO3 + Iz.
Glycerin + Phosphorus = Allylic + Phosphorous + Iodine.
iodide iodide acid
(3.) Allylic oa'alate is then formed by the action of argentic oxalate
on allylic iodide—
2C3H3T + AgeC.O., — 2AgI + (CAH5)2C2O4.
Allylic iodide + Argentic oxalate = Argentic iodide + Allylic oxalate.
(y.) Allylic alcohol (+ oxamide) is then formed by the action of
ammonia on the allylic oxalate—
(C3H5)2C2O, + 2NHA = 2(C,EI,(OH)) + N.(C.O.)"H,
Allylic oxalate + Ammonia = Allylic alcohol + Oxamide.
(2.) By the action of heat on a mixture of glycerin and oxalic
acid.
C.H.(OH)3 + C.H.O. = 2EI,0 + 2CO2 + C, H2(OH).
Glycerine + Oxalic = Water + Carbonic + Allylic
acid anhydride alcohol.
Properties.—A colorless liquid. Sp. Gr. 0-8709. Boils at 204.8°F.
(96° C). It is combustible and soluble in water in all proportions.
Its reactions resemble those of ethylic alcohol.
With the haloids it forms both derivatives, such as C3H3Br, etc., and
compounds such as C3H3Cl2(OH). With sulphuric acid it forms allylic
sulphuric acid, (CAH3)HSO4. With the alkaline metals it forms sub-
stitution products. Wascent hydrogen has no action upon it. By owida-
tion it yields acrolein, formic acid and carbonic anhydride.
The allylic sulphide constitutes the oil of garlic [(C3H5)2S], and is
formed by acting on allylic iodide with potassic sulphide (a). Oil of
THE PHENOLS. 569
mustard contains allylic sulphocyanate, and is formed artificially by the
action of potassic sulphocyanate on allylic iodide (3).
Allylic + Potassic F. Potassic + Allylic sulphide
iodide sulphide iodide (garlic oil).
(3) C3H5I + ECNCS = RI + (C.H3)(NCS).
Allylic + Potassic sulpho- = Potassic + Allylic sulphocyanate
iodide cyanate iodide (mustard oil).
SERIES III.-Formula CAHan—3(OH).
This includes—
Propargylic Alcohol (C,E,(OH)). [Specific gravity, 0-9628 at 68°F.
(20°C.). Boils at 239°F. (115° C).]
Preparation.—By the action of potassic hydrate on mono-brom-
allylic alcohol—
C, H, Br(OH) + KHO = C, H2(OH) + KBr + H2O
Monobromallylic + Potassic = Propargylic + Potassic + Water.
alcohol hydrate alcohol bromide
Properties.—A colorless mobile liquid.
Benzylic Series—The Phenols.
SERIES W.—Formula C, Han–7(OH).
These alcohols may be divided into two classes :—

I. Benzylic Series (normal alcohols). Boiling Point. Melts at
* , Specific O {O KD TE
Alcohols. Formula. Gravity. F. °C. F. °C.
1. Benzylic . . . . C.H. (OH) 1-051 at 14°C. 403-7 206' 5
2. Xylilic (toluylic). . CsII2(OH) 42'2' 6 217-0 139-1 59.5
3. Cumilic. . . . . . Ciołlis (OH) 469°4 243-0
4. Sycocerylic .. ClaRes(OH) 194-0 || 90-0
II. Phenols.
1. Phenylic C.H. (OH) 1 - 068 356 180 95-0 || 35-0
2. Cresylic . . . . Ce(CH3)HA(OH) 383—39.2 195–200
3. Phlorol. . . . . . Cº(C.H.)H, (OH) || 1:037 at 12°C. 374–392 || 190–200
4. Dimethyl phenylic | Cs(CH3). Hs(OH) 410 210
(xylenol)
5. Thymylic Cs(C.H.), H2(OH) 428 220 111-2 || 44-0
These alcohols are derivatives of the C, Hen 6 series of hydro-
carbons, by the substitution of a semi-molecule of hydroxyl for one atom
of hydrogen.
They form well-marked substitution compounds when acted on by
570 HANDBOOK OF MOIDERN CHEMISTRY.
chlorine, nitric acid, etc., but they never form additive compounds; for
like the hydrocarbons, from which they are derived, they are fully
saturated bodies.
The haloid acids are without action on them, whilst with sulphuric
acid they yield sulphonic acids, which, by fusion with potassic
hydrate, are convertible into dihydric alcohols.
It will be noted that all the series of alcohols preceding the phenols,
differ strikingly in these respects from the phenols. (a.) They neither
form substitution compounds under the same circumstances, nor with
the same ease, as the phenols. (3.) With the haloid acids they form
derivatives, and (y) with sulphuric acid they form acid ethereal salts,
which, when treated with water, re-produce sulphuric acid and the
alcohol.
Lastly, the products of the oxidation of the phenols and of the
alcohols of the preceding series, are completely different.
Preparation.—(1) From the benzenes (C, H2n-6). The conversion may
be effected in one of two ways:—
(A.) By first acting on the hydrocarbon with sulphuric acid, and
afterwards fusing the potassic salt of the monosulphonic acid formed,
with potassic hydrate.
(B.) By the action of nitrous acid on the amido-derivative of the
hydrocarbon.
Benzylic Alcohol (C, H.OH or C6H3(CH2)OH). [Specific gravity,
1.051 at 14°C. Boils at 206.5°C.]
Preparation.—(1.) By the action of alcoholic potassic hydrate on
benzoic aldehyde (oil of bitter almonds)—
2C6H3COH + KHO C.H. (OH) + K(C, H,0)0.
Benzoic + Potassic = Benzylic + Potassic
aldehyde hydrate alcohol benzoate.
(2.) From toluene. By the action of potassic hydrate on toluylic
chloride.
C.H.Cl + KHO = C, H,(OH) + ECC].
Toluylic + Potassic = Benzylic + Potassic
chloride hydrate alcohol chloride.
(3.) By the action of nascent hydrogen on benzoic or hippuric acids.
Properties.—A colorless, oily, highly refracting liquid, insoluble in
water, but soluble in all proportions in alcohol, ether, acetic acid, and
carbonic disulphide. With hydrochloric acid it forms benzylic chloride,
C.H.C.H.C). With strong sulphuric acid it forms a resinous body.
Distilled with sulphuric and acetic acids, it forms benzyl acetate
(C, H,(OC.H.,0), a liquid having a pear odor. By oridation with nitric
acid it forms benzoic aldehyde, and with chromic acid benzoic acid.
Phenylic Alcohol (C6H3(OH)).-[Molecular weight, 94. Molecular
volume | | | . Specific gravity, 1.065 at 64.4°F. (18°C.). Fuses at
93.2°F. (34°C.). Boils at 370.4°F (188°C). 100 c. i. of vapor weigh
32.945 grms., and 1 litre 4:211 grims.].
PEIENYLIC AICOHOL. 57.1
Synonyms.-Carbolic acid; Phenylic acid; Phenic acid; Oay-benzene;
Phenol; Coal tar Kreasote.
Natural History.—It is found in the urine of cows and other
animals.
Preparation.—(1.) By the action of nitrous acid on amidobenzene
(aniline). Thus –
CºH (NH2) + HNO. = C5H3(OH) + H2O + N2.
Aniline + Nitrous = Phenylic + Water + Nitrogen.
acid alcohol
(2.) By distilling salicylic acid either alone or mixed with lime, etc.
Salicylic acid F. Phenylic alcohol + Carbonic anhydride.
(3.) (Commercial preparation.) The dead oil of coaltar is first distilled,
that portion which passes over between 300° and 400°F. (149° and
205°C.) being collected separately. This is shaken up with a hot
concentrated solution of sodic hydrate, which dissolves the carbolic
acid, and enables it to be separated from the oil that floats on the
surface. The alkaline solution is then decomposed with hydrochloric
acid, when the carbolic acid separates as an oily layer on the surface.
This is drawn off, digested with calcic chloride to remove the water,
and distilled. By exposing the distilled acid to a low temperature it
solidifies. The crystals are collected, drained, and again distilled.
Sometimes the dead oil (without distillation) is treated with a
mixture of slaked lime and water, and the solution which contains
the carbolic acid, drawn off from the oil which swims on the surface.
Tests for the purity of carbolic acid—
(1.) Shake up half a dram of the acid with half a pint of warm
water. The acid is perfectly soluble in the water, whilst any dead oil
present as an impurity of the acid will float on the surface.
(2.) Five parts of pure carbolic acid are soluble in a mixture of one
part of caustic soda and ten parts of water.
(3.) Expose a mixture of carbolic acid (3 parts by weight) and
water (1 part) to the cold of ice, when crystals are deposited having
the formula 2C6H6O.H2O soluble in alcohol, in ether and in water.
The crystals melt at 61°F. (16:1°C.).
To distinguish carbolic acid from kreasote (the product of wood)–
Ö5:
CARBOLIC ACID.
, Boils at 370° F. (187.8° C.)
. Does not affect a polarized ray.
. Is solidified by cooling.
. Forms a jelly when shaken with
collodion.
. Is soluble in a strong solution of
ammonia or potassic hydrate.
. Solubility in water; 1 in 20 at 212°
F.; 1 in 80 at 60° F.
aqueous
solution blue.
5:
7
e Solubility in water ;
KREAsote.
. Dries up at 212° F (100° C.).
. Rotates a polarized ray to the right.
. Not solidified by ice and salt.
. Is unaffected by collodion.
. Is insoluble in ammonia or in potassic
hydrate solutions.
1 in 130 at
60° F.
. Solution not colored blue by ferric
7. Ferric chloride turns the
. Ferric chloride turns the solution in
alcohol brown,
chloride.
. Ferric chloride turns the solution in
alcohol green.
572 HANDBOOK OF MOIDERN CHEMISTRY.
Properties.—(a.) Physical. Carbolic acid when pure, crystallizes in
colorless needles which are very deliquescent, and melt at 93.2° F.
(34° C.), forming an oily liquid, which boils at 370.4°F. (188°C.). It
has aspecific gravity at 18°C. of 1:065. Its odor is peculiar, and its action
caustic. It is not easily decomposed even by a red heat. Distilled over
heated zinc dust, it yields benzene. It is slightly soluble in water,
but is very soluble in alcohol and in ether, and is a solvent of sulphur,
iodine, etc. Its special action is antiseptic. -
Its appearance to the naked eye closely resembles kreasote, from
which it may be known by the tests already described.
(3.) Chemical. Its solution is not acid to litmus. The haloid
elements form with it substitution compounds (as C6H3Cl2(OH)
and C6Cl3(OH) pentachlorophenol). With nitric acid it forms
C6H4(NO2)OH, C6H3(NO2)3OH, and finally the substitution product
C6H2(NO2)3(OH), or picric acid. All its nitro derivatives decompose the
metallic carbonates. With sulphuric acid it forms phenol disulphonic
acid, C6H3OH(SO3H)2. The haloid acids are without action upon it.
The alkalies (but not the alkaline carbonates) dissolve it, forming
phenates. By oridation with chromic acid it yields phenoquinone.
3(C6H3(OH)] + Os + H2O = C5H,(O.OC, H3)2 + 3H2O.
Phenylic alcohol Pheno-quinone.
Cresylic Alcohol (cresol) C6H4(CH3)OH.—This occurs in three
modifications, which yield three isomeric cresol-sulphonic acids.
(a.) Paracresol is a solid crystalline body, boiling at 392° F.
(200° C.). When fused with potassic hydrate, paracresol yields potassic
paroxybenzoate, C6H4(OH)CO.K.
(3.) Metacresol is a liquid, and boils at 392°F. (200° C.). When
fused with potassic hydrate, metacresol yields potassic metoxybenzoate.
(y.) Orthocresol is a liquid, and boils at 372.2°F. (189° C). When
fused with potassic hydrate, Orthocresol yields potassic salicylate
(orthoxybenzoate).
Thymylic Alcohol C6(C.H.5). H3(OH).-The thymols exist in two
isomeric forms. Thymol (a) is found in the oil of thyme and other
plants. It is a crystalline solid, melting at 111:2° F (44°C.), and
boiling at 428° F (220° C.). By the action of sulphuric acid it is
completely converted into a sulpho-acid. Thymol (3) is a yellow viscid
oil which, by the action of sulphuric acid, is only very partially con-
verted into a sulpho-acid. - -
SERIES WI.-Formula C, H2n-6(OH).
This includes—
Cinnamic al- C, H,(OH) | Preparation.—By heating styracin with potassic hy-
cohol. drate. With nascent hydrogen it forms phenyl-
propylic alcohol and allyl benzene. By 03:idation
it yields cinnamic aldehyde. Melting point,
91.4° F.; 33° C. -
Cholesterin . . C. H. (OH) | A crystalline solid, present in different parts of the
- animal. It forms, by oxidation with chromic acid,
oxycholic acid, CºgPI,00s.
DIEHYDRIC ALCOHOL8. 573
B.—DIHYDRIC ALCOHOLS.
The Glycols.
SERIES I.-Formula C, H2n(OH)2.
This series includes—
Boiling Point.
Glycols. Formula.
o F. o C.
Ethylene glycol C.H.(OH), 387-5 197.5
Propylene ,, C.H. (OH), 370.4—372.2 | 188–189
Butylene , , C, Hs(OH), 361:4–363-2 | 183–184
Amylene , Cs H10(OH)2 350-6 177
Hexylene , , Cs B12(OH)2 404' 6 207
Octylene , , CeBIs(OH), 455—464 235–240
The glycols (or diatomic alcohols) may be regarded (1) as deri-
vatives of the paraffins, where two atoms of hydrogen are replaced by
two semi-molecules of hydroxyl (OH). Thus—-
Ethane C.Hg forms C.H.,(OH)2, glycol.
Propane C3Hs , , C3H6(OH)2, propylene glycol, etc.,
Or (2) they may be regarded as compounds of the olefines with hydroxyl.
Thus—
JEthylene C.H., + (OH)2 forms C2H4(OH)2, ethylene glycol.
Propylene C3H6 -- (OH), , , CaFI6(OH)2, propylene glycol, etc.
Preparation.—From the olefines. We may illustrate this in the pre-
paration of glycol :— .# -
(a.) A dibromide (C.H.Br.) is first formed by the action of bromine
on ethylene:—
(3.) A diacetate of the olefine is now formed, by the action of argentic
or potassic acetate on the dibromide. Thus:—
C.H. Brz + 2AgC.H.302 = 2AgBr + C.H. (C.H.O.).
Ethylene di- + Argentic = Argentic + Pthylenic
bromide acetate bromide diacetate.
(y.) A glycol (+potassic acetate) is now formed, by treating the
diacetate with potassic hydrate. Thus:–
C.H.4(C2H5O)2 + 2E EIO - 2KC., H3O2 -- C.H.,(OH)2
Ethylenic + Potassic = Potassic + Glycol.
diacetate hydrate acetate
Properties.—(a.) Physical. Ethylene glycol (commonly called glycol) is
the only member of the series that has been particularly studied. The
glycols are colorless liquids, without odor, freely soluble in water and
in alcohol, and also (excepting ethylene glycol) in ether.
(6.) Chemical. The reactions of the glycols are similar to those of
the monatomic alcohols, excepting in this, that having two semi-mole-
cules of replaceable hydroxyl, two series of products result.
574 EIANDBOOK OF MODERN CHIEMISTRY.
f
ducts. Thus:—
C.H.(HO)(NaO); C.H., (NaO)2.
Monosodic glycol; Disodic glycol.
With sodium and potassium the glycols form two substitution pro-
These compounds form the alcoholic ethers of the glycols when
treated with a monatomic alcoholic iodide. Thus:–
C.H.,(OH)(ONa) + C.H.I = NaI + C.H.,(C.H.,0)(OH).
Monosodic + Ethylic = Sodic + Ethylic ethynate.
glycol iodide iodide
Oaygen acids form with the glycols, ethereal salts, which are mono- or
di-acid, according to the proportions of the reagents respectively
used. The haloid acids and haloid phosphorus compounds form with
them mono- and di-haloid derivatives. Potassic hydrate, when heated
with glycol, forms potassic oxalate (C.H.(OH)2+2KHO=C.O.(OK).
+4H2). By oridation glycol yields (a) first glycolic acid (other acids,
varying with the glycol acted upon, being formed), and finally (3)
Oxalic acid.
Glycol + Oxygen = Glycollic acid + Water.
(6.) CH2(OH)CO(OH) + O. = C,02(OH)2 + H2O.
Glycollic acid + Oxygen = Oxalic acid + Water.
We may here note that the relationship between ethylic alcohol,
ethylic aldehyde, and acetic acid, finds its counterpart in that sub-
sisting between glycol, glyoxal (glycolic aldehyde), and Oxalic acid.
Thus : —
CH, CH2(OH), CHACOEI, CH,CO(OH);
Ethylic alcohol, Aldehyde, Acetic acid;
CH2(OH).CH2(OH), COH.COH, CO(OH)OO(OH).
Glycol, Glyoxal, Oxalic acid.
Between glycol and ethylic alcohol this point of difference is to be
noted,—that whereas alcohol forms only one substitution compound
with sodium, Sulphuric acid, etc., glycol forms two. Thus:–
Alcohol forms— Glycol forms—
C.H3(ONa), C.H.,(OH)(ONa) and C.H.,(ONa),
C.H3(HSO); C.H.(OH)(HSO) and C.H.(HSO).
By heating glycol with ethylenic oxide in sealed tubes, a series of
compounds called polyethylenic glycols (or alcohols) are formed. They
are the result of progressive condensation (although normal condensa-
tion to two volumes) with elimination of the elements of water. They
are syrupy liquids, diethylenic glycol boiling at 473° F. (245°C.),
each succeeding term of the series boiling at about 81 degrees
Fahrenheit (45° C.) higher than the one below it. The following
compounds are known :- -
TRIHYDRIC ALCOHOLs. . 575

Alcohol. Formula.
Diethylenic glycol C.H.,0a = 20.H.,(OH), — H:0
Triethylenic ,, . . . . . . . CeBI, 10, − 39. H.Q.H.), — 2H2O
Tetrethylenic ,, . . . . . . C, H,0; = 4G.H.Q.H), — 3H.Q
Pentethylenic , . . . . . . . Çıoğ,0s– 59.H.(QH)2 – 4H.Q
Hexethylenic , C.H.s0, = 60, H. (OH), — 5H2O
Orcins—Aromatic Glycols–Saligenin Series.
SERIES II.-Formula C, Han s(OH)2.
This series, the members of which are derivatives of benzene,
include—
Melting Pt.
Alcohol. Formula. - Preparation, Properties, etc.
o F. o C. -
Hydroquinone.. CsII,(OH), 351-5 177.5 | Preparation.—By the dry distillation of
Quinic acid. By Oxidation it forms
Qulmone.
Resorcin . . . . . Ditto 210-2 99-0 | Preparation.—By fusing resin of gal-
banum or benzene disulphonic acid
with potassic hydrate. Soluble in
Water, alcohol, and ether. Aqueous
solutions give a violet with Fe,CI,
and reduce AgNO3. Forms substi.
tution compounds.
Pyrocatechin ... Ditto 2327 | 1.11-5 | Preparation.—By the distillation of

(oxyphenol) Catechin, etc., and by the action of
. alkalies on meta-iodophenol. With
Fe2Cls gives a dark green color, and
With plumbic acetate a white pre-
cipitate.
Orcin . . . . . C.H. (CH)(OH), 186-8 86-0 | Found in the lichens used for the prepa-
ration of cudbear, litmus, etc. May
be formed artificially. By the action
of ammonia and free oxygen, it
forms orcein (C, H, NO, P), the color-
ing matter of archil and cudbear.
It forms numerous substitution pro-
ducts with the haloids and with
nitric acid.
Salicylic alcohol CH,(OH)OH,(OH) 179.6 82.0 Preparation.—By the decomposition of
(saligenin) Saliein under the influence of a fer-
ment as Synaptase, or of dilute sul-
phuric acid. By oxidation it yields
salicylic aldehyde, CH,(OH)OOH.
With ferric salts, its aqueous solu-
tion gives an indigo blue coloration.
—w
C.—TRIHYDRIC ALCOHOLS.
Glycerin Series.-SERIES I. Formula C.H...- (OH)s.
This includes—
Glycerin ... * * * ... CSPIs(OH)3.
Amylglycerin * * * ... C. Hi(OH)3.
576 HANDBOOK OF MODERN CHEMISTRY.
Glycerin.—(C3H3(OH)3 = C(CH2OH).H.OH.) [Specific gravity
at 60° F (15.5° C), 1:27. Boils at 355.1° F. (179.5° C).]
Symonym.—Propenyl alcohol.
Natural History.—It occurs in most animal and vegetable fats
in combination with the acids of the acetic and oleic series, that
is, as glycerides or ethereal salts. Olive oil, for example, con-
tains olein, or a glyceride of oleic acid; Suet contains stearin, or a
glyceride of Stearic acid; palm oil contains palmitin, or a glyceride of
palmitic acid. From these bodies glycerin is usually prepared as a
bye product in the manufacture of soap and candles.
Preparation.—(1.) By the action on fats of superheated steam.
C3H3(ChełissO4)3 + 3H2O = C, H3(OH)3 + 3Chaha;02.
Stearin + Water = Glycerin + Stearic acid.
Thus, glycerin may be prepared by merely distilling the fat with
superheated steam (see Saponification by steam), when decomposition
occurs, and the distillate, on standing, separates into two parts, the
fatty acids floating on the surface of the glycerin.
(2.) By the action of a base on fats (saponification). (See Soaps,
Candles, etc.)
CŞH3(CaFIaş02)3 + 3NaHO C3H3(OH)3 + 3ClaRIaşNaO2.
Stearin + Sodic hy- = Glycerin -- Sodic stearate.
drate
The glycerin solution, or spent lye as it is called, (the stearate hav-
ing been first rendered insoluble by the addition of sodic chloride,) is
drawn off, and distilled in a current of superheated steam. The water
is removed from the distillate by evaporation.
Glycerin is formed in small quantity during the fermentation of
Sugar. -
(3.) Glycerin may be prepared synthetically, by digesting trichlor-
hydrine (C3H3Cl3), a compound formed by heating together propylene
and iodine chlorides with water in closed tubes at 338° F. (170° C.)
C.H.Cls + 3H2O = CsPIs(OH)3 + 3HCl.
Trichlorhydrine + Water - Glycerin + Hydrochloric acid.
Properties.—(a.) Physical. A viscid liquid without color or smell.
It has a sweet taste. Specific gravity 1-27.
Action of heat.—At ordinary pressure glycerin cannot be distilled
without undergoing decomposition, darkening in color, and evolving
(amongst other products) acrolein. When however it is distilled, either
in vacuo at 410°F. (210°C.), or in an atmosphere of steam, it passes
over undecomposed. It is soluble in water in all proportions.
(6.) Chemical.-It has no reaction on red or blue litmus, or upon
any vegetable colouring matter. A solution of glycerin with
yeast does not undergo vinous fermentation, but is gradually con-
verted into propionic acid (C, HaOs = Cs H6O3 + H2O). By the
action of dehydrating agents it forms acrolein (C3H8O2 = 2 H2O +
FYROGALLIC SERIES. 57.7
C3H40). It combines with sulphuric acid to form sulpho-glyceric
acid (CsPIAO3S03), which forms soluble salts with lime and baryta.
With a mixture of strong nitric and sulphuric acids it forms nitro-
glycerin, or glonoin (Nobel's blasting oil), (C.H3(OH)3 + 3FINO3 =
3H2O + Cº. H3(NO3)2), an oily and highly explosive liquid (Specific
gravity 1-6). The monatomic organic acids, such as glacial acetic acid,
when heated with it in closed tubes, form glycerides or glyceric ethers,
as mon-, di-, or tri-acetin, as e.g., monacetin, C3H3(OH)2(C2H5O2).
Hydrochloric and hydrobromic acids or the compounds of phosphorus with
chlorine or bromine, form substitution compounds with glycerine, called
mono-, di-, or tri-chlorhydrins or bromhydrins, where the group OH
is replaced by chlorine or bromine; as e.g., Monochlorhydrine, C3H3Cl
(OH)2, etc.
[Monochlorhydrine by the action of nascent hydrogen forms propylic
glycol, C.H3(OH)2.]
Hydriodic acid or phosphorus iodide forms with glycerin, isopropylic
iodide (C3H71) and allylic iodide (C,EISI). By slow oridation with nitric
acid, glycerin forms glyceric acid (C3H8O3 + Og=C3H6O4+ H2O), and
by the further action of the acid oxalic acid (C.H.O.), which contain-
ing as it does fewer carbon atoms than glyceric acid, is clearly to be
regarded as the result of its decomposition.
Pyrogallic Series.
SERIES II.—Formula C, H2A-6(OH)3.
These alcohols, like the phenyls and orcins, are direct derivatives
of benzene.
This series includes:—

Melting point.
Formula.
o F. o C.
Pyrogallol . . © º tº gº w tº CeBI2(OH), 239 115
Phloroglucín . . . . ditto 248 120
Pyrogallol (C6H3(OH)2) (Pyrogallic acid). Melts at 239° F.
(115° C.). Boils at 410°F. (210°C.).
Preparation.—By the action of heat on gallic acid.
C6H2(OH)3CO2H = C6H3(OH)3 + CO2.
Gallic acid = Pyrogallic acid + Carbonic anhydride.
Properties.—A crystalline body, soluble in water, alcohol, and in ether.
It does not neutralize alkalies, nor does it form true salts. It decomposes
at 482°F. (250° C.), leaving a residue of metagallic acid (C6H,02).
When dissolved in a strong potassic hydrate solution, it rapidly
P P
578 - HANDROOK OF MODERN CHEMISTRY.
absorbs free oxygen (see page 98). With pure ferrous salts it forms
a fine blue color. Distilled at a red heat over zinc dust, it yields
benzene.
E–HEXHYDRIC ALCOHOLS,
Formula C, H2n-4(OH)6 Series.
This includes the two natural sugars mannite and dulcite.
Mannite, C5H8(OH)6. Natural History.—It is found in manna,
(the sap derived from different species of ash; Fraxinus ornus), and
also in other plants, such as seaweed, mushrooms, etc.
Preparation.—(1.) By the action of boiling alcohol on manna.
(2.) By the action of nascent hydrogen (sodium amalgam) on an
aqueous solution of glucose.
Properties.—Mannite crystallises in four-sided crystals, which are
Sweet to the taste, soluble in water and in alcohol, and insoluble in
ether. -
It does not ferment, thus differing from cane-sugar. It has no
action on polarised light, nor does it reduce an alkaline solution of
cupric hydrate on boiling, thus differing from grape-sugar.
Its relationship to the alcohols, and its hexatomic character, is
marked as follows:–(1.) By the action of nitric acid and of stearic
acid [ChełIaş0(OH)] it forms nitromannite and mannite herastearate
respectively, six hydrogen atoms in these compounds being replaced
loy six of the group (NO2), or by six of the radical of stearic acid
(CiałIssO). Thus : —
C6Ha(OH)6 ; C6Hs(ONO.)6; C6H2(OCs H350)6.
Mamnite ; Nitro mannite ; Mannite hexastearate.
(2.) With hydriodic acid it forms iodohewane (C6H, I), from which,
by the action of argentic oxide and water, normal secondary hexylic
alcohol may be obtained.
(3.) By owidation (as by the action of platinum black) it yields manni-
tic acid, C6H12O+, and (by the action of dilute nitric acid) saccharic acid,
C6H10O3.
Dulcite (C6Ha(OH)6) closely resembles its isomer mannite. Naturally,
it is obtained from the expressed juice of the melampyrum memoro-
sum ; artificially, it is prepared by the action of nascent hydrogen on
inverted milk-sugar.
By oxidation with nitric acid it forms mucic acid, an isomer of
saccharic acid.
Mercaptans or Thio-Alcohols.
Therelationship subsisting between potassic hydrate (KHO)and potassic
sulphydrate (KHS), has its counterpart in the relationship between
MERCAPTAINS OR THIO-ALCOHOLS. 579.
an alcohol, as ethylic alcohol (C2H5OH)), and a mercaptan or thio-
alcohol, as ethylic sulphydrate (C2H5OSH)). The name mercaptan was
originally applied solely to ethylic sulphydrate the first discovered of
these compounds, but it is now applied to the whole class of like bodies.
Preparation.—(1.) From the corresponding alcohols by distillation with
phosphorus pentasulphide :-
5[C.H3(OH)] + P2S5 – 5|C., H3(SH)] + P.O.5.
Bthylic alcohol + Phosphorus = Ethylic sul- + Phosphoric
pentasulphide phydrate anhydride.
(2.) From certain hydrocarbons; by acting upon their haloid deriva-
tives with potassic sulphydrate. Thus:–
CH2Cl + KHS = CH3(HS) + KCl.
Methylic chloride + Potassic sul- = Methylic sul- + Potassic
phydrate phydrate chloride.
The mercaptans are mostly offensive-smelling liquids, but some are
solid. By the action upon their alcoholic solutions of certain metals
(as K and Na), or of certain metallic oxides (as HgC) or salts (as
HgCl2), the mercaptans form stable crystalline metallic derivatives, as
e.g., potassic mercaptide, (C2H5(KS), mercuric mercaptide (C2H5)2(Hg"S2)
etc. By 0&idation with nitric acid, the mercaptans form sulphonic acids.
580 HANDBOOK OF MODERN CHEMISTRY.
SUPPLEMENTARY CHAPTER TO THE
ALCOHOLS.
CARBO-HYDRATES.
The sugars, gums, starches, etc., are called carbo-hydrates, inas-
much as combined with carbon they contain hydrogen and oxygen in
the proportions to form water. They may be arranged as follows:—
Those that rotate a ray of polarised light to the right are marked +,
and those that rotate it to the left —.
Group I.-SUCROSES: Composition C12H22O11.
1. Cane or sparkling sugar (sucrose) +.
2. Milk sugar (lactose) +.
3. Melitose —. 4. Melizitose —. 5. Trehalose—. 6. Mycose +.
Group II.—GLUCOSES: Composition C6H12O6.
. Grape sugar (dextrose) +.
. Fruit or mucoid sugar (laevulose) —.
. Galactose +.
. Sorbite+. 5. Eucalyn-i-. 6. Inosite 0.
º
Group III.-AMYLOSES: Composition (C5H10O3).
. Starch +.
. Dextrin +.
. Gums.
. Cellulin.
:
GROUP I.—THE SUCROSES.
Formula C12H22O11.
(1.) Cane or Sparkling Sugar (C12H22On).--Sucrose.
Natural History.—It is only found in the vegetable kingdom, as e.g.,
in the sugar-cane (saccharum officinarum), to the extent of 20 per
cent. ; the Asiatic sugar-cane (sorghum saccharatum), 9.5 per cent. ;
the maple (acer saccharinum), 5 per cent. ; the white beet, 7 to 11 per
cent. ; the date palm (Saguerus Saccharifer); and maize (7.5 per cent.)
Probably sucrose is present in all plants just before flowering,
at which time the soluble nutriment of the plant is most abundant.
Preparation.—(1.) The juice is first expressed from the plant. This
SUCROSES, 581
is effected by rollers in the case of the sugar-cane, by cutting in the
case of the beet, by tapping in the case of the maple, etc.
(2.) The free acid of the juice is as soon as possible after extrac-
tion neutralized with lime, and heated to 140°F. (60°C.). A coagulum
separates, containing albumen, earthy phosphates, etc. There must
be no delay in this part of the process, otherwise the albumen present
in the juice would set up fermentation, and cause a loss of sugar.
The free acid must be neutralised with lime before boiling, otherwise
it would, on boiling, convert a portion of cane into grape sugar, and
So cause loss.
(3.) The clear liquor is now evaporated in open pans. (No doubt
the large quantity of molasses formed is greatly due to this part of
the operation.)
(4.) It is now crystallised in open wooden troughs, and at the same
time briskly stirred, to prevent the formation of large crystals. The
solid sugar formed, is separated in casks with perforated bottoms from
the uncrystallisable syrup. The former, dried in the sun, constitutes
raw or Muscovado sugar (foots), and the latter molasses.
Sugar Refining.
(1.) The raw sugar is dissolved in water, and the solution in which
a little lime, some ground bone-black (4 to 100 of sugar), and albu-
men, such as the serum of bullock’s blood has been mixed, is then
boiled by steam (blow up). The albumen, as it coagulates, carries
up with it the impurities suspended in the juice. The bone-black is
added to assist in decolorising the solution.
(2.) The clear liquor is now further decolorised by filtration through
animal charcoal.
(3.) The colorless filtrate is now evaporated “in vacuo.” By this
means, the boiling-point of the syrup is reduced from 230°F. (110°C.)
to 150°F. (65.5°C.), that is, below the temperature at which heat
injuriously affects sugar. The evaporation is continued until the
syrup is sufficiently concentrated to “draw out.”
(4.) The syrup is now run into coolers, and well stirred until
crystallisation commences, when it is poured into moulds. After it has
set, the treacle is drained off, the sugar washed with a little clean
syrup in order to remove adhering coloring matters, and the solid mass
finally dried and polished in a lathe. This constitutes “loaf sugar.”
It may be roughly stated that the raw sugar obtained is one-tenth
the weight of the original juice, that is, about one-half the quantity
of sugar the juice is known to contain. The raw sugar yields about
60 per cent. of pure cane sugar, the remainder consisting of water,
uncrystallisable sugar, coloring matters, etc.
Properties.—(a.) Physical. Sugar is a colorless and sweet body, orys-
tallizing in oblique rhombs; Sp. Gr. 1-6. It rotates a ray of light to
the right (73° 8').
582 HANDBOOK OF MODERN CHEMISTRY.
Action of heat.—(a.) On dry sugar.—Sugar melts at 365°F. (185°C.),
changing without loss of weight into a mixture of dextro-glucose
and lavulose (C2H22On = C6H12O6 + C6H10O3). The action of this
mixture on a ray of polarized light is directly opposite to that of
cane sugar. Hence it is called inverted sugar (fruit sugar), the spe-
cific rotatory power of the lavulose being greater than the specific
rotatory power of the dextro-glucose.
At from 365° to 400°F. (185° to 204-5°C.) the sugar gives off water
and becomes discolored, forming “toff).”
At from 400° to 420° F (204.5° to 215.5°C.) it gives off more water,
blackens, and leaves a brown residue called “caramel’’ (C12H2O).
Above this temperature it gives off inflammable and other gases
(CO; CH4; CO., ; etc.), and a liquid distillate consisting of acetic acid,
acetone, aldehyde, and a brown oil containing furfurol and assamar.
Charcoal only remains in the retort after the operation.
(6.) On a solution of sugar in water.—By boiling a solution of cane
Sugar, it becomes inverted sugar (C12H22On + H2O=C6H12O6+ C6H12O6).
This change is assisted by the presence of dilute sulphuric or other
mineral or organic acid, and also of certain salts. By prolonged
boiling with dilute acids, brown products such as ulmine, are
formed.
Heated to 365°F. (185°C.) with a very little water, sugar becomes
vitreous, and solidifies to an amorphous mass, called “barley sugar,”
which is an admixture of amorphous and crystallizable sugar. The
amorphous sugar contained in barley Sugar gradually becomes crys-
talline and opaque by keeping.
Solubility.—Sugar is soluble in cold water (1 in 2 aq. by weight), its
solubility in boiling water being almost unlimited. It is almost
insoluble in alcohol, and in ether. Boiling absolute alcohol dissolves
ºth part of its weight, but gives it up again on cooling. I
Action of acids.-Strong mineral acids rapidly decompose it. With
sulphuric acid the sugar is completely decomposed, carbon being sepa-
rated and SO2 evolved. This reaction is peculiar to came sugar. With
mitric acid, oxalic and saccharic acids are formed. With hydrochloric
acid, ulmin and ulmic acid are formed. With nitro-sulphuric acid, an
amorphous, explosive, nitro-compound is formed (C12His(NO2),0,1).
The action of weak mineral or vegetable acids is to convert sucrose,
which is non-fermentable, into dextrose and lavulose, both of which
may be fermented.
Action of alkalies.—Concentrated solutions of the alkalies form with
cane sugar bodies called sucrates. Dilute solutions act feebly and
slowly, forming ulmic acid. Triturated with the dried caustic alkalies,
it does not turn brown, thereby distinguishing it from grape sugar.
Action of oacidizing bodies.—By oxidation with sulphuric acid and
manganic peroxide, sugar yields formic acid, but with dilute nitric acid
it yields saccharic and oxalic acids. It burns vividly when a mixture
SUCROSES. . 583
with potassic chlorate is touched with a drop of sulphuric acid. It
fires when triturated with plumbic peroxide. It reduces silver and
mercury salts by heat. Pure cupric hydrate is very slowly reduced
by it even when the solution is boiling, but in the presence of an
alkali a blue solution is formed, which, slowly and imperfectly, pre-
cipitates cuprous oxide on boiling.
Cane sugar does not ferment directly, but it does indirectly by con-
version into dextrose and lavulose.
(2.) Milk Sugar (Lactin or Lactose) Clofſz. On.
Natural History.—Found only in animals (milk of mammalia).
Preparation.—From the whey of milk by evaporation and crystal-
lization. -
Properties.—(a.) Physical. A hard gritty substance, crystallizing in
square prisms. It is not very sweet. It has a specific gravity of 1-5,
and rotates a ray of light + 59° 3'.
Solubility.—Soluble in water (1 in 6 at 60°F.; 1 in 2-5 at 212°F.).
It is insoluble in alcohol and ether. -
Action of heat.—At 284°F. (140°C.) two molecules of lactose lose one
molecule of water. At 400°F. (204-5°C.) it fuses and loses more water.
In other respects the action of heat upon it, corresponds to that on
cane sugar.
(ſ3.) Chemical. Milk sugar is decomposed by strong acids. Nitric acid,
by oxidation, converts it into mucic, saccharic, tartaric and oxalic acids.
Boiled with dilute acids, it is changed into a fermentable sugar called
galactose (C6H12O6), a body which, with nitric acid, forms mucic acid,
and rotates a ray of light + 83°3'. Lactose does not itself undergo
winous fermentation, but under the action of yeast rapidly changes to
the fermentable body (galactose). Under the action of chalk and
cheese it forms lactic acid, a certain quantity of alcohol being formed
simultaneously. Boiled with an alkaline solution of cupric hydrate,
it precipitates seven-tenths as much cuprous oxide as dextrose.
(3.) Melitose (C12H22O11).-This is obtained from various species of
eucalyptus. The crystals have a slightly saccharine taste. It is
soluble in water (1 in 9 at 60°F.; 1 in 3 at 212°F.), and in boiling
alcohol. It is dextro-rotatory 102°.
By the action upon it either of dilute sulphuric acid and heat,
or of yeast, it forms two kinds of sugar, a fermentable sugar,
glucose, and an unfermentable sugar, eucalyn. Nitric acid oxid-
izes it to mucic and Oxalic acids. It does not reduce an alkaline
cupric solution.
(4.) Melizitose (C6H22On) is obtained from the larch. It is dextro-
rotatory 94° 1'. With nitric acid it forms oxalic acid. On boiling with
dilute sulphuric acid it yields glucose. It ferments with difficulty.
(5.) Trehalose (C12H22O11), is obtained from the trehala manna of
Syria. It is dextro-rotatory 200°. It forms a detonating compound
with strong nitric acid ; with dilute nitric acid it forms oxalic acid.
584 HANDBOOK OF MODERN CHEMISTRY.
It ferments very imperfectly, and does not precipitate cuprous oxide
from alkaline cupric solutions. .
(6.) Mycose (C12H22O11) is obtained from ergot, mushrooms, etc.
It is dextro-rotatory 173°. It ferments slowly.
GROUP II.--THE GLUCOSES.
Formula C6H12O6.
(1.) Grape Sugar (Glucose; Dextrose; Dectro-Glucose ; Granular
Sugar) (C6H12O6).
History.—It is found both in the vegetable and animal kingdoms.
(a.) In the vegetable kingdom it is found in fossil ferns and in vegetable
Imould ; in sweet fruits and in honey; in chestnuts; in growing pota-
toes and in malt. In ripe fruits and in honey, it usually occurs together
with lavulose and cane sugar.
(6.) In the animal kingdom it is found in the urine, in very mi-
hute quantity in health, but often in enormous quantity in diabetes.
It also occurs in the liver and in the stomach during digestion.
Preparation.—(1.) From fruits, etc., by solution in water and preci-
pitation with spirit. From honey, by washing with dilute alcohol,
which dissolves the lasvulose but leaves the glucose.
(2.) By the action of diastase (malt) on starch, or by merely boiling
the starch in dilute sulphuric acid. The acid is to be neutralized with
chalk, and the clear solution evaporated to a syrup and crystallised.
C6H10O3 + H2O F. C6H12O6.
Starch + Water – Glucose.
Glucose is also formed by the action of dilute acids on cellulose.
(3.) By the action of dilute acids on the glucosides, such as aesculin,
amygdalin, chitin, glycyrrhizin, Salicin, etc. $
Properties.—A granular non-sparkling body, forming nodular masses
of minute acicular radiating crystals (C6H12O6, H2O). Its sweetening
power is about one-half that of cane sugar. Specific gravity 1.4. It
is dextro-rotatory 54°.
Action of heat.—It suffers no decomposition up to 266°F. (180° C.)
At 338°F. (170° C.) water is evolved, and glucosan (C6H10O3) formed.
By the further action of heat, it forms caramel. --
It is soluble in water in all proportions. It is not soluble in
spirit. .
Action of acids.--Strong sulphuric acid converts grape sugar into
sulpho-saccharic acid. (This acid forms a soluble baric salt.)
Nitric acid oxidizes it to saccharic or oxalic acid. Hydrochloric acid
decomposes it. Heated with organic acids, it forms conjugate acid
compounds, such as tri-aceto-dextrose, C6H6O4(C2H5O2)3. Boiled with
dilute sulphuric or hydrochloric acid, it forms various brown compounds
called ulmin, ulmic acid, etc.
GLUCOSES. 585
Solutions of alkalies and alkaline earths decompose it even in the
cold, but more rapidly when heated, forming a brown compound
(Moor's Test). With yeast, it ferments rapidly and directly at a tem-
perature of 77° F (25°C.). It unites with certain salts (as NaCl)
and metallic oxides (as CaO, BaO, etc.), forming unstable compounds
such as (C6H12O6), NaCl.OH, and (C5H12O6)2(BaO)3,2H2O, etc.
It is rapidly oxidized. Hence when boiled in alkaline solutions of
silver and copper salts, it quickly reduces them, precipitating metallic
silver or the red cuprous oxide. Five molecules of cuprous oxide are
exactly reduced by one molecule of grape Sugar.
(2.) Laºwulose (Lavoglucose ; Left-handed Glucose ; Mucoid Sugar)
(C6H12O6).
Natural History.—This sugar occurs, together with glucose, in
honey, ripe fruits, etc. -
Preparation.—(1.) By heating cane sugar with dilute acids, when a
mixture of dextrose and laevulose (i.e., inverted sugar) is formed. On
neutralizing with lime, calcium compounds of both glucose and
lavulose result, the glucose compound being soluble, and the lavu-
lose compound insoluble, in water. The latter after separation is sus-
pended in water, and decomposed by the action of carbonic anhy-
dride or oxalic acid. •
(2.) By the action of dilute acids on inulin.
Properties.—A sweet syrup. It may be obtained as an amorphous
solid but with difficulty. It is more soluble in water and in spirit
than dextrose. It rotates a ray of polarized light to the left. The ro-
tation of glucose to the right is the same at all temperatures, but the
extent of rotation to the left in the case of laevulose, varies with the
temperature from 53° at 194°F. (90° C.) to 106° at 57.2° F (14° C.).
Inasmuch as inverted sugar consists of equal parts of glucose
(= + 56°) and lavulose (= — 106°), it follows that inverted sugar is
laevo-rotatory (= — 50°). By heat lavulose forms a body isomeric with
glucosan, called laevulosan (C6H10O3). On oxidation it yields saccharic
acid. Its reactions with a ferment and with metallic salts are similar
to those of glucose.
(3.) Galactose (C6H12O6) is prepared by boiling milk sugar in
dilute acids. It is dextro-rotatory 83 °3'. It ferments easily. It re-
sembles glucose, except that, unlike it and all preceding sugars, it
yields mucic acid on oxidation with nitric acid.
(4.) Sorbite (C6H12O5) is prepared from the juice of the berries of
the mountain ash. By oxidation with hot nitric acid, it forms oxalic
acid. It does not yield alcohol by fermentation with yeast, but it
yields lactic and butyric acids with alcohol in contact with cheese
and chalk. It is dextro-rotatory 47°.
(5.) Eucalyn (C.H.O.) is a sugar separated when eucalyptus sugar
is fermented. It will not ferment, nor is it rendered fermentable by
the action of dilute sulphuric acid. It is dextro-rotatory (+ 50°).
586 HANDBOOK OF MODERN CHEMISTRY.
(6.) Inosite (C6H12O6). This is the sugar of muscle. It is also
found in kidney beans. It does not undergo alcoholic fermentation,
but forms lactic, butyric, and carbonic acids by the action of chalk
and cheese. It is without action on a polarized ray.
Glucosides.
There are various bodies found in plants, called glucosides, that
are in reality compound ethers of glucose, which yield on decompo-
sition a glucose, together with other substances. The following are
the most important of these bodies:– -
(1.) Amygdalin (CoHº, NOh + 3H2O). Source; bitter almonds.
T]nder the action of synaptase it forms glucose, bitter almond oil,
and hydrocyanic acid. Thus :-
Cao H2, NO.11 + 2 H2O = C, H30 + HCN + 2C6H12O6.
Amygdalin + Water = Hydride of +Hydrocyanic-i- Glucose.
benzoyl acid
(2.) AEsculin (C2H24O13). Source; horse-chestnuts.
(3.) Chitin (CoHisNO6). Source; wing-cases of insects.
(4.) Glycyrrhizin (C24H8609). Source; liquorice sugar.
(5.) Indican (C26H31NO17). Source; indigo.
(6.) Myronic Acid (CoHoNS,0,0). Source; black mustard. By
the action of the myrosin (an albuminous ferment) present in the
seed, myronic acid forms oil of mustard, glucose, and sulphuric acid.
(7.) Phlorizin (C2, EI24Olo,2H,0). Source; Root bark of apple and
cherry-tree. & -
(8.) Quercitrin (C3sFIs On). Source; Quercitron bark.
(9.) Salicin (C3II,807). Source; bark of willow, poplar; also
found in the castoreum, contained in a gland of the beaver. It forms,
under the action of synaptase or emulsin, glucose and saligenin
(C7H8O2), and by distillation with sulphuric acid and potassic bichro-
mate, salicylol (C7H6O2), or the artificial oil of the meadow sweet
(Spiraea ulmaria).
(10.) Populin (C20H24Os). Source; bark of aspen.
(11.) Ruberythric Acid (C26H26O11). Source; madder root.
(12.) Solanin (C15H7NO.6). Source; woody nightshade.
(13.) Tannin (Cor HøgOT). Source; gall-nuts.
GROUP III.—AMYLOSES,
Starches: Fecula-Amidine.
Watural History.—The starches are organised, non-crystalline bodies,
found in cells in every part of the vegetable, except in the tip of the
bud and in the extremities of the rootlets. Starch is also found in
animals, especially in embryonic tissues, as well as in the brain, liver,
spleen, and kidneys of adults.
AMYLOSES. 587
Preparation.—The tissue is first broken up, and the starch washed
out with cold water, in which it is insoluble.
Warieties.—We may recognise four varieties:-
(1) Common starch; (2.) Lichen starch; (3.) Inulin; (4.) Paramylon.
(1.) Common Starch (CoH10O3)4.
Preparation.—(a.) From wheat, which contains 60 per cent. It is
extracted either (1) by fermenting the wheat flour for three or four
weeks, during which time the gluten putrefies, thereby assisting the
separation of the starch (old method); or (2), by simple washing.
(3) From rice (83 per cent.), extracted by washing the powdered
rice with a weak alkaline lye to dissolve the gluten (Jones patent).
(y.) From potatoes (20 per cent.), extracted by rasping and
washing.
(6.) From arrowroot, Jatropha manihot, etc. -
Properties.—A white pulverulent crepitating solid. The form and
size of the starch corpuscles vary with its source. It is insoluble in
cold water, alcohol or ether. Specific gravity, 1:5.
Action of heat. (a) On the dry starch. A moderate heat merely dries
the starch corpuscles. A temperature of 320°F. (160° C.) discolors
the starch a little, and renders it soluble (dextrin). At higher tem-
peratures it becomes of a buff colour, and evolves water, leaving
dextrin. At a still higher temperature, it evolves more water, and
leaves caramel. At a still higher temperature, it is decomposed, a
carbonaceous residue being left, and carbonic and acetic acids,
together with certain empyreumatic oils, evolved.
(ſ3.) Heated with water to 158° F (70° C.) the starch corpuscles split,
and form with the water a thick paste, called starch paste. Boiled for
a long time, the solution becomes clear. On the addition of alcohol
to the clear solution, it deposits a white precipitate of soluble starch.
Action of acids.--All acids decompose starch; (a.) Strong sulphuric
acid dissolves it, forming a compound acid. Dilute sulphuric acid
and heat change it into glucose ; (3.) Nitric acid, when concentrated,
forms xyloidin, which is precipitated on the addition of water
(C12H10ONO2)O10). A weaker acid converts it into oxalic acid. A very
weak acid changes it to dextrin; (y.) Hydrochloric acid changes it into
glucose. The action of oxalic and tartaric acids (but not of acetic
acid) is similar to that of HC1.
Action of alkalies.—These cause starch to form a paste when in solu-
tion without heat. Fused with it they form oxalates.
Action of haloids.-Neither chlorine nor bromine have much action
on starch in the cold, but when starch is heated in chlorine it is
decomposed. The action of iodine is to color the starch blue, the
color being destroyed at a little below 212° F (100° C.), reappearing
(if the heat has not been too great) as the solution cools. Ferments,
such as yeast and diastase, (like dilute sulphuric acid,) change it into
dextrin and glucose. t
588 * HANDBOOK OF MODERN CHEMISTRY.
(2.) Lichen Starch is found in most lichens, such as Iceland and
Carageen moss. When boiled with water it forms a jelly. It is con-
verted by acids into glucose. Iodine turns it a greenish brown color.
It does not ferment whenºmixed with yeast or diastase.
(3.) Inulin Starch is found in the roots of most of the Compositae,
such as the dahlia, chicory, elecampane, etc. It is an amorphous
white substance, decomposed, like starch, by heat. It forms dextrin by
long-continued boiling. By the action of dilute acids, it yields laevu-
lose. Iodine has no action upon it.
(4.) Paramylon, glycogen, or animal starch, is found in certain of
the lower animals, and also in certain viscera of the higher animals,
especially in the placenta. Acids change it into glucose. Iodine has
no action upon it.
Uses.—In the vegetable, starch acts as a store of nutriment. In the
animal, its use is a respiratory food. The essential condition for ren-
dering starch useful, either to the vegetable or to the animal, is its
conversion into soluble dextrin and sugar.
GUMS (C6H1605).
Gums are organic bodies occurring in the juices of plants. They
are amorphous, tasteless, and inodorous bodies. They are distin-
guished from sugars by not being susceptible of fermentation, and by
forming mucic acid when oxidized with nitric acid. From resins they
may be distinguished by their solubility or by their softening in water,
and by their insolubility in alcohol. .
Varieties.—Deatrin, arabin, cerasin, tragacanthin, bassorin, calendulin,
Saponin, pectin, carrageemin, cydonin.
(1.) Dextrin (C6H10O3). Dextrin occurs in all vegetable juices, and
may be prepared artificially (constituting artificial or British gum),
either—
(a.) By heating starch with or without water.
(3.) By heating starch with dilute sulphuric acid.
(y.) By the action either of diastase, such as is contained in an
infusion of malt, or of a similar compound present in the stomach
during digestion, on starch.
The properties of dextrine vary somewhat with its source. It dis-
solves in water, forming a mucilage, from which solution it is pre-
cipitated by alcohol and by acetate of lead. Its action on a ray of
polarized light is dextro-rotatory (138° 7').
Iodine colors some specimens of dextrin brown, whilst on others it
is without action. By boiling with dilute acids it forms dextrose. It
does not ferment with yeast. The pure gum does not reduce an
alkaline copper solution.
(2.) Arabin (C12H22On) is the principle of gum arabic, and con-
stitutes the soluble portion of other gums. . It is soluble in its own
weight of water, the solution being unacted upon by iodine. The

GUMS. 589
arabin may be precipitated from its aqueous solution by alcohol, by
basic acetate of lead, and by potassic silicate.
Arabin is probably a gummate of lime. On incineration, arabin
yields 3 per cent. of ash, which is almost entirely lime. Gummie
acid is said to be soluble in water, like gum, but not to be precipitated
from its solution by alcohol, unless an acid or a salt be present. It is
laevo-rotatory 36°. By a heat of 212° F. (100° C.) it forms meta-
gummic acid which is insoluble in water.
(3.) Cerasin (C6H10O3) is the insoluble part of cherry-tree,
peach, and other such gums. It is said to be a compound of lime
and metagummic acid. By long continued boiling it is changed
into arabin.
(4.) Tragacanthin is the soluble portion of gum tragacanth.
(5.) Bassorin is the insoluble portion of gum tragacanth, and
forms the chief part of gum bassora. It is soluble both in cold
and boiling water. -
(6.) Pectin. Unripe fleshy fruits contain an insoluble body called
pectose, to which the hardness of unripe fruits is due. By the action of a
ferment present in the fruit, this body forms in the ripe fruit a soluble
substance called pectin. The peculiarity of pectin is the property it
possesses of forming a jelly with acids or alkalies. It is soluble in
water, insoluble in alcohol, and without action on a polarized ray.
The solution of pectin is neutral. It is precipitated by alcohol, but
not by plumbic acetate. By boiling with water it forms parapectin
which is precipitated by plumbic acetate. By boiling with dilute acid
it forms meta-pectin, which is acid to litmus, and is precipitated by
baric chloride. By the action of bases, all these varieties of pectin are
changed into pectic acid.
We are unable to fix definite formulas for these bodies.
REACTIONS TO BE NOTED,
Alcohol (Ethylic alcohol, C.H.3(OH)):—
1. It absorbs moisture. It mixes with water, contraction and heat
occurring at the time.
2. Heated in a test tube, (a.) it volatilizes without blackening;
(3.) the vapor has a peculiar odor, and (y.) burns with a blue, smoke-
less, non-luminous flame.
3. Heated with sulphuric acid, (a.) alcohol does not blacken; (3.)
it evolves an ethereal odor. [Methylated spirit turns brown.]
4. Heated with potassic hydrate it gives no action.
Glycerin, C.H. (OH)3:—
1. Heated in a test-tube glycerin decomposes without blackening,
emitting acrid fumes of acrolein.
2. Its behaviour when heated with sulphuric acid or with potassic
hydrate is similar to the action of heat without these reagents.
590
HANDBOOK OF MODERN CHEMISTRY."
3. It has no action on vegetable colors.
4. Nitro-sulphuric acid forms with it the substitution compound
nitro-glycerin (C3H5 (NO2)3O3)
Sugars —
Sucrose.
Glucose.
5:
6
. Taste e e º # * *
. Action on polarized ray. .
. Heated in a test tube .
. Heated with H.S0,
. Heated with potassic
hydrate s tº ſº sº
. Heated with potassic
cupric tartrate . . . .
Very sweet
Dextro-rotatory 73.8°
Chars; odor of caramel
Chars rapidly; SO2 evolved
No change
No red ppt. of Cu,0
Not very sweet.
Dextro-rotatory 54°.
Chars.
Chars slowly, forms sul-
pho-saccharic acid.
Becomes dark brown.
Red precipitate of Cu,0.
7. Add to the solution, two | Turns blue; on heating | Turns blue; on heating an
drops of cupric sulphate, little alteration occurs at immediate yellow pre-
and then KHO e Q first; a slight red precipi- cipitate occurs, becoming
tate falls after a time, dark red (Cu,0), the
but the blue color of the solution rapidly losing
Solution remains. its color.
Starch :—
(1.) Under the microscope, starch cells appear as rounded grains,
which polarize light.
(2.) Insoluble in cold water.
When boiled the cells burst, and the
starch forms a paste, shreds of membrane being apparent in the
solution.
(3.) It forms a blue compound with free iodine; this compound is,
(a) soluble in pure water, and (3.) insoluble in solutions containing
free acid; (y.) is destroyed by heat, temporarily if the heat be slight,
but permanently if the heat be considerable.
4. It is soluble in strong nitric acid, forming xyloidin.
Gum :-
1. It softens in cold water.
2. Gives no reaction with tincture of iodine.
3. Basic acetate of lead gives with it a white precipitate.
591
CHAPTER XXIV.
TEIE ORGANIC ACIDS.
Relationship to other bodies. MosobAsic ACIDs: Acetic—Acrylic—Sorbic–
Benzoic—Cinnamic—Naphtoic. DIBASIC ACIDs: Succinic–Fumaric—Phthalic.
TRIBASIC ACIDs: Tricarballylic—Mesitic. Reactions of the acids.
SUPPLEMENTARY CHAPTER.—Fats and Oils—Soaps—Candles—The Tannins—Ink—
Tanning.
ORGANIC ACIDS.
An organic acid may be regarded as an alcohol derivative. It is a
compound of a semi-molecule of hydroxyl (OH) with an oxygenated
radical.
(1.) An alcohol is derived from a hydrocarbon by the substitution of
one or more equivalents of the group (OH), for one or more equiva-
lents of H. Thus—
C.HG = Ethane and forms C2H3(OH) Ethylic alcohol.
C3Hs = Propane , , ,, C3H7(OH) Propylie alcohol. -
TJpon the number of equivalents of (OH) substituted for hydrogen
atoms, depends the atomicity of the alcohol, by which we mean the
number of ethers that an alcohol can form by the substitution of a
monatomic alcohol radical for the hydrogen of the group (OH);
Thus—
Monatomic alcohol T)iatomic alcohol Triatomic alcohol.
C.H. (OH) CAH6(OH)2 CaFI5(OH)3.
Propyl alcohol ; Propene alcohol ; IPropenyl alcohol.
(2.) An organic acid is derived from an alcohol by the equivalent
substitution of O'' for H2, or of O2 for H4, etc. Thus—
C.H3(OH) Ethylic alcohol forms C.H.O(OH) Acetic acid;
C3H1(OH) Propylic alcohol ,, C3H5O(OH) Propylic acid.
(3.) An alcohol may yield more than one acid. The number of
acids an alcohol is capable of forming may be determined by the
number of times that the group (CH2.OH) enters into the molecule of
the alcohol. Thus—
JEthylic alcohol C.H3(OH) contains but one of the group CH2OH
(+CH3). It therefore forms only one acid.
Ethene alcohol C.B., (OH)2 contains two of the group CH2OH. It
therefore forms two acids.
(4.) But inasmuch as the change of an alcohol into an acid, consists
in the substitution of O for H2, or in other words in the conversion of
the group CH2OH of the alcohol, into COOH in the acid (which latter
592 - HANDBOOK OF MODERN CHEMISTRY.
group is termed carboayl), it follows that the number of equivalents of
carboxyl in the acid, determines the basicity of the acid; in other
words, that the number of groups of carboxyl indicates the number
of hydrogen atoms in the acid that may be replaced by metals to form
salts. Thus, C.H.O., is acetic acid. It contains only one of the group
COOH ; it therefore is a monobasic acid, i.e., only one atom of its
hydrogen can be replaced by a metal in the formation of salts.
C2H2O, is oacalic acid. It contains two of the group COOH ; it
therefore is dibasic, i.e., the molecule may have two atoms of its
hydrogen replaced, either by two of a monad metal, or by one dyad
metal, in the formation of salts.
(5.) It is evident, therefore, that the basicity of any acid, corresponds
with the basicity of the alcohol from which the acid was derived.
Many of the acids known have been actually derived from alcohols,
whilst many, as yet, have not been classified.
Constitution of the Acids.-Acids have been regarded as formed
on the type of a molecule of water, by the substitution of an acid
or oxygenated radical for one of the hydrogens (if the radical be
univalent) of the water molecule, just as alcohols are regarded as
formed on the type of a molecule of water by the substitution of an
alcohol or hydrocarbon radical for one of hydrogen. If the radicals
be divalent, the acids and alcohols are then regarded as formed on
the double water type, etc. Thus—
(a.) #} O = Water; º O
(single mol.).
EI - (CAH6)" _Propene (C.H.,0)" Lactic
(3.) #}o-water #" | 0–’. “H. 0–’.
Ethylic C.H.O O Acetic
alcohol; H T acid.
-
(double mol.).
The acid radicals are denoted by names ending in yl, as acetyl, the
radical of acetic acid, etc.
Acid Derivatives.
(1.) Salts.--Organic acids (as we have said) are of different basici-
ties, according to the number of times that the group CO.OH occurs
in the molecule. When the acid is acted upon by a metallic carbonate,
hydrate or oxide, the H of this group (carboxyl) is exchanged for
a metal to form a salt.
(a.) Monobasic acids, such as acetic acid, CH3CO(OH), forms (1)
normal salts, as sodic acetate, CH3CO(ONa); (2) acid salts, formed by
the combination of a normal salt with a molecule of the acid, as
acid potassic acetate, (C.H.,0),(OK)(OH); and (3) basic salts, formed by
the combination of a normal salt with one or more molecules of a
metallic oxide or hydrate, as triplumbic acetate, Pb"(C2H5O2)2,2PbO,
etc. * -
ACID DERIVATIVES. - 593
(6.) Dibasic acids, such as oxalic acid, C,02(OH)2, form (1) normal
salts, as ammonic oxalate, C.O.(ONH4)2, where all the displaceable
hydrogen is replaced by a metal; and (2) acid salts, as acid ammonic
oxalate, C.O.(OH) (ONEL), where one - half of the displaceable
hydrogen is replaced by a metal.
(2) Acid Anhydrides or Oxides.—These are bodies formed by
the substitution of the hydrogen of the carboxyl in the acid, by an
acid radical. Thus, CH3CO(OH) being acetic acid, -
(a.) [CH2CO(CH3CO)0] = acetic oxide or anhydride.
(3.) [CH3CO(CH2O)0] = acetobenzoic oxide.
Thus the acid radical may be the same as that already present in
the body, as in (a), or it may be different, as in (3). Various mixed
anhydrides may in this way be formed.
Preparation.—(1.) By the action of the acid chlorides either on the
acids or on their salts.
(2.) By the action of acid chlorides on metallic oxides.
Properties.—(1.) By the action of water, the anhydrides become
acids; (2) with phosphoric chloride (PCls), they form acid chlorides ;
(3) by the action of alcohols, they form ethereal salts; (4) with
ammonia, they form acid amides.
(3.) Acid Peroxides.—These bodies bear the same relationship to
acid oxides, that PbO bears to PbO2. Thus:–
(CH3CO)2O = acetic oxide; (CH3CO)2O2 = acetic peroxide.
Preparation.—By the action of a metallic peroxide (as BaO2) on an
acid anhydride or chloride.
Properties.—The acid peroxides are powerful oxidising agents.
(4.) Compound Ethers.-Ethereal salts. Bodies formed by the
substitution of the replaceable hydrogen of an acid, by an alcohol
(hydrocarbon) radical. Thus:—
Acetic acid, CH3CO(OH), forms CH3CO(OC.H3), ethylic acetate.
A similar formation takes place in the case of the mineral acids.
Thus:—
Sulphuric acid, H2SO, forms (C.H3)2SO, ethylic sulphate.
Further, as we have normal and acid metallic salts, so we may also
have normal and acid ethereal salts.
Preparation.—(1.) By the action of alcohols, either on the acids,
the acid chlorides, or the anhydrides.
(2.) By the action of the acid ethereal salts of sulphuric acid on the
alkaline salts of the acids.
Properties.—Stable bodies. When heated with water they form the
acid and the alcohol from which they were derived.
(5.) Acid Chlorides, Bromides, and Iodides. These are bodies
formed by the substitution of the (OH) in the carboxyl group of the
acid, by either chlorine, bromine, or iodine. Thus—
Acetic acid, CH,CO(OH), forms CH3CO(Cl), acetyl chloride.
Succinic acid, C.H.C.O.(OH)2, forms C.H.C.O.(Clo), succinyl chloride.
Q Q
594 HANDBOOK OF MODERN CHEMISTRY.
Preparation.—By the action of the haloid phosphorus compounds on
the acids, or on their metallic salts.
Properties.—Decomposed by water into the organic and haloid
acids. Thus:–
CH,CO(Cl) + H2O = CH,CO(OH) + HC1.
Acetyl chloride + Water = Acetic acid + Hydrochloric
- acid.
(6.) Acid Amides (Amidated acids).-Bodies formed by the sub-
stitution of the (OH) in the carboxyl group of the acid by amidogen
(NH2). The monobasic acids yield normal amides only, whilst the
dibasic acids yield both normai and acid amides. Thus:–
Acetic acid CH3CO(OH), forms CH2CO(NH2) Acetamide (neutral).
Succinic acid C.H.C.O.(OH), forms C.H.C.O.(NH2)(OH) sº
(acid).
} ) 7 j ,, C.H.C.O2(NH3). Succinamide
(neutral).
Preparation.—(1.) By the action of heat on the ammonic salts of
the acids, whereby water is abstracted. Thus –
CH3CO(ONH,) -- CH,CO(NH.) + H.O.
Ammonic acetate - Acetamide + Water.
(2.) By the action of ammonia either (a) on the compound ethers or
(ſ3) on the acid chlorides. -
(a.) CH2CO(OC.H.) + NH, - C.H. (OH) + CH,CO(NH.).
Ethylic acetate + Ammonia = Ethylic alcohol + Acetamide.
(3) CH,CO(Cl) + 2NH, - NH,Cl + CH,CO(NH2).
Acetyl chloride + Ammonia = Ammonic + Acetamide.
- chloride *
Properties.—When the acid amides are heated with water, the
ammoniacal salts are re-formed. When distilled with phosphoric
anhydride, they become “nitriles” or alcoholic cyanides. Thus:—
CH,CO(NH.) + P.O. = CH,CN(or(C.H.)"N) + 2 HPOs.
Acetamide + Phosphoric = Methyl cyanide (or + Phosphoric
- anhydride ethenyl nitrile) acid.
(7.) Haloid salts of the acids. These are compounds formed
from the metallic salts, by the substitution of the metal by chlorine, etc.
Thus :—
Potassic acetate CH,CO(OK), forms CH,CO(OCl) chlorine acetate.
Properties.—Very unstable bodies. They explode at a low tem-
perature. -
(8.) Substitution Derivatives.—By the direct action of the haloid
elements on the acids, the substitution of one or more chlorine atoms
for hydrogen may be effected. Thus :—
CH,C0[OII) = Acetic acid.
CH,ClCO(OH) Monochloracetic acid. CH, BrCO(OH) Monobromacetic acid.
CHCl,CO(OH) Dichloracetic acid. CHBr,00(OH) Dibromacetic acid.
CC1,000H) Trichloracetic acid. *
ACID DERIVATIVES.
595
These substitution acids form salts, compound ethers, acid chlorides,
etc., like the original acid.
The organic acids are divided into three great classes according to
the number of carboxyl groups (CO.OH) which they contain, or in
other words, according to their basicity –
I. Monobasic acids; II. Dibasic acids; ITT. Tribasic acids.
These may be further subdivided as follows:–
(A.) Monobasic Acids.
$
Pſydrocarbon
SERIES. from which Formula. Example.
derived.
I. * º ) CnH2n + , CnH2n+100(OH) Acetic acid CH,CO(OH)
atty acids -
(a.) Lactic series ... CnH2n(OH),CO(OH) Lactic acidC, H,(OH)CO(OH)
(3) Pyruvic series C Han–0CO(OH) Pyruvic acid C, H,000(OH)
(y.) Glyoxylic CnH2n-1(OH)2. CO(OH) alsº acid C.H.(OH)OH(OH)
series º O(OH)
II, Acrylic series CnH2n Ǻn-1999H) Acrylic acid C.H.CO(OH)
!!. Sorbic series CnH2n-2 CnH2n-400 § Sorbic acid C.H.C0(OH)
IV. º: . º CnH2n-6 CnH2n-2C0[OH) Benzoic acid C.H.CO(OH)
a.) Uxybenzolc
(3 º benzoic CnH2n-4(OH)00(OH) | Salicylic acid C.H. (OH)00(OH)
.) U1Oxybenzolc
series & a 9 | CnH2n-6(OH),CO(OH) Oxysalicylic acid C.H.,(OH),CO
tº º - (OH) -
W. %) Gallic series.. CnH2n-1 (QH),000H) Gallic acid C.H.,(OH)2CO(OH)
Cinnamic series . . . CnH2n-s | CnH2n-6C0(OH) Cinnamic acid CeB,CO(OH)
WI (ºn-ſº CnH2n-11C0[OH) rºle acid C.B.C,CO
Naphtoic series . . . CnH2n-1, CnH2n-12CO(OH) Naphtoic acid Clo H,CO(OH)
(a.) CnH2n-1, CO CnH2n-16CO(OH) Anthracene-carboxylic acid C.H.,
(OH) . . . . . . CO(OH)
(B.) Dibasic Acids.
Hydrocarbon
SERIES. from which Formula. Example.
derived.
I. Succinic series CnH2n+2 CnH2n(COOH), Succinic acid C.H.(COOH),
(a.) Malic series ... - Gahan (QH)(COOH), Malic acid C.H. (OH)(COOH),
(3) Tartarie series Qn Han (QH)2(COOH), Tartaric acid C.H.(QH),(COOH),
II. Fumaric series CnH2n n Han (COOH), Fumaric acid C.H.(QQQH),
II. Phthalic series . 'nH2n-6 | CnH2n-s(COOH), Phthalic acid C.H.(COOH).
* (C.) Tribasic Acids.
Hydrocarbon -
SERIES. from which Formula of Acids. Example.
derived.
| | Tricarballylic series | Cain it a ºn Han- (QQQH)3 Tricarballylic acid C.H.(COOH),
II, Mesitic series CnH2n-6(COOH)3 Mesitic acid C.H. (COOH)

'In 4+2n-6
596 HANDBOOK OF MODERN CHEMISTRY.
A. MONOBASIC ACIDS.
Acetic Series.
SERIES I. Formula (C.H., 11.00(OH)).
Of these we recognize three groups—
(a.) Normal or primary acids | §ºn,
derivatives of primary alcohols (see page 559), i.e., an alcohol where
one hydrogen atom of carbinol CH3(OH) has been replaced by a radical
of the formula C, H2n+1
(6.) Secondary acids | §ºn,
derivatives of secondary alcohols, i.e., an alcohol where two hydrogen
atoms of carbinol CH3(OH) have been replaced by two radicals of
the formula C, H2n+1.
(y.) Tertiary acids - {{#ſº
derivatives of tertiary alcohols, i.e., an alcohol where three hydrogen
atoms of carbinol CH3(OH) have been replaced by three radicals of
the formula C.H2n+1. Thus—
t
From the alcohols we obtain the acids:—
Alcohols. Acids. Example. '
-- C(C,EIan 1)H, , | | C(CH3)H
(a.) C(C,EI2n+1)H,(OH) | §§ 1)H, {{ # 2
Primary alcohol. Primary acid. Propionic or
4. methacetic acid.
Ha
(3.) C(CAHza-1), H(OH) | §º + 1). H ; | º
Secondary alcohol. Secondary acid. Isobutyric or di-
methacetic acid.
C(CAH2n+1)s. C(CH
(y.) C(C.H2n+1)3(OH) | § ÖHº +1)s; {3}. #):
Tertiary alcohol. Tertiary acid. Trimethacetic acid.
ACETIC SERIES.
597
& ... ...... ſ C(CH2n+1)H
.) Normal acids of the acetic series n++2n + 1/++2
(a.) N yf CO(OH)
3.3
Fusing Pt. Boiling Pt. #3
ACIDS. Formula. Sp. Gr. 3: Remarks.
Ç
o F. o C. o F. o C. o C. :=
Formic acid. . . . HCO(OH)* 33°8 1 212 °0 || 100 || 1:23 at 16 30 | See page 599.
(Methylic acid)
Acetic acid ... ... CH3CO(OH)f 62°6 17 | 242-6 || 117 | 1.002 at 20 | 60 | See page 600.
(Ethylic acid)
Propionic acid ... C2H2CO(OH) 285'8 || || 41 | "996 at 19 74 | See page 602.
(Propylic acid) below
Butyric acid. . . . . . CaFI.CO(OH) —4 || –20 321°8 | 161 *981 at 0 88 See page 602.
(Tetrylic acid)
Valeric acid. . . . . C. HsCO(OH) 34.7-0 || 175 '957 at 0 || 102 | See page 603.
(Pentylic acid)
Caproic acid. . . . Cs H, 1CO(OH) || 41-0 || 5-0 || 388°4 || 198 || '943 at 0 || 116 || See page 603.
(Hexylic acid) .
CEnanthylic acid... Cali, a CO(OH) 413-6 || 212 ’934 at 0 || 130 See page 604.
(Heptylic acid) tº sº sº
Caprylic acid . . . . C. HisCO(OH) 57°2 || 14-0 || 456-8 ; 236 144 || Occurs as a glyceride in the
(Octylic acid) butter of cows' milk and in
COC08 Inuit oil.
Pelargonic acid ... Cs H17CO(OH) 64'4 18 || 500-0 || 260 9065 at 17 | 158 || Occurs in the leaves of the
(Nonylic acid) geranium, and may be pre-
pared by the action of nitric
- acid on oil of rue.
Capric acid . . . . . Cs. His CO(OH) 86°0 30 172 || Occurs as a glyceride in butter,
(Rutic acid) and also in cocoa nut oil, and
in fusel oil. May be prepared
by the oxidation of oleio
acid.
Lauric acid . . . . . Cao H21C0(OH) || 110°4 || 43-6 200 || Occurs as a glyceride in the
fats of the bay tree, pichurim
beans, cocoa nut oil, sper-
Inaceti, etc.
Myristic acid CraHa2CO(OH) 128-8 53.8 228 Occurs as a glyceride in nut-
meg butter, cocoa nut oil,
Spermaceti, and otaba fat.
Palmitic acid ... C1s HanCO(OH) | 1.43-6 62-0 256 See page 604.
Margaric acid Cae Haa CO(OH) || 140-0 || 60-0 258 See page 604.
Stearic acid. . . . . Car Ha:CO(OH) 156°5 69-2 1:01 at 0 284 || See page 604.
Arachidic acid Cas Has CO(OH) | 167-0 || 75°l 312 | A white crystalline fat, pre-
pared by the saponification
of the oil of the earth-nut
(arachis hypogaea).
Behenic acid ... | Cai Has CO(OH) | 168°8 || 76-0 340 | A white crystalline fat, pre-
pared by the saponification
of oil of ben.
Hyaenasic acid ... C2a Has CO(OH) || 170-6 || 77:0 * & tº
Cerotic acid. . . . . Cae HsaCO(OH) || 172°4 78-0 410 | Prepared from cerin (viz., that
- portion of bees' wax soluble
in boiling alcohol), or from
Chinese wax, a fat produced
on certain trees in China by
the puncture of a species of
COCCUls.
Melissic acid ... Cao Hs,CO(OH) || 190°4 88-0 452 | Prepared by heating melissic
alcohol with potassic hy-
drate.

* The radical C(C, Han 4: 1)H, in formic acid is replaced by H.
t The value of the s in the general formula for acetic acid - 0.
Natural History (General).—Many of these acids are met with in
nature in a free state; e.g., Formic acid is found in ants and in nettles,
valeric acid in valerian root, etc.
ethereal salts, such as, e.g., cetylic palmitate in spermaceti, glyceric
Stearate in beef and mutton fat, and glyceric palmitate in palm oil, etc.
(Hence the reason that these acids are called the fatty series of acids).
The first nine terms of the series have been prepared artificially.
Certain of them occur naturally as
598 HANDBOOK OF MODERN CHEMISTRY.
Preparation (General):—
(1.) From the corresponding primary alcohols. By simple oxidation
by such means as exposure to air on platinum black, or by heat-
ing with a solution of chromic acid, etc.,
CH.CH2OH + Og - CH.CO(OH) + H.O.
Ethylic alcohol + Oxygen = Acetic acid + Water.
(2) From the corresponding aldehydes. By oxidation.
CH,COH + 0 = CH3.CO(OH).
Acetic aldehyde + Oxygen = Acetic acid.
(3.) From the cyanides of the hydrocarbons C, Han 1.1. By the action
either of acids or of alkalies.
(a.) C.H., 11,0N+2H2O+HCl=C, H2n+1,CO(OH)+NH,Cl.
(3.) C.H., 11, CN + H20+ KHO=C,Han 1,000K)+NH3.
[The cyanides are formed by the action of potassic cyanide on a
haloid derivative of a hydrocarbon, and in some cases by distilling
potassic cyanide with the potassic salts of the sulphonic acids.]
(4.) By the action of carbonic anhydride on a compound of the
alcohol radicals of the methyl series with potassium or sodium.
Thus:– , .
CH,Na + CO2 = CH3CO(ONa).
Sodic methide + Carbonic Sodic acetate.
anhydride
–
(5.) By the action of water on the corresponding acid chlorides.
Thus —
Acetyl chloride + Water = Hydrochloric + Acetic acid.
acid
General Reactions of the Acids of the Acetic Series.
1. When these acids are submitted to electrolysis, the nascent
oxygen evolved from the positive pole sets free the radical and resolves
the carboxyl into water and carbonic anhydride (2(CH3CO.OH) + 0
= (CH3)2 + 2CO3 + H2O).
2. When the ammonic salt of these acids is heated with phosphoric
anhydride, the salt parts with its water, and forms a nitrile or
abnormal cyanide of the radical next below it. Thus:–
CHA.CO(ONH,) + 2P.O. = CH3(CN)” + 4HPOs.
Ammonic acetate + Phosphoric = Methylic nitrile + Metaphosphoric
anhydride acid.
ACES: IC SERIES. 599
3. By distilling the potassic salt of an acid of the acetic series with
an equivalent quantity of potassic formate, the acid is converted into
the aldehyde. Thus:—
CH,CO(OK) + HCO(OK) = CH3COH + K.CO,.
Potassic acetate + Potassic formate = Acetic aldehyde + Potassic car-
& bonate.
When this aldehyde is treated with nascent hydrogen it is con-
verted into a primary alcohol.
4. By the distillation of the dry baric or calcic salt of an acid, a
ketone is formed. Thus:—
Ca(C2H5O2)2 = CO(CH3)2 + Ca"COs.
Calcic acetate :- Acetone + Calcic carbonate.
When the ketone is treated with nascent hydrogen it is converted
into a secondary alcohol.
5. By heating the acids and the alcohols together in sealed tubes,
the compound ethers are formed (see page 593).
We now proceed to examine the acids in detail.
Formic Acid (HCO(OH)=CH.O.). [Molecular weight, 46. Specific
gravity of liquid, 1:23. Fuses at 33.8°F. (1*C.), and boils at 212°F.
(100° C.)
Synonyms.-Methylic acid; Hydric formate.
Natural History.—It constitutes the active principle of the stinging
matter of ants, nettles, etc...
Preparation.—(1.) By the oxidation of methylic alcohol.
CH3(OH) + O. = HCO(OH) + H2O
Methylic alcohol + Oxygen = Formic acid + Water.
(2.) By the oxidation of numerous organic bodies, such as gum,
sugar, starch, etc.
(3.) By the action of heat on Oxalic acid. (The acid should in
the first place be mixed with sand or glycerine.)
C2H2O, - HCO(OH) + - CO2.
Oxalic acid :- Formic acid + Carbonic anhydride.
(4.) By the action of water vapor and carbonic anhydride on potas-
sium, the potassic salt of formic acid is produced.
K. -- 2CO3 + H2O = HCO(KO) + KHCOs.
Potassium-i- Carbonic + Water = Potassic formate + Hydric potassic
anhydride carbonate.
(5.) When silent electrical discharges are passed through a mixture
of hydrogen and carbonic anhydride, traces of formic acid are said
to be produced. (Brodie.)
600 HANDBOOK OF MODERN CHEMISTRY.
(5.) By the action of potassic hydrate (a) on chloroform, (3) on
carbonic owide, and (y) on hydrocyanic acid. "
(a.) CHCl2 + 4.KHO = HCO(KO) + 3KCl + 2.H.O.
Chloroform + Potassic = Potassic formate + Potassic + Water.
hydrate chloride
(3.) CO + KHO = HCO(OK).
Carbonic oxide + Potassic hydrate = Potassic formate.
(y.) HCN + KHO + H2O = HCO(OK) + NH3.
Hydrocyanic + Potassic + Water = Potassic + Ammonia.
acid hydrate formate
Properties.— (a.) Physical. A colorless, inflammable, corrosive
liquid, burning with a blue flame. The vapor has a very penetrating
odor. Sp. Gr. 1:23. When cooled to below 32°F. (0°C.) it forms
brilliant tabular crystals. It boils at 212°F. (100°C.). It dissolves
in water freely, the solution having a very acid reaction. It decom-
poses carbonates readily. By the action of alcohol it may be partially
converted into ethyl formate.
(3.) Chemical. With sulphuric acid, formic acid breaks up into
water and carbonic oxide ; with strong bases it forms oxalic acid,
hydrogen being evolved (2HCO(OH)) + Ba0 = C.O.(BaO2) + H2
+ H2O). With chlorine, it forms hydrochloric acid and carbonic
anhydride (HCO(OH) + C), E= 2PICl + CO2).
It is a powerful reducing agent. Thus it converts mercuric
chloride into mercurous chloride (calomel), and reduces metallic
mercury when mixed with mercuric oxide (HCO(OH)+ Hg.0=CO2+
Hg-i-H2O). This reducing action of formic acid on metallic salts,
distinguishes it from all other acids of this group.
It forms salts called formates, all of which are soluble, and may be
expressed by the formulae HCO(OM); 2 HCO(O.M"); 3HCO(O.M").
Acetic Acid (C2H4O2 = CH3CO(OH)). | Molecular weight, 60.
Specific gravity, 1.063. Fuses at 62-6°F. (17°C.), and boils at 246.2°F.
(119°C.).
Synonyms.—Ethylic acid; Hydric acetate; Spirits of vinegar.
Natural History.—It occurs in small quantities in animal fluids, and
also in the juices of plants.
Preparation.—By the general processes already described (page
598).
(2.) It is also produced during the destructive distillation of wood
(see page 497); and
(3.) During the (so-called) acetous fermentation (see page 485).
Glacial acetic acid (C2H4O2) is prepared by distilling sodic acetate
with concentrated sulphuric acid.
Properties.—Acetic acid is a colorless, pungent, corrosive liquid,
METALLIC SALTS OF ACETIC ACID. 601
solidifying to a white crystalline mass at 62.6°F. (17° C), and
boiling at 246.2°F. (119°C.). Sp. Gr. 1.063. The vapor is inflam-
Imable.
Its vapor density exhibits an anomalous behaviour. Thus, at a
very high temperature, its vapor has a normal density of 30 (Mol. Wt.
60), whilst at a few degrees above its boiling point, the vapor has the
abnormal density of 45. This is explained by supposing that at the
lower temperature the vapor is not a true gas, but commences, so to
speak, to behave, at this low temperature, as a liquid.
It mixes with alcohol, ether, and water, in all proportions. On the
addition of water its specific gravity rises, until the proportions corre-
spond to a hydrate of the formula C2H10, H2O. By adding more water
the specific gravity sinks. The acid dissolves camphor, etc. When
potassic acetate is distilled with arsenious oxide, it yields kakodyl.
Metallic Salts of Acetic Acid.
Of these the following are the most important :—
Formula. Remarks.
Potassic acetate, normal ... KC,EI,02 A deliquescent salt, soluble
in water and alcohol.
3 J. acid . . . KC, H2O2, C.H.O., Decomposes at 392° F.
(200° C.), giving off the
glacial acid.
Sodic acetate . . . . . . . NaC, H,02,3LI,0 Melts at 550.4°F. (288°C.);
decomposes at 599° F.
(315° C.).
Ammonic acetate, neutral.. NIH,C,EI,0, Spiritus Mindereri is the
aqueous solution of the
IB.P.
acid . . . NH,C.H.O., C.H.0,
5 y
Plumbic acetate, normal . . Pb"(C.H.,0),3H,0 Prepared by dissolving li-
(Sugar of lead) tharge in acetic acid.
2Pb"(C.H.,0), PbO The solution constitutes
3 y basic goulard water.
Pb"(C.H.,0),2PbO
Cupric acetate, normal . . . Cu"(C.H.O.),4-aq
tº ºb.6H.0
35 * Guº (dibjöuð.3io
Argentic acetate. . . . . . Ag(C.H.G.)
Aluminic acetate, neutral (Al...)"(C,E,02)6 Much used in calico print-
ing, the acetic acid being
capable of being driven
offat a low temperature.
}} basic . . . Al
Ferrous acetate . . . . . . . Fe
Ferric acetate . . . . . . . (Fe...)" º
Zincic acetate . . . . . . Zn"(C,Eis .#,0
–s
The further important derivatives of acetic acid are stated in the
following table —
602
EIANDBOOK OF MODERN CHEMISTRY.
Derivatives of Acetic Acid.

Boiling Pt.
Names. Formula. Sp. Gr. Remarks.
o F. o C, -
Methylic acetate .. CH2CO(OCHA) 0-9562 1319 55°5 Soluble in alcohol, water, and ether.
Ethylic acetate CHs CO(OC2H3) 0-890 1706 || 77'0 With ammonia it yields acetamide.
(Acetic ether). Hydrogen is said to be evolved when
- ethylic acetate is heated with sodium.
Amylic acetate . . CH2CO(OC-H 12) 300-2 149-0 || Odor.of Jargonelle pear.
Acetic chloride . . . . . CH3COCI 131-0 || 55'0 | A colorless liquid, decomposed by water.
(Acetyl chloride). Prepared by the action of PCle on
glacial acetic acid.
Acetic anhydride . . . . §§ } O 280°4 || 138'0 A heavy oil; prepared by the action of
3. acetyl chloride on potassic acetate.
& o C.H., COO Prepared by the action of BaO2 on
Acetic peroxide .. Čijööö acetic anhydride. ~.
Monochloracetic acid ... CEI2Cl.COOH 366-8 1860 | Prepared by the action of chlorine on
glacial acetic acid in sunlight. A
solid body, melting at 147.2° F.
(610 C.).
Dichloracetic acid .. CHCl2COOH 1-5216 221-0 || 105-0 | Prepared by exposing monochloracetic
acid to the action of dry chlorine. A
liquid.
Trichloracetic acid . CCla.COOH 1-617 | 390-2 | 199-0 | Prepared by exposing a little of the crys-
Of fused tallized acid in a bottle of chlorine to
acid. sunlight for several hours. A solid
body, melting at 11 4-80 F. (469 C.).
Monobromacetic acid CH. BrCOOH These acids are prepared by heating
Dibrom acetic acid. . CHBr, COOH bromine with glacial acetic acid in
Tribromacetic acid CBraCOOH Sealed tubes.
Thiacetic acid CH,CO(SH) 203-0 | 95-0 | Prepared by distilling together acetic
acid and P2S5. A colorless liquid.
Iodacetic acid.. CH, ICO(OH)
Acetamide . . CH2CO(NH2) 429.8 |221-0 | A solid, melting at 172.4° F. (78° C.).
Prepared by the distillation of am-
monic acetate. It combines with
acids, and yields metallic derivatives.
Amidoacetic acid. . . . . CH2(NH2)CO(OH) A solid, formed by the action of am-
(Glycocine, Glycocol). monia on brom-acetic acid.
Methyl glycocine . º CaLI., NO2 Prepared either by digesting ethyl
(Sarcosine).
chloracetate with an excess of a
concentrated solution of methyl-
amine, or by boiling kreatine with
baryta water,
Propionic Acid (C, H2O3=CH3COOH).
Boils at 284°F. (140°C.).]
Synonyms.-Methacetic acid; Propylic acid.
Preparation.—(1.) By the general methods already described (page
598).
[Molecular weight, 74.
(2.) By the action of hydriodic acid on lactic acid.
(3.) By the fermentation either of glycerine or of sugar with putrid
cheese, in the presence of calcic carbonate.
Properties.—A crystalline solid, boiling at 284°F. (140°C.). It is
soluble in Water.
at 321.8° F (161° C.).]
Synonyms.-Ethacetic acid; Diethacetic acid; Tetrylic acid.
Natural History.—It is found in butter, in tamarinds, in various
animal secretions, and in various kinds of decomposing animal and
vegetable matters.
It forms salts called propionates.
Butyric Acid (C, H.O. = C, H,CO(OH)).
Specific gravity of liquid, 0.9886.
[Molecular weight, 88.
Fuses below — 4°F. ( — 20°C.) Boils
ACETIC SERIES. 603
Varieties.—The acid is known in two isomeric conditions; viz., as
normal butyric acid (CH, CH2CH2CO(OH)), and as isobutyric acid
CH(CH3)2CO(OH). They are both colorless liquids, and both, when
heated, yield acetic acid and carbonic anhydride.
Preparation of (a) normal butyric acid.—(1.) By the oxidation of
normal butylic alcohol (CHA.C.H.CH3.CHz.OH).
(2.) By the fermentation of sugar with cheese and chalk (see page
485).
Properties.—At 32°F. (0°C.) it has a Sp. Gr. of 0.981. It boils at
323.6° to 325.4°F. (162° to 163°C.).
Preparation of (a) isobutyric acid.—By the oxidation of isobutylic
alcohol (CH(CH3)2CH2OH). -
Properties.—At 0°C. it has a Sp. Gr. of 0.959. It boils at 309.2°F.
(154°C.). It is more easily decomposed by heat than the normal
acid.
Valeric Acid, C.H.O.-C, H,CO(OH). Molecular Weight, 102.
Sp. Gr. of liquid, 0-937. Boils at 347°F. (175°C.).
Synonyms.-Valerianic acid; Pentylic acid.
Natural History.—It is found in valerian root, in the berries of the
guelder rose, and in many other plants.
Varieties.—It exists in four isomeric states, viz. –
(a.) Normal valeric or valerianic acid (propylacetic acid)—
CH.C.H.C.H.C.H.CO(OH).
Preparation.—By the oxidation of normal amylic alcohol.
Properties.—An oily liquid, having an acid taste, burning with a
smoky flame, and boiling at 365° F. (185° C.). It has a specific
gravity of 0.9577 at 32°F. (0°C).
(3.) Iso-valeric acid (iso-propylacetic acid) CH(CH3)2.C.H.CO(OH).
Preparation.—By the oxidation of iso-amylic alcohol.
Properties.—A liquid boiling at 347°F. (175°C.). It has a specific
gravity at 0°C. of 0.9468.
(y.) The third modification of this acid has not, as yet, been pre-
pared. Its suggested formula is CH(CH3)(C2H3)CO.(OH) (meth-
ethacetic acid). Unlike the other acids, it rotates a ray of light to
the right.
(3.) Tertiary valeric acid (trimethacetic acid) C(CH3)3CO(OH).
Preparation.—From tertiary butylic alcohol.
Properties.—A white crystalline body, melting at 95°F. (35° C.),
and boiling at 321.8° F (161° C.).
Valeric acid forms metallic and ethereal salts, called valerates, and
also substitution compounds, such as chlorovaleric acid (C,EICl2O.).
Caproic Acid, C6H12O3=C5Hu.CO(OH). Molecular weight, 116.
Sp. Gr. at 32°F. (0°C.) 0-943. Solidifies at 15.8°F. ( 9°C.) Boils
at 388.4°F. (198° C).
Synonym.—Heaylic acid.
Natural History.—It occurs as a glyceride in the butter of cow's
milk, and also in cocoa-nut oil.
604 HANDBOOK OF MODERN CHEMISTRY.
y
Preparation.—(1.) By the action of alkalies on amyl cyanide
(C.Hu.CN).
(2.) By the oxidation of poppy oil, of casein, and of many fatty
acids. 4.
(3.) By the Saponification of cocoa-nut oil, and distilling the soap
formed with dilute sulphuric acid.
Properties.—A clear oil. It forms salts called caproates.
Leucine, or Amido-caproic acid, C6H3NO2, or C6Hu(NH2)02, is
formed by the decomposition of, or by the action of acids and alkalies
on, various animal substances. It has not as yet been obtained from
any caproic acid derivative. It consists of volatile crystalline scales,
which melt at 212°F. (100° C.).
GEmanthylic Acid, C.H.O., or C6H3CO(OH). Molecular weight,
130. Sp. Gr, at 32°F. (0°C.) 0.934. Boils at 413.6°F. (212° C).
Synonym.—Heptylic acid.
Preparation.—By the oxidation either of castor oil or of oenanthylic
aldehyde (C,Eſi,0), a body obtained from castor oil by dry dis-
tillation.
Palmitic Acid, C6H3CO2, or C15H,CO(OH). Molecular weight,
256.
Natural History.—It occurs in many, if not in most natural fats,
as a glyceride, associated with stearin, as, e.g., in palm oil, as glyceric
palmitate; in spermaceti, as cetylic palmitate; in bees'-wax, as
myricyl palmitate (melissin), etc.
Preparation.—(1.) By Saponifying palm oil, and decomposing
the soap formed with sulphuric acid.
(2.) By melting oleic acid with potassic hydrate. ‘.
Properties.—A colorless, odorless, tasteless body, insoluble in water.
It forms normal, and in some cases (as with K and Na) acid metallic
salts (M'C6H2O2, or M"(C6H102)2.) It also forms ethereal salts,
such as glyceryl palmitates or palmitins.
Margaric Acid, Cz Hay03, or C6H3CO(OH). Molecular weight,
258.
History. — This was originally supposed to be a distinct acid,
obtained by the saponification of natural fats. It is now proved,
however, that what was originally called margaric acid, is simply a
mixture of stearic with palmitic or other acids. s
Preparation.—By the action of an alcoholic solution of potassic
hydrate on cetyl cyanide, and decomposing the resulting potassium
salt with dilute hydrochloric acid.
Stearic Acid, CeBI.6O2=Cz HagGO(OH). Molecular weight, 284.
Natural History.—A constituent of Solid animal fats, such as suet.
It always occurs in conjunction with palmitic acid. It is also found
in certain vegetable fats, such as the fat of cacao beans, the berries of
the cocculus Indicus, etc. It always occurs in nature as a glyceride.
Preparation.—The ſat is first saponified with an alkali, and then
LACTIC SERIES. . 605
decomposed by heating with dilute sulphuric acid. The free acid is
then dissolved in alcohol and crystallized. It may be separated from
palmitic acid as an insoluble magnesic stearate. &
Properties.—A white crystalline body, melting at 156.5°F. (69.2°C.).
It distils unchanged. It forms ethereal salts, and also metallic salts
called stearates, most of which are insoluble.
See SUPPLEMENTARY CHAPTER FOR FATs, OILs, etc.
Lactic Series.
SERIES I. (a.)—Formula C, H2A(OH)CO(OH).
The acids of this series are monobasic dihydric acids. They are
derivatives of the acetic acid series, one of the hydrogens being
substituted by one semi-molecule of hydroxyl. Thus—
C, Han CO(OH) -º- C.H. (OH)CO(OH).
Acid of acetic series -*- Acid of lactic series.
Varieties.—(Each variety includes both normal and iso-acids.)
C(C.H.A. i.).H.OH
CO.OH
C(CAH2n+1)2.OH
CO.OH
1. Primary acids
2. Secondary acids
CH, OH
3. Primary olefine acids CAH, | CO.OH
4. Secondary olefine acids C, H2, | ºf. Jiron
5. Tertiary olefine acids C.H., | §º- 1)2OH
The following acids belong to the lactic series:—

Mole-
NAME. w Formula. cular
Wt.
Carbonic acid * & ſº wº & © ... CO(OH), =CH,0, 62
Glycollic acid e & * * © e ... CH,(OH)00(OH) =0, H.0, 76
Laºtic acid. . . . . . . . . . . . HofſjöööH) = Hº. 90
Oxybutyric acid . . * - tº º tº e §§§§ =C, H,0s 114
(Butylactic acid)
Oxyvaleric acid .. tº - tº º C.Hs(OH)00(OH) =C.H.0, 12S
(Valero-lactic acid)
Leucic acid. . • * * - * & ... C.H.10(OH)00(OH)=CH20, 132
Amylhydro-oxalic acid . . . . . ... CeBI,(OH)OO(OH)=C, H.O. 146
Diamyloxalic acid .. tº tº * * ... CuH,(OH)00(OH)=C\,H,0, 216
606 HANDBOOK OF MODERN CHEMISTRY.
General Preparation of the Normal Acids of the Laotic Series.
(1.) From the glycols (i.e., a dihydric alcohol, such as C.H.(HO)2
(glycol)). By Oxidation with nitric acid, platinum black, etc.
CH2(OH).C.H.(OH) + O. = CH.(OH)OO(OH) + H.O.
Glycol + Oxygen = Glycollic acid + Water.
(2.) From the monochlorinated or monobrominated acids of the acetic
series. By the action of argentic hydrate.
C.H.ClCO(OH) + Ag|HO = C, H,(OH)OO(OH) + AgCl
Chloropropionic acid + Argentic = Lactic acid + Argentic
hydrate chloride.
(3.) From the amidated derivatives of the acids of the acetic series. By
the action of nitrous acid.
CH2(NH2)CO(OH) + HNO. = CH3(OH)CO(OH) + H2O + No.
Amidoacetic acid + Nitrous = Glycollic acid + Water + Nitro-
acid gen.
(4.) From the ketones and aldehydes of the acetic series. By first
digesting these bodies with hydrocyanic acid, and acting on the
resulting cyanides with dilute hydrochloric acid.
The acids may be prepared as potassic salts,
(5.) By the action of a solution of potassic hydrate on the cyanides,
or on the acid chlorides of the monochlorinated acids of the acetic
series.
They may be prepared as ethylic salts of the secondary acids,
(6.) By the action of the zinc organo-metallic compounds on ethylic
oxalate and the subsequent addition of water.
C0.0C.H. ſ C(CnH2n + 1)2(0ZnCnH2n+1)
easºn CAH n +
(a.) } ãº--2/n(CAH, -)={ºfi, + Zn} 0%.
- () n++2n + 1
Ethylic oxalate-HZinc compound.
C(CnH2n + 1),(0ZnCnH2n C(CnHon
(3)}º n++2 *H,0–£º
Secondary acid.
),(OIl) +Zn(OH)2+CnH2n+2
Properties (General).--All the acids of this series furnish metallic
salts by their action on metallic carbonates; ethereal salts, by their
action on alcohols; acid chlorides, by their action on phosphoric
chloride; acids of the acetic series, by their action on hydriodic acid ;
and either anhydrides or acids of the acrylic series, by the action of
heat.
Carbonic Acid; CO(OH)2 = H,CO. The constitution of this
acid allies it to the lactic series, but unlike the other acids of the
series it is dibasic. #
LACTIC SERIES. 607
We need only note here that it forms:—
(a.) Ethereal Salts, such as, e.g., ethylic carbonate (C2H3)2CO3.
This is prepared by the action of argentic carbonate on ethylic iodide
(Ag.,CO3 + 2C.H.I=2AgI + (C.H3)2CO3). Ethylic carbonate is a
colorless liquid, boiling at 257°F. (125°C.). Derivatives of this ether
are known where the oxygen is wholly or partially replaced by
sulphur, as, e.g., -
Ethylic monosulphocarbonic acid ... ... (C.H.) H.C.O.S.
Ethylic disulphocarbonic acid (acanthic acid) (C2H3)HCOSs.
Ethylic trisulphocarbonic acid * - - ... (C2H5)HCS3,
(3.) Amidogen Derivatives, as, e.g., carbamic acid CO(NH2)(OH), and
carbamide (or urea) CO(NH2)2 from which latter body many compound
ureas may be formed by the introduction of hydrocarbon groups in the
place of hydrogen. When the oxygen, moreover, is replaced by
sulphur, sulpho-carbamide or sulpho-urea (CS(NH2)2) is formed.
Glycollic Acid (mono-oxy-acetic acid) (CH2(OH)CO(OH) = C.H.O.).
Molecular weight, 76. Melts at 176° F. (80° C.). Boils at 212° F.
(100° C.).
Preparation.—(1.) By the general processes already described
(page 606).
(2.) By the action of nascent hydrogen on oxalic acid.
CO(OH)CO(OH) + 2H. = CH3(OH)CO(OH) + H.O.
Oxalic acid + Hydrogen = Glycollic acid + Water.
Properties.—These vary somewhat according to its preparation. It
is a white crystalline solid, soluble in water, in alcohol, and in ether.
It is decomposed by a heat of 302°F. (150° C.). It yields oxalic acid
by oxidation, and paramalic acid by dehydration.
Lactic Acid ; C.H. (OH)OO(OH) = C3H60s. There are at least
two, and possibly more modifications of this acid.
(a) Ordinary lactic acid (CHs.CH(OH)CO(OH)). This acid is pro-
duced (1) by the lactic acid fermentation ; (2) by the oxidation of
propene glycol; (3) by the action of argentic hydrate on chloro-
propionic acid ; (4) by the action of nascent hydrogen on pyruvic
acid; and (5) by the action of hydrocyanic acid on acetic aldehyde,
and the subsequent digestion of the cyanide formed with hydrochloric
acid.
(3) Paralactic or ethylene lactic acid (CH2(OH)OH,CO(OH). This is
prepared by decomposing paralactyl chloride (formed by com-
bining ethene with carbonyl chloride) with an alkali. It may also
be obtained from the gastric juice, from the saliva of diabetic patients,
from various secretions, and also from muscle, by the action of cold
water or of dilute alcohol.
Properties.—Lactic acid has never been obtained in the solid state,
but its solution may be concentrated until it becomes a thick, color-
less, syrupy liquid, having a specific gravity of 1:215. It is very
608 HANDBOOK OF MODERN CHEMISTRY.
acid and very soluble in water, alcohol, and ether. By the action
of a continuous heat upon it, lactide, or lactic anhydride (C3H4O2) is
formed. This body is a white crystalline substance, melting at 256-19
F. (124.5°C.), combining with water to form lactic acid, and with
ammonia to form lactamide (C.H. (OH)CO(NH2)).
Heated with dilute sulphuric acid, lactic acid forms aldehyde and
formic acid; heated with hydriodic acid, it is reduced to propionic acid
(C, HGOs -- 2HI = CsPI602 + H20 + Ic): by oa;idation, it yields acetic
acid, formic acid, and carbonic anhydride; by the action of
phosphoric chloride, it forms chloro-propionic chloride (C.H.ClCOCl).
All the lactates are soluble.
Lactic acid may be known from glycollic acid by its yielding no
precipitate with plumbic acetate.
Paralactic acid by oxidation yields malonic acid. Varieties of this
acid are said to have different actions on a polarized beam of light.
Pyruvic Series.
SERIES I. (ſ3.)—Formula C, H2n-10.CO(OH).
The acids of this series are monobasic and dihydric. They may be
regarded as derivatives of the lactic acid series by the abstraction of
C.H. (OH)CO(OH); CAH2n-10.CO(OH).
Acid of lactic series ; Acid of pyruvic series. –
It includes—
Mole-
NAME. Formula. cular Remarks.
Wt.
Glyoxalic acid C, H,0a 74
Pyruvic acid . . . . . CaFI,03 88 A liquid prepared by the dry distillation
(Pyroracemic acid) - - of tartaric, glyceric or racemic acids.
Boils at 329° F. (165° C.). With
sodium amalgam or with FII (i. e., by
nascent hydrogen) it forms lactic acid.
Epihydric acid . . . . . C.H.80s 102
Acetopropionic acid ... C, H,0a 116
Convolvulinoleic acid. . . ClaRI2,03 228 By the action of acids or alkalies on
certain glycerides contained in the
tubers of the jalap and the convol-
vulus orizabensis.
Jalapinoleic acid. . . . . CigHao(). 270
Ricinoleic acid . . . C O3 298 || The glyceride of this acid is the chief
constituent of castor oil. It is a
yellow inodorous oil, becoming solid
at 32° F. (0° C.).
ACRYLIC SERIES.
609
Glyoxylic Series.
SERIES I. (y.)—Formula C, Han (OH)2CO.OH.
The acids of this series are monobasic and trihydric. They are
derivatives of triatomic alcohols. Thus—
C3H8O3 - - C3H6O4.
Glycerin - Glyceric acid.
It includes—
Mole-
Name. . Formula. cular Remarks.
Wt.
|
Glyoxylic acid CHI(OH),CO(OH)=C.H.0, 92 | Prepared by the oxidation of
(Dioxyacetic acid) glycol and of alcohol, and
by the action of nascent hy-
drogen on oxalic acid. A
colorless syrup; distils at
212° F. (100° C.) without
change. Dissolves zinc with-
out the evolution of hy-
- - - drogen.
Glyceric acid CII,(OH), CPI(OH).CO(OH) 106 | Prepared by the action of nitric
(Dioxypropionic
acid)
=C3H604
acid on glycerine, and by the
spontaneous decomposition of
nitro-glycerin. A thick sy-
rup, forming iodopropionic
acid (CAHs IO), when the pro-
duct formed with phosphorus
iodide is treated with water.
Acrylic Series.
SERIES II.-Formula C.H., CO(OH).
The acrylic series of acids are mostly oily liquids, the primary
acids existing as glycerides in natural fats and oils.
They are mono-
basic, that is their salts are formed by the substitution of one equi-
Fused with potassic hydrate,
they eliminate hydrogen and form potassic acetate and a potassic salt
of another acid—
valent of a metal for one of hydrogen.
ClaRs40.
Oleic acid
Nascent
series.
+ 2 ECHO
+ Potassic =
hydrate acetate
This series includes:—
IR. R.
+
palmitate
C.HsKO, + Cl6EIs. KO2 + H3.
Potassic
Potassic
+ Hydro-
gen.
hydrogen converts them into the acids of the acetic
610
HANDBOOK OF MODERN CHEMISTRY.
Name.
Acrylic acid ..
Crotonic acid. .
Angelic acid . .
Pyroterebic acid
Damaluric acid
Damolic acid..
Moringic acid
Cimicic acid .. |
Physetoleic acid
Hypogaeic acid
Gaidic acid ..
Oleic acid
Elaidic acid ' ..
Doeglic acid . .
Brassic acid . . . .
Erucic acid
Secondary Acids.
Methacrylic acid ..
Methylcrotonic acid
Ethylcrotonic acid
Formula.
Remarks.
C.H.CO(OH)
C.H.CO(OH)
C, H,CO(OH)
C.H.I.O.,
Cºho,0,
C15H230,
CIGI1900,
C15H200,
CigHap),
Cisſiº,0,
Crºſſa,0,
18
C19H860,
C.H.20,
C.H.20,
C.H.CO(OH)
C
O(OH)
*E 7
O(OH)
C.
#
§
{}
C.H.CO(OH)
}
Preparation.—By the oxidation of acrolein
C, H,0. A colorless liquid freezing at
44-6° F. (7° C.), and boiling at 284° F.
(140° C.). By the action of nascent hydro-
gen, it is converted into propionic acid
(C, H.O.), and by the action of bromine into
dibromopropionic acid.
It was supposed to be the acid obtained by the
saponification of croton oil, but this is
doubtful. It is prepared by the oxidation
of crotonic aldehyde. It is a white crys-
talline body melting at 161-6°F. (72° C.),
and boiling at 357.8°F. (181° C.), evolving
hydrogen when heated with potassic hydrate.
Found in angelica or sumbul root, and also
prepared by heating oil of camomile (an-
gelic aldehyde) with potassic hydrate. A
crystalline solid, melting at 113° F. (45°
C.), and boiling at 374° F (190° C.).
A liquid boiling at 410° F. (210°C.) prepared
by the distillation of terebic acid.
Acids existing in the urine of cows and
horses.
Present in the oil of ben, together with stearic
acid, etc. -
A yellow crystalline acid extracted from a kind
of bug. -
A crystalline acid obtained from sperm oil. It
melts at 86° F. (30° C.).
Exists as a glyceride in earth-nuts with pal-
mitic acid, etc. It melts at 93.2° F. (34° C.)
Colorless crystals, melting at 100:4°F. (38°C.),
prepared by the action of nitrous acid on
hypogaeic acid.
An acid present as a glyceride (olein) in most
natural fats and non-drying oils (see Can-
dles). Crystallizes in white needles, which
melt at 57.2° F. (14° C.). Specific gravity
at 66.2°F. (19° C.) 0-898. Insoluble in
water; soluble in alcohol, ether, and in
sulphuric acid. Nitric acid converts it
into acids of the acetic series, and
nitrous acid converts it into elaidic acid.
The solid acid is oxidized slowly, and the
liquid acid rapidly, by exposure to air.
Fused with potassic hydrate it yields acetate
and palmitate of potassium.
By the action of nitrous acid on oleic acid.
A crystalline body melting at 111:2° F.
(44° C.).
An acid prepared from the oil obtained from
the doegling or bottle-nose whale.
An acid obtained from the oil of a species of
brassica (colza).
An acid from the oil of the black mustard.
An acid isomeric with crotonic acid. A color-
less oily liquid, prepared by the action of
phosphorous chloride on ethylic dimeth-
oxylate. Fused with potash, it yields hy-
drogen and potassic propionate and formate.
BENZOIC SERIES. 611
Sorbic Series.
SERIES III.-Formula C, H2n-2CO(OH).
This includes:—

Fusing Point. Occurrence and
Sr.
Name. Formula. Preparation.
i
• F. 2 C,
Tetroleic acid . . . . . C.H.CO(OH)=C, H,0, 84 168-8 76-0 | Prepared by the
action of po-
tassic hydrate
on chloro-cro-
tonic acid.
Sorbic acid . . . . . . C.H.CO(OH)=C, H,0, 112 || 273-2 || 134-0 || Found in moun-
tain ash berries.
Stearolic acid . . . . Cribſ, CO(OH)=Cls H,0, 280 | 118.4 || 48-0 | Prepared by the
action of po-
tassic hydrate
on bromoleic
acid.
Benzoic Series.
SERIES IV.-Formula C, H2n-CO(OH).
Preparation.—(1.) By the oxidation of the corresponding aldehydes
and alcohols. Thus benzoic acid may be obtained either from
benzoic aldehyde (C6H4CHO), or from benzylic alcohol (C6H4CH2OH).
(2.) By the action of alkalies on the nitriles (abnormal cyanides).
C6H3CN + KHO + H2O = C6H3CO(OK) + NH3.
Benzo- + Potassic -i- Water = Potassic + Ammonia.
nitrile hydrate benzoate
(3.) By the action of water on the corresponding acid chlorides.
(4.) By the action of sodium and carbonic anhydride on the mono-
brominated derivatives of the CAH2n-6 series of hydrocarbons—
C6H3Br + Nag + CO, - C6H,CO(ONa) + NaBr.
Bromo- + Sodium + Carbonic = Sodic benzoate + Sodic bromide.
benzene anhydride
612 - IEIANT)|BOOK OF
MODERN CIIEMISTRY.
This series includes : —


Melting Pt. Boiling Pt.
T Mol. r
Name. Formula. Wit.
o F. o C. o F. C.
Phenoic acid . . 140° 0 || 60’0
Collinic acid .. C.H.C.9(HO) 108 2ſ 6'6 97-0
º ge - *-6 - 4 - 0
Benzenic acid.. 230'0 | 11 0-0 || 455-0 || 235'0
ſ Present in gum ben-
zoin and in other gums.
Preparation. See General
methods. Also (1) by the
oxidation of a mixture of
benzene and formic acid ;
(2) by boiling hippuric
acid with hydrochloric
acid ; (3) By the oxida-
tion of certain organic
Celºſ,CO(OEI) bodies, as casein, gelatin,
g G [15 22 * e •2 * etc. Properties. Feathery
Benzoic acid . . =C. He Oa 1 250-5 1214 |4622 239:0 & crystals, soluble in alco-
hol and boiling water.
Nitric acid has no action
upon it. With fuming
nitric acid it forms a,
substitution product.
With the haloids it also
forms substitution pro-
ducts. With PCls it
forms benzoic chloride.
With nascent hydrogen it
forms hydrobenzoic acid
UCe Ho CO(OH),
ſ Exists in three modifi-
e ºn g - cations: (1.) Parato/uic.
Toluic acid C.H.Cºlon) 136 |347.0 | 1750 | (2.) # (3.) Or-
8 *-* 8. Sº 2 thotoluic. A crystalline
| body with similar reac-
Utions to benzoic acid.
* , it CeBIs CH,CO(OH) Prepared by General
Alphatoluic acid *** {...i 186 1697 || 76.5 509-0 || 265-0 || Process 2. A crystalline
8 *-*-8 V in body.
Xylic acid ... C, H., (CEI.,)., CO(OH) , , - a A. J tº ºf º s Exists in two forms
ği. acid) • aſ {} i. × ) 150 248-0 | 120° 0 || 523°4 || 273-0 }: xylic and parasyid
acids.
º ºr ſ CPI,
Alphaxylic acid |** {{#ico(OH) | 150 | 107.6 42.0
FV 0 II loº).3
Cumylic acid ... 9aºzº).9995) 164 | 802.0 | 1500
-- Nº. 10 *-i- 12 v 3
i tº Tº ſº -
Culmic acid C.H.(gH2)CŞ(OH) 164 1976 92.0
- N2 lo lº S-73
ºr ſ Caſſ
Homocumic acid C.H., { ČičO(OH) || 178 || 1256 || 52.0
FV 11 [114.V2
Some of the derivatives of benzoic acid need further notice.
Benzoic Chloride; Benzoyl chloride (C7H3001).
Preparation.—By the action of phosphorus pentachloride on benzoic
acid.
Properties.—A colorless, pungent liquid. Specific gravity 1-106.
Its vapor is heavy, and burns with a greenish flame.
OXYBENZOIC OR SALICYLIC SERIES. 613
Benzoic Anhydride or 0xide (C14H10O3). *
Preparation.—By the action of benzoyl chloride on potassic benzoate
(C, H.O(ONa) + C, H,001 = (C.H.O)2O + NaCl).
Properties.—It forms oblique rhombic prisms, melting at 42°C.
Benzoic peroxide (C14H10O.).
Chlorobenzoic Acid, C6H3Cl.CO(OH).
Preparation.—By the action of potassic chlorate and hydrochloric
acid on benzoic acid.
Bromobenzoic Acid, C6H4BrCO(OH).
Preparation.—By the action of bromine on argentic benzoate.
Nitrobenzoic Acid, CsPI (NO3)CO(OH).
Preparation.—By boiling benzoic acid in fuming nitric acid.
Properties.—A crystalline substance.
Hippuric or Bénzamidacetic Acid (CoHoNOs).
Natural History.—Hippuric acid occurs as a potassium and sodium
salt in the urine of horses, cows, etc., and also in human urine,
more especially after the administration of benzoic acid.
In preparing the acid from urine it is necessary that it should be
fresh, otherwise it evolves ammonia, benzoic acid being formed by the
action of heat on the hippuric acid.
Preparation.—By the action of the zinc salt of amidacetic acid on
benzoic chloride.
Properties.—The acid crystallizes in slender prisms. It melts when
heated, and at a high temperature is decomposed, forming benzoic
acid, benzonitrile, etc. It is slightly soluble in water (1 in 400 at
60°F.), and in hot alcohol.
Its reaction is acid. With hot sulphuric acid, it yields benzoic
acid; with hot hydrochloric acid, amidacetic acid and benzoic acid;
with mitric acid, benzoglycollic acid with the evolution of nitrogen.
It is monobasic, and forms salts called hippurates.
Oxybenzoic or Salicylic Series.
SERIES IV. (a.)—Formula C, Han g(OH)CO(OH).
The acids of this series are monobasic and dihydric. They are
related to benzoic acid in the same manner as the lactic series is
related to the acetic series. t
It includes—
614
HANDBOOK OF MODERN CHEMISTRY.
Name.
Formula.
Preparation and Properties.
Salicylic acid (orthoxy-
benzoic acid) . .
Oxybenzoic acid (metoxy-
benzoic acid)
Paraoxybenzoic acid
Anisic acid . .
Cresotic acid (carbocresy-
lic acid) . .
Oxymethylbenzoic acid
Mandelic acid (formo-
benzoic) . . * *
Phloretic acid
Hydrocoumaric acid
Hydroparacoumaric acid
Phenyllactic acid ..
Thymylcarbonic acid or
thymotic acid . . . .
-
-
C.H.,(OH)00(OH)
C.H.O
7+5 - 3
do.
do.
CeBIOs
ſ Preparation.—(1.) By passing CO2
into phenol containing small
pieces of sodium. (2.) By melt-
ing salicin or coumaric acid with
potassic hydrate (C, H20,--KHO
=C, H.KO,-i-H.). (3.) By dis-
tilling oil of wintergreen with
potash. Properties.—A crystal-
line body, melting at 368-6°F.
(187°C.), decomposed at 428°F.
(220°C.), evolving phenol. Dis-
solves in cold water (1 in 1,000).
With PC], it forms chloroben-
zoic chloride. Its solution gives
\ a violet color to ferric salts.
ſ Preparation.—By the action of
nitrous acid on amido benzoic
acid. Properties.—A crystalline
body, melting at 390-2° F.
(199° C.). Requires a high
temperature to decompose it.
It gives no violet color with
ferric salts.
Prepared by heating anisic acid
with HI. Soluble in water (1
in 126 at 60°F.) Melts at 410°F.
(210°C.) With ferric salts gives
a yellow precipitate.
U
Prepared by oxidizing anisic alde-
hyde (CsII,0) or crude oil of
aniseed. Colorless crystals,
melting at 347° F. (175° C.).
Soluble in alcohol, ether, and
hot water.
Prepared by the action of CO., and
Na on cresol (C, HSO). Ortho-
cresotic acid melts at 237-2°F.
(114°C.); paracresotic acid at
298.4°F. (148° C.), and meta-
cresotic acid at 338° F. (170° C.).
They all produce a deep violet
color with ferric chloride.
Prepared by the action of HCl on
} bitter almond oil.
Melts at 264-2°F. (129°C.). Pre-
pared by the action of potash
on phloretin. Phloretic acid gives
a green color with ferric chlo-
ride, whilst isophloretic acid has
no action.
Preparation. — By the action of
C0, and Na on thymol. It melts
at 248° F (120°C.), and gives
a blue color with ferric chloride.
GALLIC SERIES. 615
Dioxybenzoic Series.
SERIEs IV. (3)—Formula C, Han–0(OH)2CO(OH).
These are monobasic acids, and include—
Names. Formula. Preparation and Properties.
Pyrocatechuic acid .. Prepared by melting potash either
Carbo-hydroquinonic with piperic or quinic acid, or
acid. with kino, catechu, etc. When
the acid is heated, it yields CO2
and pyrocatechin.
Oxy-salicylic acid ... C.H. (OH)2CO(OH) | By the action of potash on iodo-
salicylic acid. It melts at
379.4° F. (193° C.), and is de-
composed at 418.6° F. (212° C.),
yielding anthrachrysone. It is
soluble in water, alcohol, and
ether. It strikes a deep blue
with ferric chloride.
Dioxybenzoic acid ... C.H. (SO, H),CO(OH)
-a-
Gallic Series.
SERIES IV. (y.)—Formula C, Hea-loſQH)3CO(OH).
Gallic Acid (Trioxybengoic acid) C6H2(OH)3CO(OH) = C, HSO5.
Molecular weight, 170.
Natural History.—It is found in gall nuts, acorns, hellebore root,
black and green tea, etc.
Preparation.—By the action of argentic hydrate on di-iodo-salicylic
acid.
Properties.—(a.) Physical. A white crystalline body (C7H60s.OH.)
having a powerful astringent taste. At 419°F. (215°C.) it is decom-
posed into CO2 and pyrogallic acid (C6H6Os), whilst by a heat of
4802°F. (249°C.) it is resolved into carbonic anhydride, water and
metagallic acid (C5H2O2). It is soluble in water (1 in 100 at 60°F.,
and 1 in 3 at 212°F.).
(3.) Chemical.—The solution has an acid reaction and rapidly
decomposes. It does not precipitate gelatine. It forms a black
precipitate with iron salts, the color disappearing by heat in the case
of ferric salts, but not in the case of ferrous salts. It is readily
oxidized, and hence rapidly reduces gold and silver salts. When
boiled with a solution of arsenic acid, tannic acid is formed.
(For the TANNINs see SUPPLEMENTARY CHAPTER.)
616
HANDBOOK OF MODERN CHEMISTRY.
Cinnamic Series.
SERIES W.—Formula C.H., CO(OH).
This series is monobasic.
acetic series of acids.
C.H2n+1CO(OH)
Acetic
C, H2n-1CO(OH)
Benzoic
It includes—
The cinnamic series is related to the
benzoic series in a similar manner as the acrylic is related to the
Thus:–
C.Hon—CO(OH);
Acrylic.
C, H2n-6CO(OH)
Cinnamic.

Acids. | Formula.
Cinnamic C.II,000H)
Atropic ditto
Isatropic ditto
-|
º
148
• F.
#|Melting Point.
° C.
248-0
222-8
392.0
120-0
106-0
200 - 0
ſ . Preparation.—(1.) By heating benzoic
aldehyde with acetic chloride (C,EI.0
+ C, H,00] = HCl + C, H,0.). (2.) By
the oxidation of cinnamon oil. . It is
present ready formed in the balsams of
Peru and Tolu. Properties.—A crystal-
line body, boiling at 559.4°F. (29.3°C.).
Soluble in alcohol, not very soluble in
Y water. With nitric or with chromic acid
it forms benzoic acid and benzoic alde-
hyde. With nascent hydrogen (water
and sodium amalgam), or heated with
hydriodic acid, it forms hydrocinnamic
acid (CoIIIo9,). Fused with potassic
hydrate it forms potassic benzoate and
acetate. By heat it forms CO., and
cinnamene (CsIIs).
Formed together with tropine (C.H., (NO))
from atropine, by the action of alkalies.
SERIES W. (a.)—Formula C, H2n-nCO(OH).
This includes phenyl-propiolic acid, C6H3C2CO(OH), a crystalline
acid melting at 276.8°F. (136°C.). It is prepared by the action of
potassic hydrate on bromocinnamic acid, and is converted by nascent
hydrogen into hydrocinnamic acid.
Naphtoic Series.
SERIES WI.-Formula C.H., 13CO(OH).
This series includes two isomeric acids, viz., a-naphtoic acid, and
B-naphtoic acid. The former melts at 320°F. (160° C.), and the
SUCCINIC SERIES. 617
latter at 359.6°F. (182° C). By the action of sodium and carbonic
anhydride on a- and 3-naphtol, the two isomeric acids a- and 3-oxy-
naphtoic acids are formed.
SERIES VI. (a.)—Formula C.H2n-16CO(OH).
This includes anthracene carboaylic acid, C14H9CO(OH), a solid body,
melting at 402.8°F. (206°C.). It is prepared by heating anthracene
with carbonic oxychloride. When heated it yields anthracene and
carbonic anhydride.
B.—DIBASIC ACIDS.
That is acids containing two semi-molecules of carboxyl (COOH).
Succinic Series.
SERIES I.-Formula C, Hen(COOH)2.
Preparation (general).--(1.) By the oxidation of many fatty Organic
bodies, such as suet, etc., with nitric acid.
C4H8O. + O3 - H2O + CAH6O4.
Butyric acid + Oxygen = Water + Succinic acid.
(2.) By the oxidation of the primary glycols.
C.H. (OH)2 + 2O2 F 2H2O + C.O2(OH)2.
Glycol + Oxygen = Water + Oxalic acid.
(3.) By the action of potassic hydrate or hydrochloric acid on the
the nitriles (cyanides) of the dyad radicals.
C, Hen(CN) t _ ſ C, Hon(COKO)
{{º} + 2KHO + 2H.0 = {{#sº
(4.) By the action of sodium or silver on the iodo-derivatives of the
acetic acid series. Thus :-
2CAH2, ICO(OH) + Age = Cs, Hin(COOH)2 + 2AgI.
Properties (general).-These dibasic acids are all crystalline solids,
yielding by heat either the anhydride and water, or carbonic anhy-
dride and an acid of the acetic series.
Thus it will be noted that the acids of the succinic series are related
to the glycols, as seen by the second method of preparation described
above; to the dyad radicals, as seen by the third method, and by the
further fact that in some cases they yield the hydride of the radical,
when heated with an excess of caustic baryta; and also to the acids of .
the acetic series, as seen by the fourth method of preparation, whilst con-
versely, in some cases, the succinic series may be converted into the
acetic, by the abstraction of carbonic anhydride. -
+ 2NHs
618 HANDBOOK OF MODERN OBEMISTRY.
This series includes—


#-
É £ |Melting Pt. Boiling Pt.
Names. Formula. §§ Remarks.
3P= o F. o C. o F, o C.
Oxalic . . . . §: 90 See below.
Malonic. . . . CH3(COOH)2 104 || 284-0 || 140 Prepared by the oxidation of malic
acid and of propene glycol. De-
oomposed at 3020 F. (150° C.).
Succinic ... C., H., (GOOH)2 128 356-0 | 180 455 235 | See page 620.
Pyrotartaric | Ca Ha(COOH), 132 || 233°6 || 112 Prepared by heating tartaric acid.
It volatilizes at 3929 F. (2009 C.)
Adipic . . . . . C. He (COOH)2 146 284-0 || 140 | } By the oxidation of fats with nitric
Pimelic C. H. oGCOOH)2 160 273-2 || 134 ſ acid.
Suberic CeBI, 2 (COOH)2 174 257-0 || 125 Prepared by the oxidation of cork
with nitric acid, and by the
action of nitric acid on certain
fats. Fusible and volatile.
Anchoic ... Cz Haa (COOH)2 | 188 240.8 116 By the action of nitric acid on
(Separgylic) Chinese wax, and on the fatty
acids of cocoa nut oil.
Sebacic .. CeBI, e(COOH), 202 || 260-6 || 127 Prepared by the destructive distil-
lation of oleic acid.
Rocellic ..] C18Hao(COOH)2] 300 269-6 || 132 Present in certain lichens. Wola-
tile at 392° F. (2000 C.).
Oxalic Acid.—(COOH)2=C, H2O4; (crystals=C.H.O.,2H2O).
Natural History.—Oxalic acid is present in most plants, either in a
free state, or as a lime or alkaline oxalate. It occurs very frequently
as a lime-salt in the urine (mulberry calculus). Its formation in this
latter case is no doubt due to some imperfection in the normal
oxidising process going on in the body, the carbon and hydrogen
not being converted, as usual, into water and carbonic anhydride.
Preparation.—(1.) By the oxidation of organic compounds, such as
sawdust, sugar, etc., either by the action of nitric acid, or by their
fusion with potassic hydrate, whereby a potassic oxalate is formed.
Clºfſz. Qu + Ola 6C2H2O4. + 5H2O
Sugar + Oxygen Oxalic acid + Water.
(2.) By the direct combination of an alkaline metal with carbonic
anhydride.
-
2CO3 +
Carbonic anhydride +
Nag
Sodium
Na,CaO4.
Sodic oxalate.
(3.) By the decomposition of cyanogen with water.
C3N2 + 4H2O C2H2O4. +
Cyanogen + Water Oxalic acid +
(4.) By the action of heat on potassic formate (2HCO(OK)=H.--
K2C2O4).
(5.) By the oxidation of ethylene glycol (see page 617).
Commercial preparation of oacalic acid.—A thick paste is first prepared
by mixing sawdust with a solution containing potassic hydrate (1 equiv.)
and sodic hydrate (2 equiv.), the alkaline solution having a specific
gravity of 1:35. This paste is then heated on iron plates at 400°F. (204°C.)
for some hours, whereby hydrogen is evolved from the decomposition
2NH.
Ammonia.
*-
SUCCINIC SERIES. 615
of the water of the alkaline hydrates, whilst the oxygen liberated
oxidises the sawdust. The grey mass formed contains about one-fourth
its weight of oxalic acid. This is then treated with water, which leaves
the oxalate of soda undissolved, owing to its insolubility in water. The
insoluble residue, after the action of the water, is then boiled with
lime, and the resulting calcic oxalate decomposed with Sulphuric acid.
The clear liquor containing the Oxalic acid is then evaporated down
and crystallised.
The sawdust yields on an average about half its weight of crystal-
lised oxalic acid.
The alkalies are recovered from the liquid with which the mass is
first treated by evaporating the solution to dryness, calcining the
residue, in order to destroy any organic matter present, and after-
wards decomposing the carbonates with calcic hydrate. The recovered
alkalies may then be used for a new operation.
Properties.—(a.) Physical. Oxalic acid consists of colorless crystals
(oblique rhombs). At a heat of 212°F. (100°C.) the water of crystal-
lisation is driven off; at 320°F. (160° C.) the acid sublimes, but at a
temperature above this it is decomposed into formic acid and carbonic
anhydride (C.H2O,-CH2O2+ CO2), the formic acid being afterwards
further decomposed by heat into water and carbonic oxide (CH2O2= .
CO+ H2O). It is soluble in water (1 in 8 at 60°F., and 1 in 1 at
212°F.), and also in alcohol. The acid is poisonous. Chalk and
magnesia constitute the proper antidotes.
(a.) Chemical. The solution of Oxalic acid is very acid to litmus.
Sulphuric acid converts it into H2O, CO2 and CO. Nitric acid acts
slowly upon it, converting it into CO2, Heated with alkalies, it yields
hydrogen and an alkaline carbonate. -
Uses.—In calico-printing; in cleansing brass and leather; also as a
solvent for Prussian blue in the manufacture of blue ink.
It forms salts called oxalates, a few of which we note as follows:–
Solubility in water.
Names. Formula. Remarks,
- 0 F. 2120 F.
E. g. ( Neutral . . . . . . . CaRAQ.12aq l in 3
# g \ Acid (binoxalate or
; : salt of sorrel) ... CaBKO,2aq l in 40 1 in 6
Tº : / Hyperacid or quad-
pi o roxalate . . . . . CaFIKO4,CaFi 203,2aq
Sodic oxalate . . . . . . almost insoluble
5 g / Neutral . . . . . . Ca(NH4)2012aq not very | very Yields by heat oxamide ; ,
## heated with phospho-
53 ric anhydride it form
5 : e * * * * Cyanogen. -
5 8 \ Acid (binoxalate) . . . CaFI(NHA)O4aq Yields oxamic acid by
heat.
Calcic oxalate . . . . . . . C., Ca"0,4aq insoluble
Ferrous oxalate . . . . . . . C., Fe"0, insoluble
Ferric oxalate . . . . . . . Fea (C30a).s3.aq very solu-
- ble
Ethyl (Oxalic ether) . . . . . (CoHs)2C2O4. Sp. Gr. 1-09. Boils at
1838° F. (84:30 C.),
Acid ethyl oxalate or ethyl- | (C.Hs)C., H04
oxalic acid * * * *

620 HANDBOOK OF MODERN CHEMISTRY.
All the oxalates are decomposed by heat. The alkaline and the
earthy oxalates, if not too strongly heated, evolve CO, and leave
carbonates of the metals, whilst the oxalates of other metals leave
metallic oxides. With sulphuric acid the oxalates break up into CO
and CO2, leaving a residue of Sulphate, which residue, however, does
not blacken by the action of the acid, inasmuch as no separation of
carbon takes place. -
| Succinic Acid.—Caf14(COOH)2=C4H6O4. [Molecular weight, 128.
Fuses at 356°F. (180° C.). Boils at 455°F. (235 °C.).]
Watural History.—It is found in amber, in some lignites, and occa-
sionally in animal and vegetable substances.
Preparation.—(1.) By the action of potassic hydrate on ethylene
cyanide—
C.H.(CN)2 + 4H2O = 2NH3 + C, H60.
Ethylene cyanide + Water = Ammonia + Succinic acid.
(2.) By the oxidation of butyric acid—
C4H8O2 + O3 H2O + C.H6O4.
Butyric acid + Oxygen Water + Succinic acid.
(3.) By the action on malic acid, either of (a) nascent hydrogen,
or (3) fermentation (see p. 489), or (y) hydriodic acid.
(a.) C, HSO5 + H2 = H2O + C.II6O4.
(y.) C, HSO5 + 2HI = H2O + H2 + C, HSO4.
Properties.—Colorless crystals (oblique rhombs). It melts at 356°F.
(180° C), and boils at 455° F (235° C), water and succinic anhy-
dride (C, H,0s) being formed. [Iso-succinic acid melts at 266°F.
(180° C.), and boils at 802°F. (150°C.), forming CO2 and propionic
acid (C3H6O2).]
It is soluble in water (1 in 5 at 60°F., 1 in 3 at 212°F.). With
nascent oxygen it yields ethylene, CO2, and H2O ; (C4H6O4+O =
C.H.,4-200,--H2O). Nitric and hydrochloric acids have no action
upon it. Distilled with H.SO, and MnO, it yields acetic acid.
Distinctive Reactions of Succinic Acid.—Succinic acid (as a sodic salt)
gives a red-brown precipitate with ferric chloride. Isosuccinic acid
gives none.
Succinic acid is not precipitated from its Salts by the mineral acids.
It gives a white precipitate with BaCl2, on the addition of an alcoholic
solution of ammonia. Benzoic acid is precipitated from its salts by the
mineral acids. It gives no precipitate with BaCl2.
Malic Series.
SERIES I. (a.)—Formula C, H2n-1(OH)(CO.OH)2.
Those acids are trihydric and dibasic —
TARTARIC SERIES. . 621
NAMEs. Formula. Remarks.
Tartronic . . . . . CH(OH)(COOH), Preparation.—By the spontaneous decom-
(oxymalonic). F U3114U5 position of nitro tartaric acid.
ſ Malic acid is widely distributed in plants as
in the juices of apples, pears, etc. (with
citric acid), or of rhubarb (with acid
potassic oxalate), or in the berries of the
mountain ash, or in tobacco leaves (as
bimalate of lime). Preparation.—(1.)
From the above juices. (2.) By the
action of nitrous acid on asparagine
(CHSN,03) and on aspartic acid
. (C.H.N.O.), bodies found in º #.
Malic. . . . . . . C.H. (OH)(COOH), J gus, the marsh, Ingllow, etc. (C.HsN398
(Oxysuccinic). *s *" § ), asparagine + 2 HNQ,+C, H,0; +2H.0
s + 2N.). (3.) By the action of argentic
hydrate on monobromo-succinic acid.
Properties.—Crystalline, soluble in water
and in alcohol. With ferments, such as
putrifying cheese, it yields CO2, succinic
and acetic acids; digested with hydriodie
acid in sealed tubes, it yields succinic
acid; fused with potassic hydrate, or
boiled with a strong mineral acid, it
- yields sorbic acid.
Citramalic. . . . . C.H.(OH)(COOH)
Glutanic . . . . . CAEIs(OH)(COOH), Preparation.—By the action of nitrous acid
on glutamic acid, obtained by heating
casein, etc., with hydrochloric acid.
2
Oxyadipic.. ... C.H.(OH)(COOH),
Oxysuberic ... CsIII (OH)(COOH),
Tartaric Series.
SERIES I. (3.)—Formula C, H2n-2(OH)2(COOH)2.
These acids are tetrahydric and dibasic —
NAMEs. Formula. Remarks.
it forms tartronic and afterwards ma-
lonic acid.
C.H.,(OH)2(CO.OH), See below.
Mesosalie tº e is tº C(OH),(CO.OH), A uric acid derivative. By deoxidation
Tartaric *
(dioxysuccinic).
Dioxyadipic ... C.Hs(OH)2(CO.OH),
Dioxysuberic . . . C. HiſOH),(C0.0H),
Tartaric Acid, C.H. (OH)2(CO.OH)4=CH606—Molecular Weight,
150. -
Natural History.—Ordinary tartaric acid constitutes the acid of
grapes, and, together with citric, oxalic, and malic acids, is found in
numerous plants.
622 ELANDBOOK OF MODERN CEIEMISTRY.
Commercial Preparation.—(a.) Argol or tartar (hydric potassic tartrate,
KHC, H4O6), a substance deposited from fermenting grape juice, is
first purified by solution in hot water, and subsequent crystallization
(cream of tartar).
(3.) This purified residue is now dissolved in hot water and boiled
with powdered chalk, whereby an insoluble calcic tartrate, and a
Soluble potassic tartrate are formed :
2KHC4H4O6 + CaCO3 = K2C4H4O6 + Ca"C.H.O6+ H2O + CO2.
Hydric potas- + Calcic = Potassic + Calcic + Water + Carbonic
sic tartrate carbonate tartrate tartrate. anhydride.
(y.) Calcic chloride is now added to the clear solution, whereby
the whole of the tartaric acid is precipitated as calcic tartrate : thus,
E.C.H.4O6 + Ca"Cl2 = 2KCl + Ca"C.FIAO6.
Potassic tartrate + Calcic = Potassic —H Calcic tartrate.
chloride chloride
(8.) This tartrate of lime is now collected and boiled with dilute
sulphuric acid, whereby an insoluble calcic sulphate is formed, whilst
the filtered solution contains the free tartaric acid :
Ca"C4IHAO6 + H2SO4 - C4H6O6 + Ca"SO,.
Calcic tartrate + Sulphuric = Tartaric + Calcic
acid acid sulphate.
Tartaric acid may also be prepared by the action of nitric acid on
gum or sugar of milk.
Varieties.—There are four modifications of tartaric acid;—
(a.) Dewtro- or common tartaric acid, so called from its property of
causing the plane of polarization to rotate to the right.
(3.) Lavo-tartaric acid, which rotates the plane of polarization to
the left.
(y.) Inactive or meso-tartaric acid, which is without action on a
polarized ray. It, moreover, cannot be resolved into dextro- and
laevo-tartaric acids. In this latter respect it differs from paratartaric
or racemic acid, which is also without action on a polarized ray, but
which is a compound of dextro- and lavo-tartaric acid, and is capable
of resolution into these two modifications of the acid.
(3.) Metatartaric acid. An uncrystallizable modification produced
by fusing the ordinary acid. +
Properties of common tartaric acid.—(a.) Physical. Colorless crystals
(oblique rhombs), inodorous, having an acid taste, permanent in
the air, and very soluble in water and alcohol. The crystals fuse at
340° F. (171.1° C.), forming metatartaric and isotartaric acids, both
of which are uncrystallizable acids. At 374° F. (190° C.) it loses
water, and becomes tartaric anhydride (CaFISOro), which, by long
FUMARIC SERIES. 623
boiling in water, may be converted into tartaric acid. At a tem-
perature of 401°F. (205°C.) it forms paratartaric acid and CO2.
(6.) Chemical.—Its solution is very acid, and rapidly decomposes
by keeping, acetic acid being formed and a fungus deposited which
contains 3-5 per cent. of nitrogen.
With Hydriodic acid, it forms succinic and malic acids; with
powerful oxidizing agents, it forms formic acid; with mild oacidizing
agents, tartronic acid; fused with potassic hydrate, it yields potassic
oxalate and acetate, but no hydrogen is evolved; with concentrated
sulphuric acid, it is carbonized; with phosphorus pentachloride, it forms
chloromaleic chloride; with acetic chloride, it forms diaceto-tartaric
acid, C.H. (OC.HsO)2(COOH). ; and with alcohols, it forms the various
ethereal salts.
The following represent the formulas of some of the tartrates —
Names, Formula. Solubility in water.
{ neutral . . K.C, H,0s Very soluble.
Potassic tartrates { acid (Cream RHC, H,0s Soluble in boiling but
of tartar) .. H not in cold water.
* s ) neutral ... (NH4)2CH,0s-Haq. Soluble.
Ammonic tartrates | acid $ tº (NH. #&#. t; Do.
º * neutral . . . Na,CAH,0s--2 aq. Do.
Sodic tartrates ... }. ... Na. Öğ. +aq. Do.
Rochelle salt | *
Potassic and *
Or & RNaCH,0s--4 aq. 1 in 1; at 60°F. (15:5° C.)
Seignette salt ſ sodic tartrate 4*-* 4 × 6 2 *-
Potassio-antimonious tartrate, | K(SbO)C.H.95 Eaq. 1 in 15 at 60° F (15.5° C)
& heated to 400°F. be- te O 1 ºo (O
Or tartar emetic . . comes KSbC, H,0s. 1 in 3 at 212°F. (100° C.)
Racemic Acid has the same composition as tartaric acid. It yields
the same products as tartaric acid by heat, and forms analogous salts.
It differs, however, from tartaric acid in being less soluble in water,
and in its solution neither rotating the plane of polarization, nor
precipitating a neutral calcic salt.
Fumaric Series.
SERIES II.-Formula C.H. (COOH),
These dibasic acids form succinic acid with nascent hydrogen, and
substitution derivatives of succinic acid with the haloid acids and with
the halogens. They also form monochlorinated acids of the malic series
with hypochlorous acid.
624
HANDBOOK OF MODERN CHEMISTRY.
The series includes the following:—

ACID. Formula.
Fumaric C.H.(COOH),
Maleic .. Do.
Citraconic .
Itaconic ...|} C,EI,(C00II),
MeSaconic ..
Melting Pt.
° F. o C.
Remarks.
About
392-0 | 200-0
266-0 || 130-0
176.0 80.0
320-0 | 160-0 |4
392.9 || 200.5
See above for preparation.
The acid of the common fumitory.
Prepared, together with maleic
acid, by the action of heat on
malic acid. It is a crystalline in-
soluble acid (1 in 200 at 60°F.).
By heat it forms maleic anhy-
dride. With nascent hydrogen
it forms succinic acid.
A crys-
talline volatile soluble acid. Its
reactions are similar to those of
fumaric acid.
ſ Prepared from citric acid. Citra-
conic acid is formed by the pro-
longed action of heat on citric
acid. It is very soluble in water.
Itaconic acid results when citra-
conic acid is heated with water
for some hours. It is not very
soluble in water. Mesaeo??c acid
is formed by decomposing the
product of the action of heat on
a mixture of citraconic and hy-
drochloric acids. With nascent
hydrogen all three yield pyrotar-
taric acid. The three acids when
treated with bromine yield three
isomeric brominated acids.
Phthalic Series.
SERIES III.—Formula C, H2n-6(CO.OH)2.
These include—

Melting Point.
ACID. Formula.
o F. o C.
Phthalic ... 365 - 0 185 By oxidizing benzene
and formic acid by
C.H.(CO.OH), MnO, and H.S0.
Isophthalic . . Above 572 | Above 300
Terephthalic Do. Do.
Mesidic 550-4 288
Xylidic C.H.,(CH)(C0.0H), 54 l'4 283
Isoxylidic . . 707-0 375
Cumidic C.H.(CH.),(CO.OH), Sublimes.
PHTELATIC SERIES. 625
C.—TRIBASIC ACIDS,
and Acids of Higher Basicity, etc.
Tricarballylic Series.
SERIES I.-Formula C, H2n-1(CO.OH)3.
Tricarballylic Acid, CH3(CO.OH)4=C5H,06 is a trihydric acid,
and is produced by heating citric acid with hydriodic acid—
Citric acid + Hydriodic = Tricarballylic + Water + Iodine.
acid acid.
Citric Acid (oxytricarballylic acid) CŞEI,(OH)(COOH)4=C5H8O.
Natural History.—This acid is found in the juice of lemons and
oranges, and also in many fruits, such as gooseberries, etc., in con-
junction with malic acid.
Preparation.—The lemon juice is first allowed to ferment, so that
mucilage and other impurities may be separated. The clear liquor is
then neutralized with chalk, whereby an insoluble calcic citrate
(Ca32C6H507) is formed. The precipitate is collected and decomposed
with dilute sulphuric acid, the citric acid being afterwards crystallized
from the solution.
Properties.—(a.) A crystalline dimorphous body, freely soluble in
hot and cold water. The crystals fuse at 212°F. (100° C.), and de-
compose at 300° F. (149° C.), forming aconitic acid. Heated to
338° F. (170° C.), it forms itaconic acid.
(3.) Chemical.-A tribasic tetrahydric acid. The solution reddens
litmus and rapidly decomposes.
It ferments with putrid flesh, forming butyric and succinic acids;
sulphuric acid decomposes it ; nitric acid converts it into oxalic acid.
With potassic hydrate, it forms acetic and oxalic acids.
Citric, like tartaric acid, prevents the precipitation of ferric oxide
by ammonia. The soluble compound formed has not been very well
made out.
The acid is used in medicine, in dyeing, and in calico printing.
Desoxalic or Trioxycarballylic Acid, (CsII2(OH)3(COOH)s=
C6H6Oo, is an unstable acid, and forms, when heated, tartarie and
glyoxylic acids.
Meconic Acid (C, H.O.) is a tribasic acid present in opium, and
consists of mica-like plates, soluble in alcohol and in boiling water,
but insoluble in cold water.
Mellitic Acid C6(CO.OH)6 is a hexabasic acid, existing as an
aluminic salt in “honey Stone.”
We may note that, with one exception, the whole of the benzene
(C6H6) series of acids, derived by the substitution of the group COOH
for the hydrogen of the benzene, are known. Thus—
S S
{
626 HANDBOOK OF MOIDERN CHEMISTRY.
Benzoic acid ... g º 'º ... CºH,COOH.
Phthalic acid, etc. ... ... C6H4(COOH)2.
Trimellitic acid, etc. ... ... C6H3(CO.OH)3.
Pyromellitic acid, etc. ... ... C6H2(COOH)4.
Unknown ... tº Q tº ... C6H(CO.OH)3.
Mellitic acid ... * - ſº ... Co(COOH)6.
REACTIONS OF SOME OF TELE CHIEF ACIDS.
(I.) Group reactions. (II.) Special reactions.
I.—Group Reactions.
1. Heat the acid in a test tube—

Forms a white
Fuses and - Not blackened. Not
º blackens after . White blackened.
y. a short time. blackening sublimate. Wolatile.
ackening.
Tartaric (caramel Citric. Malic. Oxalic. Acetic (yields
odor). Meconic. acetone).
Uric (burnt feather Pyrogallic. Formic.
odor). Benzoic.
Hippuric (benzene Succinic.
odor). - Butyric. .
Gallic. - Hydrocyanic.
Tannic. Phenic.
2. Heat the acid in a test tube with sulphuric acid—

Blackens Blackens Not - te
instantly. after a time. blackened, Wolatile.
Tartaric. Citric. Oxalic. Evolves C0, Acetic
Pyrogallic. Malic. and CO. Formic Evolve CO
Gallic (red). Uric. Sulphocyanic. Evolves | Benzoic WO1V6 UU).
Tannic (brown). Meconic. CSO, giving odor of | Succinic
Hippuric. 2"
Hydrocyanic and other
cyanogen acids. E-
volve CO and NH,
3. Render the acid solution neutral, and add calcic chloride.
Filter off the precipitate—
Precipitat If soluble in acetic acid = Tartaric acid.
* † If insoluble in acetic, but soluble in HCl = Oxalic acid.
"Boil with lime water; a precipitate indicates citric acid.
Filtrate. 3 Boil for a long time with lime water and alcohol; a
l precipitate indicates malic acid.
REACTIONS OF ACIDS. 627
4. Add to the acid solution ferric chloride—
A Red Coloration, but no ppt. Other Reactions.
Acetic ; color disappears with HCl Carbolic; purple.
Formic; 5 y } % Gallic and tannic; black.
Pyrogallic ; , , 3 y Ferrocyanic; blue.
Sulphocyanic ; color disappears with Ferricyanic; brown (blue with FeSO.).
HgCl2, but not with HCl. Benzoic
Meconic ; color neither discharged by Succinic light red.
HgCl, nor by HC1. Hippuric |
5. Add to the neutral solution argentic nitrate.
White precipitates occur with the following acids, all of which are
soluble in ammonia; viz.: hydrocyanic (insol. in HNO3; sol. in
RCy); sulpho-, ferro-, and ferri-cyanic ; meconic ; Oxalic; succinic;
benzoic; tartaric (see Tests); citric; malic; acetic. The silver salt is
reduced by formic and pyrogallic acids.
6. Add to two portions of the solution, potassic hydrate and
hydrochloric acid respectively—
Potassic Hydrate. Hydrochloric Acid (to neutral solution).
Tartaric ; white ppt. on addition of acetic Uric; white ppt. (powder).
acid. Benzoic ; , , (flakes).
Gallic ; green ppt. Hippuric ; , (feathety-crystals, solu-
Tannic ; brown ppt. ble in boiling water).
Pyrogallic ; black ppt.
II.-Special Reactions.
Acetic Acid (C,EI.O.) and the Acetates.
1. The acid is soluble in all proportions in water, alcohol, and ether.
It dissolves camphor and several resins.
2. Heat. The acid and its salts are decomposed, yielding acetone
(CAH60). -
3. When a mixture of sodic acetate and soda lime is heated, it
yields methane or marsh gas (3.NaC.H.O., +NaHOCa"H2O, (soda
lime)=2|Na,CO3--CaCO3 + 3CHA).
4. The acetates, heated with alcohol and sulphuric acid, yield the
fragrant ethylic acetate (C.H.S.C., H3O4)(characteristic).
5. The solid salts, heated with sulphuric acid, yield acetic acid.
6. Ferric chloride gives on boiling a deep red coloration, with the
precipitation of a basic ferric acetate.
628 HANDBOOK OF MODERN CEIEMISTRY.
Oxalic Acid (C2H2O).
1. Heat ; (a) fuses ; (3) gives a white sublimate if carefully
heated ; (y) produces dense white fumes towards the end of the
reaction, but never blackens. (The oxalates of the alkalies and alkaline
earths, when heated, leave carbonates, which effervesce with acids;
but the oxalates of other metals leave metallic oxides.)
2. HaSO4 and heat; CO and CO2 are evolved, but without blacken-
ing. (The reaction with the oxalates is similar, a residue of sulphate
remaining.)
3. Calcic chloride (Ca"Cl2) gives (a) in very dilute solutions a ppt.,
after a time, of calcic oxalate, Ca"C.O., ; (3) in moderately strong solu-
tions, it gives an immediate ppt. The ppt. is soluble in HCl or HNO,
(but not in acetic acid, as in the case of phosphates) and is repre-
cipitated by ammonia.
The reaction is not interfered with by the presence of ammoniacal
salts.
4. Argentic nitrate gives a white ppt., Ag3C,04.
|Uric Acid ( C;NH,0s).
1. Heat; (a) blackens immediately; (3) odor of burnt hair.
2. A drop of nitric acid, mixed with uric acid in a capsule, and
evaporated to dryness, yields, when the cold residue is touched with
ammonia, the deep red tint of murexide (CaMgHaO6).
Hippuric Acid (C6HoNO3).--Crystals; rhombic prisms, and acicular
crystals.
1. Heat. (a.) Fuses directly, and volatilizes with partial decom-
position, yielding benzoic acid, ammonic benzoate, and benzo-nitrile.
(6.) A carbonaceous residue left; any sublimate formed is of a red
tint. (y.) Odor of benzo-nitrile.
[N.B. Hippuric acid is insoluble in ether, but benzoic acid is soluble.]
The hippurates, when fused with excess of potassic hydrate, give
off ammonia, and yield benzene by distillation.
Citric Acid (C6H6O7).—1. Heat, (a) does not blacken immediately;
(3) evolves pungent acid fumes; (y) blackens ultimately (distin-
guishes it from malic acid).
2. Sulphuric acid and heat blackens the acid, but not immediately
(distinguishes it from tartaric acid).
3. Calcic chloride gives no ppt. on boiling in a solution of the free
acid, but on neutralizing the solution with KHO a white insoluble
ppt. of calcic citrate is thrown down. The ppt. is insoluble in KHO
(distinguishing it from calcic tartrate), but is soluble in NH,Cl.
Boil the ammonic chloride solution, when a white ppt. is thrown down,
which is no longer soluble in NH,Cl.
4. Calcic citrate heated with ammonia and argentic nitrate, yields
no metallic mirror, thus distinguishing it from tartaric acid.
Malic Acid (C, H605).—Crystals; colorless prisms.
1. Heat chars the acid, and yields fumaric acid.
REACTIONS OF ORGANIC ACIDS. 629
2. Calcic chloride; no ppt. in very dilute aqueous solutions, but
a ppt. forms when alcohol is added (calcic malate).
3. Plumbic acetate, in neutral solutions a white ppt. (plumbic malate),
sparingly soluble in ammonia, distinguishing it from plumbic citrate and
tartrate, which dissolve easily.
Tartaric Acid (C, Hö06).
1. Heat (a) blackens immediately; (3) caramel Odor; (y) gives no
sublimate.
2, H2SO, and heat; (a) blackens immediately; (3) caramel odor.
(Reaction similar with tartrates.)
3. Potassic (chloride or) acetate gives a precipitate (with moderately
strong solutions) of acid potassic tartrate, KHC, H,06. The delicacy
of this reaction is increased—(a) by shaking ; (3) by the addition of
alcohol.
4. Calcic chloride (in eaccess) gives, in moderately strong solutions,
an immediate white precipitate of calcic tartrate, Ca"C, H,06, which
rapidly becomes crystalline. The precipitate is soluble in KHO or
NaHO. Ammoniacal salts prevent the reaction.
Eilter off the precipitate and dry gently. Place it in a test-tube with
a drop of ammonia and a crystal of argentic nitrate, and heat very
gently, when a brilliant silver mirror will be obtained. (This distin-
guishes it from citric acid.)
5. Lime and baryta waters, and plumbic acetate; white precipitates,
soluble in excess of acid.
6. In neutral solutions of tartrates :-
Argentic nitrate; a white precipitate, soluble in ammonia.
Calcic chloride; a white precipitate.
N.B.-Tartaric acid interferes with the precipitation of ferric
hydrate by ammonia, owing to the solubility of the hydrate in a
tartaric acid solution.
Benzoic Acid (CFH6O2), Crystals, prismatic needles.
1. Heat, (a) in a test-tube; melts at 212°F. (100° C.), and a little
above this sublimes; emits an aromatic odor; (3) On platinum foil;
burns with a smoky flame.
2. Sulphuric acid and heat does not blacken, but dissolves the acid.
3. Witric acid; no action.
4. Distilled with excess of CaO, yields benzene—(C, HGO,--CaO=
C6H6+ CaCOs).
5. Ferric chloride; a pale, yellow-brown precipitate of basic ferric
benzoate (BzóFe2O",Fe2O3 + 15 aq.).
Succinic Acid (C, HSO4); Crystals; oblique, rhombic prisms.
1. Heat; (a) in test tube; melts at 356°F. (180°C.), and sublimes
in silky needles, emitting an irritating odor; (3) On platinum foil :
burns with a blue flame, without smoke.
2. Ferric chloride gives, in neutral solutions, a brownish-red preci-
pitate of basic ferric succinate, Sn, Fe,0", Fe,0s, soluble in mineral
acids; darkened by ammonia.
6 30 HANDBOOK OF MODERN CHEMISTRY.
3. Nitric acid, no action.
Note the distinctions between benzoic and succinic acids, as:
follows:–
1. Benzoic acid heated on platinum foil burns with a smoky flame,
which succinic acid does not.
2. Ferric chloride gives a brown precipitate with both acids. Treat
this with ammonia. One portion is decomposed whilst another forms
a soluble succinate and benzoate. Filter, and add alcohol and baric
chloride to the clear filtrate :-
(a.) With a ferric succinnate, a white crystalline precipitate is formed.
(6.) With a ferric benzoate, no precipitate is formed.
Tannic Acid—
1. Heated in tube, fuses, blackensimmediately, and gives no sublimate.
2. Sulphuric acid and heat; turns dark brown. (See Gallic Acid,
which turns red.)
3. Nitric acid and heat, a yellow solution, turning red on boiling.
4. Ferric chloride, a black precipitate and coloration.
Gallic Acid—
1. Heated in tube, fuses, blackens immediately, giving an orange-red
sublimate.
2, Sulphuric acid and heat; turns magenta red, becoming more
intense as the heat increases. (See Tannic Acid, which turns brown.)
3. Nitric acid and heat; same as Tannic Acid.
4. Ferric Chloride ; same as Tannic Acid.
Hydrocyanic Acid (See page 522).
Ferrocyanic Acid (See page 523) (H,Fe"Cyg).
1. Reaction acid; decomposes alkaline carbonates; stable.
2. Ferrous sulphate; a light blue ppt., K. Fe. FeCyg.
3. Ferrio chloride; a deep blue ppt. (prussian blue) 'Fe", Fe"3Cyrs.
Ferricyanic Acid (See page 524) (HSFe"Cyg).
1. An unstable acid.
2. Ferrous sulphate; a deep blue ppt. (Turnbull’s blue) Fe"3 Fe",Cyg.
3. Ferric chloride; a deep brown coloration. -
Sulphocyanic Acid (See page 524) (HONS).
1. Reaction acid; easily decomposed.
2. Ferric chloride; a blood-red coloration, but no ppt., even on
boiling; color discharged by mercuric chloride (HgCl2).
Meconic Acid (C, H2O+).
1. Ferric chloride ; a blood-red coloration; color not discharged by
mercuric chloride,
631
SUPPLEMENTARY CEIAPTER.
SUPPLEMENT TO THE FATTY ACIDs (page 605).
Fats and Oils.
Definition.-The fats and oils are combustible bodies, having an
unctuous feel, communicating a greasy stain to paper, in soluble in
water, but soluble in alcohol and in ether. They are all compounds
of glycerine with palmitic, oleic, or stearic acid.
Natural History.—They are found in all parts of the vegetable,
but chiefly in the seeds (rape) and fruit (olive.) They also occur in the
animal, formed by the conversion of starch and saccharine matters,
and are found located chiefly under the cuticle, or in the omentum
or round the kidneys. The fat is generally lodged in cells, the en-
velope of which consists of cellulin or gelatinous tissue. Fat not un-
frequently occurs as a product of tissue degeneration (as in the
kidney, liver, etc.), and is also found as a product of secretion (as in
milk). 3.
Preparation.—(1) By simple pressure (croton, olive, almond, lin-
seed, mustard, etc.).
(2.) By heat and pressure, as in the case of the solid fats (such as
lard, human, cod-liver (dark colored), castor (hot drawn), etc.
(3.) By cold and pressure (castor and cod-liver (cold drawn), lard).
(4.) By distillation (volatile oils); (see page 551).
(5.) By destructive distillation (coal-tar oils).
(6.) By solution in a fived oil, in alcohol, or in ether (yelk oil).
(7.) By fermentation (oil of bitter almonds).
CLASSIFICATION.
I. Faced oils; that is, oils which decompose at a temperature below
that at which they distil, and impart a permanently greasy stain to
paper. -
II. Volatile oils ; that is, oils which may be distilled unchanged,
and that impart a greasy stain to paper, which is not permanent.
I.-Fixed Oils,
The fixed oils are composed of two or more neutral substances,
632 HANDBOOK OF MODERN CHEMISTRY.
combined with some of the acids of the acetic series, or with acids
closely allied to them.
These are divided into two classes:–
(A.) Saponifiable oils.
(B.) Won-saponifiable oils.
(A.) Saponifiable Fixed Oils.-Some of these are solid, as, e.g.,
palm oil; and some are liquid, as, e.g., olive oil. Of animal fats,
those from warm-blooded animals are usually solid at ordinary tem-
peratures (such as Suet); whilst those from cold-blooded animals are
commonly liquid (such as the fish oils). The fats and oils have very
little odor or taste. Their specific gravity varies from 0-91 to
0-94.
The action of heat.—The liquid oils may be solidified by cold. The
solid fats melt at from 70° to 140°F. (21.1° to 60° C). At 500°F.
(260° C.) they usually undergo slight decomposition. At about 600°F.
(315.5° C.) (that is, below the temperature at which they distil—
hence they are termed ficed oils), they decompose, giving off carbonic
anhydride and acrolein. At a higher temperature, as, e.g., when
dropped on a red-hot iron plate, they are decomposed into various
hydrocarbons (oil gas).
Solubility.—They are all insoluble in water, but soluble in boil-
ing alcohol and in cold ether. They are solvents of sulphur, phos-
phorus, etc.
Action of Air.—(a.) Rancidity. By exposure to air the oils com-
monly turn rancid. This, however, does not occur in the case of
pure oil. Rancidity is brought about by the presence in the oil
of certain albuminous matters, which, during decay, decompose the
glyceric oleate, or the glyceric salts of other acids.
(6.) Drying and non-drying oils.--Most fats and oils, when exposed
to the air, absorb oxygen (some at the same time evolving carbonic
anhydride), ultimately becoming solid. These are called “drying
oils,” of which linseed, rape, and mustard are illustrations. They contain
glyceric oleate (olein), or glyceric salts of acids homologous to oleic
acid. This oxidation process has, in some cases, been so rapid that
active combustion has resulted. This property of drying is, in many
cases, increased by dissolving in the oil when hot a twentieth part of its
weight of litharge or oxide of manganese. This constitutes (as in
the case of linseed) what is called “boiled oil.” Other oils do not
absorb oxygen –chemically, they differ from the drying oils in con-
taining glyceric salts of acids other than those belonging to the
oleic series, as linoleic acid, the acid of linseed ; nevertheless, they
gradually alter by exposure, though in a different manner. These are
called “non-drying oils,” such as Olive, almond, rape-seed oils, etc.
The oils are all decomposed by the action of the haloids.
Acids act on them, forming various compounds.
With the fixed alkalies they form salts called soaps (saponification).
FDXED OILS.
633
Potash forms with them soft soap, and Soda hard soap. Ammonia
does not form true soaps with the oils, but compounds called
amides.
The fats combine with metallic oxides and hydrates to form
plasters, glycerin being set free.
3PbO + 3H,0 + 2(CAH3.3C18H350.)
Plumbic + Water + Oleate of glyceryl
oxide
(olive oil)
Thus—
sºmº
sº
3(Pb2Cls Haº,0.) + 2(CAH;3|HO).
Oleate of lead
+
Glycerin.
(lead plaster)
The following is a tabulated list of the principal fats and oils:–
Name. Source. Sp. Gr. Fuºus.
1. Won-drying Oils.
Olive . . . . Olea europaea.. 0°918 Solid below 32° F. Virgin oil is the oil obtained by
(0° C.) pressure without heat.
Almond . . . . . Amygdalus com- 0:918 at Solid below—13° F. Seeds yield 50 per cent. of oil.
munis 609 F. (—25° C.)
Sesamé .. Sesamum indi-
CUlDil
Rapeseed ..
Mustard . . . . Yields erucic acid on saponifica-
tion.
Colza. Brassica oleifera 0°913
Yelk º -
Male fern . . Filix mas Contains filicic acid, C14H is O.
Human Contains olein and margarine.
2. Drying Oils.
Linseed Linum usitatis- 1.939 at Solid at –15° C.) 25 per cent. extracted from seed;
Simum 549 F. 12 per cent. left in the cake.
Walnut . . ſº e
Hempseed .. º at
Poppy seed teºes * * *
Croton Tiglic acid, but not crotonic acid,
- is obtained from the oil.
Castor Ricinus com- 0.969 Solid at - 14°F. A riconoleate of glyceryl (C, Hs
Imunis (—25-69 C.) 3C1sbias Os).
3. Fish Oils.
Sperm Liquid fat in 0-868 Solid at 45° F. Contains phocenin.
head of sper- (7.2° C.)
maceti Whale.
Common whale | Counmon whale 0°927 Solid at 320 F.
(00 C.)
Cod liver .. Gadus morrhua Solid at 30° F. Contains constituents of bile;
(—1° C.) also a phosphorized fat (the oil
4. Solid Fats. gives a crimson with HaSOA).
Tallow ... | Fat of OX, sheep, Suet; almost entirely stearine.
etc.
Lard .. Soft fat of pig
Butter Milk *
Palm . . . . . . . . . Elais guineensis $1°F. (27:2° C., | Becomes more solid by keeping.
Nutmeg butter Myristica 87° F (30-5°C.) | Volatile oil and myristin (CAHs
º 3C14H270s).
Cocoa nut. . . . . Cocos Inucifera 68°F (20° C.) | Contains "glycerin, combined
with caproic, caprylie, lauric,
myristie, and palmitic acids.
Used, for marine soap, being
soluble in NaCl.
Cacao butter ... Theobroma cacoa 85° F (29'59 C.) | Chiefly stearine.
Laurel fat..
Yellow wax ... Honeycomb of 0-96 145° F. (63° C.) | White wax is the yellow wax
º: jº cerblein
- 5 per cent.) and cerotic acid.
Solid fat in head 0-940 120° (490 C.) Palmitate of cetyl yields ethal
Spermaceti
of spermaceti
Whale
(not glycerine) on saponifi-
cation.
The following Table, from Bloxam, shows the principal fatty bodies,
and their corresponding acids and fusing points.
634 - HANDBOOK OF MODERN CHEMISTRY.

—F
* Fusing Fusing
*...* | Formula. j Fº .# Formula. Fº
Stearin Cs; Pingos Tallow. | 125 to 157| Stearic. Cls Hos0, 159
Palmitin . . . Cºho,0; Palm oil. 114 to 145 || Palmitic. C.H.O. 144
Margarin . . . C.H.,0s | Olive oil. 116 Margaric. Cº., H.O. 140
Qlein Cs, Ho,0s Do. Below 32 | Oleic. CisłIa,0. 40
Cetin Ca2Hg,02 Spermaceti. 120 Palmitic. Ciºłł.O., 144
Myricin CºgPIs,C), Bees’-wax. 162 P}o.
(B.) Nonsaponifiable Fats.-This includes certain bodies, such
as cetene and ethal from spermaceti, myricin and cerem from bees'-
wax, cholesterin, etc.
They are all solid crystalline bodies, and fuse at temperatures
varying from 180° to 300°F. (82° to 149° C.). *.
II-Volatile Oils. (See page 551.)
Soaps.
A soap results from the action of alkalies on fats and oils. If
potash be used for effecting saponification, a hard soap results; if soda,
a soft soap. Tallow, palm-oil, cocoa-nut oil, and kitchen stuff are the
fats commonly employed in the manufacture of hard soap, whilst seal
and whale oil are used for soft soap. We may here note that—
(a.) Tallow consists of about three parts of solid stearin (or the
glyceride of stearic acid), and one part of liquid olein (or the
glyceride of oleic acid).
(3.) Palm oil consists chiefly of solid palmitin (or the glyceride of
palmitic acid) and olein.
(y.) Seal and whale oils consist chiefly of olein.
I. Hard soaps.-The fat is first boiled in a soda ley. When
perfectly dissolved a quantity of common salt is added (salting out).
The soap immediately rises to the surface, being insoluble in a solu-
tion of common salt. Thus an insoluble sodic stearate (or, if palm-oil
be used, sodic palmitate) and sodic oleate are formed, whilst the
glycerin remains in solution. Thus— :
(a.) C, H2(CeBI,0),0s + 3NaHO = 3(CsIIs;O(NaO)) + C, H,0s.
Stearin ; or glyceride + Caustic = Sodic stearate + Glycerin.
of stearic acid soda
(6.) C3H3(CeBIssO)3,O3 + 3NaHO = 3(CeBIssO(NaO)) + C, HsO3,
Olein; or glyceride + Caustic = Sodic oleate + Glycerin.
of oleic acid Soda
The soap, that is, the sodic stearate and oleate, is then allowed to
collect on the surface, whilst the alkaline ley containing the glycerine
is drawn off from below. The soap is then pressed in iron moulds.
CANDLES. 635
If tallow has been used, the soap is a mixture of stearate and oleate
of soda ; but, if palm oil, of palmitate and oleate of soda.
Transparent soaps are prepared by first drying the soap, then
dissolving it in spirits of wine by heat, and pouring the solution into
moulds after a sufficient quantity of spirit has been removed by
distillation, so that the solution may set perfectly when cold.
Glycerine soap consists of a mixture of the soap and the alkaline
solution containing the glycerin, as Small a quantity of water being
used in the operation as possible.
In silicated soap, silicate of soda is mixed with the soap.
In the common yellow soaps, a quantity of common rosin is used.
Castile soap is made from olive oil, which contains the glycerides
both of palmitic and stearic acids (margarine), as well as oleic
acid. Hence Castile soap is a mixed stearate, palmitate and oleate
of soda.
The appearance of mottled soap depends on the presence of veins of
oxide of iron. It is supposed to indicate that the soap is tolerably
free from water.
II. Soft soaps.-In fish oil, which is the fat used for soft soaps,
olein, or the glyceride of oleic acid, predominates. This, with a
potash ley, yields oleate of potash, of which soft soaps are principally
composed. The separation of the soft soap is not effected by salting,
but the solution is simply evaporated to the necessary consistency.
If common Salt was used, the soft soap would then be converted into
a hard Soda Soap.
Candles.
Stearic acid is commonly employed in preference to tallow for
candles, because it fuses at a much higher temperature 159° F.
(70.5° C.).
I. The old process of Saponification by Lime.—The melted tallow is
first mixed with lime and water, and the mixture subjected to the
action of Superheated steam. In this way an insoluble stearate and
oleate of lime are formed. These are then separated from the solu-
tion which contains the glycerin, and are decomposed by the action
of sulphuric acid. The mixed stearic and oleic acids set free, are sub-
mitted to pressure in a hydraulic press, whereby the oleic acid is
squeezed out, and stearic acid, mixed with more or less palmitic acid,
obtained.
II. The process called Saponification by Sulphuric Acid—The fats
(palm oil, cocoa-nut oil, or any kind of refuse fat), are first mixed in
copper boilers with about one-sixth their weight of sulphuric acid, and
the mixture heated by steam for some time to 350° F. (176.1° C.).
The sulphuric acid converts a part of the glycerin into sulpho-glyceric
acid (C3H80s, SO3), and decomposes the remainder, a mixture of crude
palmitic, stearic and oleic acids remaining (probably as sulpho-acids),
636 EIANDBOOK OF MODERN CHEMISTRY.
together with a solid, fatty acid, called elaidic acid, isomeric with, and
derived from the liquid oleic acid. Thus it will be noted that the quantity
of solid fats obtained by this process is increased. These fatty acids,
after being collected and well washed, are distilled in a current of
steam heated to 600°F. (315-5° C.), the oleic acid being removed
from the distillate by pressure. A pitchy matter remains in the
retort, which is used in the manufacture of black sealing-wax.
III. Saponification (so called) by Steam.—The advantage of this pro-
cess is that the glycerin can be obtained at once in a pure state. It
consists in merely distilling the fat by the action of superheated
steam at 600°F. (315.5° C.), when both glycerin and fatty acids
distil over. After the distillate has stood for a short time, the fatty
acids collect on the surface of the glycerin, and on removal may be
at once subjected to pressure to separate the oleic acid. The glycerin,
as obtained by this process, is fit for the market.
The Tannins.
The Tannins are a class of amorphous bodies, widely distributed,
constituting the astringent principles of plants. Our knowledge
of these bodies, which are probably modifications of tannic acid, is
very limited. The following special reactions are to be noted:—
1. They have all a slightly acid reaction, and a very astringent taste.
2. They yield a blue-black, and in some cases a green precipitate,
with ferric salts.
3. They precipitate albumen and gelatine from their solutions.
4. They form leather (a substance having a power of resisting
putrefaction) with animal membranes. [NOTE.-Gallic acid has no
such power.]
The tannic acid of the oak, (gallotannic acid ; C.7FI22O7), or, what
is more probably a glucoside of tannic acid, is extracted by a mixture
of water and ether from certain growths called “nut-galls,” occurring
on the leaves of the Quercus infectoria, and said to be produced by the
puncture of an insect.
Tannic acid is a yellowish amorphous mass, resolved by heat into
carbonic anhydride, pyrogallic and metagallic acids. It is soluble in
water, the solution reddening litmus. When boiled with acids or
with a strong solution of potash, it splits up into glucose and gallic acid,
the same change occurring spontaneously when the powdered galls,
mixed with water, are allowed to ferment. This fermentative process
results from the presence in the nut-galls of a nitrogenized body,
capable of acting as a ferment. The glucose formed ultimately under-
goes alcoholic fermentation.
The tannins that turn ferric salts black, yield pyrogallol (C6H6O4) on
dry distillation; whilst those that turn ferric salts green, yield pyro-
catechin (C6H6O2).
THE TANNINs. 637
Ink.-This consists of a mixture of nut-galls with water, gum, and
ferrous sulphate. By standing, the ferrous salt is converted into a
ferric salt, and a black tannate of ferric oxide (?) formed. A trace of
creosote is usually added, to prevent the ink becoming mouldy. The
brown colour of old ink is due to the oxidation of the tannic acid,
leaving simply the brown ferric oxide. Ink leaves an iron-mould
stain wherever it has fallen on linen after the fabric has been washed,
from the removal of the tannic acid by the alkali of the soap.
Tanning.—The skin (that is to say, the dermis or true skin) is
converted into leather by the action of tannic acid on the gelatine.
The leather formed is tough, resists putrefaction, and is impermeable
to water.
(a.) The skin is first soaked in lime-water for the purpose of Sapo-
nifying the fat, and dissolving the sheath of the hairs, so that their
removal may be easily effected.
(3.) After the skin has been cleansed and the hair removed, it is
placed in very dilute sulphuric acid, in order that any adherent lime
may be neutralized (otherwise a tannate of lime would be afterwards
formed), and also to “raise the skin,” that is, to open the pores to
receive the tanning liquid. --
(y.) The skin is then placed in an infusion of oak-bark (ooze) for
a few weeks, and, finally, a number of skins are arranged in layers
in a pit, coarse ground oak-bark being placed between each skin.
Sometimes sumach (the ground shoots of the rhus coriaria) is used in
the place of oak-bark. On removal from the pit, the skins are dried
in a free current of air.
Currying consists in wetting the leather first with water, and after-
wards with oil. As the water evaporates the oil sinks into the skin.
In tawing (as in the preparation of kid for gloves), the lime on the
skin is removed by lactic acid (a sour mixture of bran and water
being commonly employed). The skin is afterwards impregnated
with aluminic chloride (a bath of alum and salt being commonly
used), which effectually prevents putrefaction.
In shamoying (as in the preparation of wash-leather), the skin is
first sprinkled with oil, and then beaten with wooden hammers. It is
afterwards exposed to a warm atmosphere in order to dry the oil,
any excess of oil being removed by a weak alkaline bath.
638 HANDBOOK OF MODERN CHEMISTRY.
CHAPTER XXV.
THE ETHERS.
Oxy-ETHERs—Ethers of Monohydric Alcohols—Preparation—Ethers of Di- and
Trihydric Alcohols. SULPHo-ETHERs. HALOID ETHERs.
I. Oxy-Ethers.
These ethers are the oxides of alcohol radicals. The relationship
subsisting between a metallic hydrate, as NaOH, and a metallic oacide, as
Na2O, has its counterpart in the relationship between an alcohol (that
is, a hydrate of an alcohol radical) as ethylic alcohol, C3H3(OH), and
an oacy-ether (that is, an oxide of an alcohol radical) as ethylic ether,
(C2H5)2O.
Just, too, as we have monohydric, dihydric, and trihydric alcohols,
so we have ethers of monohydric, dihydric, and trihydric alcohols
respectively.
Ethers of Monohydric Alcohols.
Boiling Pt.
ETHERs. Formula. Sp. Gr. Remarks.
• F. ° C.
Methylic . . . . (CH.),0 —5.8 —21 | 1.617 |A colorless liquid. Does

not liquefy at –16 °C.
Burns with a feebly lumi-
nous flame. The vapor
is soluble in water (33 in
1), alcohol, wood spirit,
and Sulphuric acid. It
forms substitution com-
pounds with Cl, as
(CH,Cl),O, etc.
Methylic ethylic .. (CHA)'(C.H.)"Q || 51.8 || 11
Methylic amylic .. (º)0 197.6 | 92
Ethylic (ether) .. (C.Hs),0 96.0 35-6 || 0:723 |A colorless, very volatile
liquid ; will not freeze;
combustible; vapor den-
sity (air =1) 2.586. Ex-
plodes when mixed with
oxygen. Soluble in water
(1 in 10). Miscible in
all proportions with al-
cohol. Forms with
ex ,S0, Sulphovinic acid.
Ethylic butylic ... (C.H.)(CH)0 1760 | 89 # ...”.”.
Ethylic amylic .. (Ö. H. (C.H, )0 233.6 112 posure to air, it forms
Butylic . . . . . . (9,50.9 2}.} 104 acetic acid, and by the
Amylic . . . . . . § 20 34: iſ: action of hot nitric acid,
Allylic. C.H.).0 179-6 || 8 carbonic, acetic, and ox-
Phenylic § 6),0 alic acids. With chlorine
Benzylic. . C.H.).0 it forms substitution pro-
* - tº e 2
Phenylbenzylic .. (CSHg)(C, H,)0 ducts.
oxy-ETHERs. 639
Preparation of the Simple and Miced Ethers (General).
(I.) In the case of the ethers derived from the alcohols of the methylic
series (C, H2n+10H), or of the vinylic series (CAHan 10H).
Preparation.—By the action of sulphuric acid on the alcohol. The
process takes place in two stages:—
(a.) The sulphuric acid first converts a portion of alcohol into a
sulpho-acid.
C.H. (OH) + H2SO, -: C.H.; HSO, + H2O.
Ethylic alcohol + Sulphuric = Sulpho-ethylic acid + Water.
acid (sulphovinic acid)
(3.) This sulpho-acid then reacts on a fresh portion of alcohol.
C.H.HSO, + C.H.(OH) = (C.H.).O + H2SO4.
Sulpho-ethylic acid + Ethylic alcohol = Ethylic ether + Sulphuric acid.
[NotE.—A. That the sulphuric acid concerned in the first stage of
the reaction is set free in the second stage. Thus, theoretically, a
small quantity of acid should convert an unlimited quantity of alcohol
into ether.
B. That by boiling the ethers with dilute sulphuric acid they are
converted into their corresponding alcohols. Thus :-
(a.) (C.H.).0 + 2 H2SO4 = 2C(C.H.)HSO4] + H2O.
(6.) (C.H.)HSO, + H2O = H, SO, + C.H.(OH).]
(II.) In the case of ethers derived from the alcohols of the ethylic series
(C.H2n+,OH), of the vinylic series (C, Hen OH), and of the benzylic
series (C, H2n-10H).
Preparation.—By the action of an iodide derivative of the cor-
responding hydrocarbon on the sodium or potassium derivative of the
corresponding alcohol.
Thus, say we wish to prepare ethylic ether : {}
(a.) By the action of sodium on ethylic alcohol, we first form a
sodium derivative :-
20.H.OH + Nag – 202H.NaO + H2.
Ethylic alcohol + Sodium = Sodic ethylic + Hydrogen.
alcohol -
(6.) By the action of ethylic iodide (C.H.;I) on the sodic ethylic
alcohol, we form ethylic ether and sodic iodide.
C.H.(NaO) + C.H.I = (C.H.)3O + NaI.
Sodic ethylic + Ethylic - Ethylic + Sodic
alcohol iodide ether iodide.
It will be seen that a simple ether is formed when the haloid
derivative acts on a metallic derivative of a corresponding alcohol,
e.g., when ethylic iodide acts on sodic ethylic alcohol, ethylic ether,
(C2H5)0, is formed; but that a mixed ether will be produced when
the haloid derivative acts on the metallic derivative of some isomeric
640 HANDBOOK OF MODERN CHEMISTRY.
or homologous alcohol; e.g., when ethylic iodide acts on sodic methylic
alcohol, methylic ethylic ether (CH2)(C.H.)0 is formed.
(III.) Phenylic ether is prepared by fusing together phenol and
diazo-benzene sulphate. Thus—
C6H,(NaHSO4) + C6H3(OH) = (C6Hs).0 + N2 + H2SO,.
Diazobenzene + Phenol -: Phenylic + Nitro- + Sulphuric
Sulphate ether gen acid.
Ethers of Dihydric Alcohols.
Boiling Point.
Ether. Formula.
o F. o C.
Ethylenic . . . . C.H.0 55-4 13.0
Propylenic . . . . C.H.O 63.0 35-0
Amylenic . . . . C.H100 171-0 95.0
Preparation (general).-By the action on the glycols (dihydric alco-
hols) (a), first, of hydrochloric acid, whereby a chlorhydrin is formed;
and (3), afterwards, by the withdrawal of hydrochloric acid from the
chlorhydrin, by the action of potassic hydrate. These two stages are
seen in the preparation of ethylenic ether, as follows:—
Glycol + Hydrochloric = Ethylenic chlor- + Water.
acid hydrate
(6.) C.H. (OH)C1 + KHO = C.H.O + KCl -- H.O.
Ethylenic chlor- + Potassic = Ethylenic -i- Potassic -i- Water.
hydrate hydrate ether chloride
Ethylenic Ether; Ethylenic oxide (C2H40). Molecular weight, 44.
Molecular volume, TT . Boils at 56.3° F (13-5°C.).
Preparation.—(Described above).
This ether is the only one of these ethers that has received much
attention.
It combines with acids as a base; thus, C.H,0+ HCl–C.H.,(OH)Ol.
It combines with water to form glycol; thus, C.H,0+ H2O=C.H.,(OH)2.
It precipitates many metallic salts, as hydrates, from their solutions;
thus, 2C.H.O- MgCl2 +2H,0=2|C.H.,(OH)Ol]+MgH.O.
With nascent hydrogen it forms alcohol; thus, C.H.,0+ H2=C.H3(OH).
With org/gen it forms glycollic acid; thus, C2H40+O2=C.H.403.
Ether of the Trihydric Alcohols.
Glycylic Ether, (CH3)2O, is the only ether of this class known.
It is prepared by heating together glycerin and calcic chloride, the
HALOID ETHERS. 641
calcic chloride abstracting three molecules of water from the glycerin.
Thus—
2(C3H,(OH)3) 3H2O + (C3H)2O3.
Glycerin - Water + Glycylic ether.
-:
II.-Sulpho- or Thio-Ethers.
These sulpho-ethers bear the same relationship to the mercaptans
as the ethers bear to the alcohols. Thus—
C.H.(OH) — C.H.O.C.H., ; C.H.(SH) – C.H.S.C.H.
Alcohol * Ether ; Mercaptan — Sulpho-ether.
Preparation.—(1.) By the distillation of the lead derivatives of the
mercaptans [(C.H.S). Pb=(C.H3)2S--PbS].
(2.) By the action either (a) of potassic or sodic sulphide, or (3)
of the sodic or potassic derivatives of the mercaptans, on the mono-
haloid derivatives of certain hydrocarbons. Thus:–
(a.) 20:H3Br-i-K2S=(C.H3)2S--2KBr.
(3.) C.EIAI+C.H3(NaS)=NaI+ (C.H.).S.
III.-Haloid Ethers.
These ethers are alcohols where a haloid element or a cyanogen
group has been substituted for a semi-molecule of hydroxyl.
These compounds are formed either by the action on the alcohols
(a) of the haloid acids, or (3) of the compounds of phosphorus with
the haloids; or (y) by the direct substitution of the haloids for hydro-
gen in saturated hydrocarbons. Thus : —
(a.) C.H3(OH)+HCl=C.H.Cl-i-H.O.
(3.) 30, Hs.OH--PCla=3C.H,Cl-i-H, POs.
(y.) CH,--Cl2=CH,Cl-i-HCl.
The preparation of the nitriles is described elsewhere.
The composition and properties of the most important of the haloid
ethers have been already described under the several hydrocarbons
of which they are derivatives.
642 HANDBOOK OF MODERN CHEMISTRY.
CHAPTER XXVI.
THE ALDEEIYDES.
(ALCOHOL DEHYDROGENATUM).
THE ALDEHYDES—Constitution—Preparation—Reactions—Aldehydes of the Acetic
Series—Formic Aldehyde—Aldehydes of the Acrylic and Benzoic Series—Other
Aldehydes.
The aldehydes are formed from the alcohols by the simple with-
drawal of hydrogen. Thus an aldehyde occupies an intermediate
position between an alcohol and an acid, containing, in the case of the
aldehydes of monohydric alcohols, two hydrogen atoms less than the
corresponding alcohol, and one oxygen atom less than the cor-
responding acid. Thus—
CH.CH2OH ; CH.COH ; CH.COOH.
Ethylic alcohol ; Acetic aldehyde ; Acetic acid.
There are reasons to believe that the hydrogen of the alcohol dis-
placed to form an aldehyde, is the Ho of the group CH2OH. Hence
it is customary to represent an aldehyde of a monohydric alcohol
by the formula R/COH, and of a dihydric alcohol by the formula
R"(COH), etc. The aldehydes of monohydric and of dihydric alcohols
only are known. -
The following are the formulas of the aldehydes of monohydric
alcohols : — -
Acetic series of aldehydes C, H2n + COH.
Acrylic 2 3 CnH2n-1COH.
C, H2n-3COH.
Benzoic 7 7 CnH2n-7COH.
CnH2n-6COH.
Preparation.—(General methods.)
(1.) From the alcohols; by oxidation, as, e.g., by atmospheric air;
by the action of chlorine on the dilute alcohol; by the action of dilute
sulphuric acid and potassic bichromate, etc. Thus— -
C.H.(OH) + O - CH,COH + H.O.
Ethylic alcohol + Oxygen = Acetic aldehyde + Water.
(2.) From the acids; by the dry distillation of calcic, sodic or potassic
formate with the corresponding metallic salt of a monobasic acid.
Thus—
COH(OK) + CH3CO(OK) CH3COH + K2CO3.
Potassic + Potassic Acetic + Potassic
formate acetate aldehyde carbonate.
–
ALDIEHYDES OF ACETIC SERIES. 643
Reactions.—(1.) Their conversion into the corresponding alcohols.-By
the action of nascent hydrogen (e.g., by the action of water on sodium
amalgam). Thus—
CH3COH + H2 - C2H,(OH).
Acetic aldehyde + Hydrogen = Ethylic alcohol.
(2.) Their conversion into the corresponding acids.-By Oxidation (e.g.,
by the action of air). Thus—
CH3COH + O - CH,COOH.
Acetic aldehyde + Oxygen F Acetic acid.
(3.) Their conversion into the potassic salts of the corresponding acids.-
By fusion with potassic hydrate. Thus—
CHA.COH + KHO CH3CO(OK) + H2.
Acetic + Potassic = Potassic + Hydrogen.
aldehyde hydrate acetate.
(4.) Their conversion into chloraldehydes (i.e., Cl, being substituted
for O).-By the action of phosphoric chloride. Thus—
Acetic + Phosphoric = Chlor-aldehyde. + Phosphoric
aldehyde chloride oxytrichloride.
(5.) Their conversion into acid chlorides.—By the action of chlorine
or bromine. Thus—
CH3(COH) + Cl, HCl + CH3(COCl).
Acetic + Chlorine = Hydrochloric + Acetyl
aldehyde acid chloride.
The aldehydes form crystalline compounds with the acid sulphites
of the alkali metals. The aldehydes of the acetic series form with
ammonia aldehyde ammonias. They also unite with aniline to
form phenylated aldines, and with urea to form wreides. They also
combine with hydrocyanic acid.
Aldehydes of the Acetic Series (CAH2, 4 COH).
Fusing Point. Boiling Point.
Name. Formula.
o F. o C. 9 F. o C.
Formic aldehyde .. H, COH
Acetic 33 * * CH, COH 69'S 21
Propionic ,, .. Č. H. coi 11 S-4 || 48
Butyric 2 y to tº C, H,(a)COH - 16.7-0 75
Isobutyric , §§ 143-6 62
Valeric yy tº ſº C, H,(a)COH 217-4 103
Isovaleric , & & C.H. (3)COH 199°4 93
Caproic 7 y C, Hu (8)COH 249-8 121
QEnanthylic , §§ 10-4 – 12 305-6 152
Cuprylic , tº tº Cs.HisO 352-4 178
Palmitic , tº ſº CIGHa20 125-6 52

Formic Aldehyde (Methylic Aldehyde) HCOH. A gaseous body.
Preparation.—By the action of an incandescent platinum wire on a
mixture of air and the vapor of methylic alcohol.
644 HANDBOOK OF MODERN CHEMISTRY.
Acetic (or Ethylic) Aldehyde (CHs.COH) (often simply called
aldehyde.) Molecular weight, 44. Molecular volume TT . Sp. Gr.
0-805. Boils at 69.8°F. (21°C.). *
Properties.—A colorless, volatile and very acrid liquid, soluble in
water in all proportions, having a neutral reaction, but becoming acid
(acetic acid) on exposure to air. So great is its attraction for
Oxygen that it reduces the salts of silver to the metallic state. Thus
by heating a mixture of aldehyde and argentic nitrate with a trace of
ammonia in a test tube, the silver is deposited as a brilliant metallic
mirror on the sides of the tube. When treated with potassic hydrate,
aldehyde is decomposed, and a brown substance formed, called “resin
of aldehyde.” With hydrochloric acid it forms aldol (C,EigO2).
There are three isomeric modifications of aldehyde, viz. –
Metaldehyde; crystalline; sublimes at 2.48° F (120° C.).
Paraldehyde; liquid; boils at 257°F. (125° C.).
Elaldehyde; crystalline; fuses at 35.6°F. (2°C.); boils at 201:2°F.
(94° C.).
Chloral, CCl3(COH)—By the action of chlorine, aldehyde is trans-
formed into the compound called chloral or trichloraldehyde, the H3
of the CHs being replaced by Cls. Thus—
CHA.COH ; CCls.COH.
Acetic aldehyde : Chloral.
Properties.—Chloral is a colorless liquid (specific gravity 1-5) boiling
at 2012° F (94° C.). It combines rapidly with water to form chloral
hydrate, CC1,0H(OH)2. By oxidation it forms trichloracetic acid,
CCI,CO(OH), and by the action of nascent hydrogen it is reduced to
aldehyde. By the action of alkalies it is at once decomposed into
chloroform and a formate (CC1300EI+ KHO=CCls H+ HCO(OK)).
Acetal—When gaseous hydrochloric acid is passed into a solution
of aldehyde in anhydrous alcohol, a compound of aldehyde and ethylic
chloride is formed, which, by heating with sodic ethylate, forms a
compound of aldehyde and ethylic oxide called acetal (C6H4O2) =
C.H.(O.C.H.). Acetal is a colorless liquid ; specific gravity 0.821°,
boiling at 284°F (140°C.). Under the action of platinum black it
forms, first, aldehyde, and afterwards acetic acid.
Aldehydes of the Acrylic Series (C, H2A-COH).
Of this series two members are known.

Boiling Point.
Name. Formula. ---------------------.
o F. o C.
Acrylic aldehyde C.H.0 126'5 52°5 | A colorless mobile liquid. By
(Acrolein). oxidation it forms acrylic
acid (CAH (),).
Crotonic aldehyde C.H.0 220. 1 || 104 - 5
ALDEEIYDES OF BIFNZOIC SERIES. - 645
Aldehydes of the Benzoic Series (CAH2n-COH).
The following members are known —

Boiling Point.
Aldehyde. Formula.
o F. o C.
Benzoic . . . . C.H.(COH) 356-0 | 180-0 | Preparation.—(1.) By the ox-
(Bitter almond idation of amygdalin. (2.) By
oil; Benzalde- digesting bitter almonds with
hyde). water (action of synaptase on
amygdalin). Properties.—A
colorless liquid, Sp. Gr. 1043.
Absorbs oxygen from the air,
becoming benzoic acid.
Paratoluic . . . . . C.H.(CH2)(COH) || 399-2 204-0
Alpha-toluic . . . . CaFIACH,(COH)
Cumic . . . . [CSPI,(CAEL) (COH)|456-8 || 236-0 | Present in the essential oil of
cumin, and in that of the
water hemlock.
Sycocerylic .. Cish,30
Salicylic aldehyde (salicylol), an oxy-benzoic aldehyde C6H1(OH)OOH,
is a fragrant oil, boiling at 385.7°F. (196-5°C.), found in the flowers
of the meadow-sweet (spiraºa wlmaria). By oxidation it forms salicylic
acid.
Anisic aldehyde (C6H,(OCH3)COH) is a fragrant oily liquid, boiling
at 476.6°F. (247°C.), formed by the oxidation of oil of aniseed.
Aldehydes of Series (CAH2n-6COH).
This includes cinnamic aldehyde, CH(C6H5)CH.COH, the essential
constituent of oils of cinnamon and cassia. By Oxidation it forms
cinnamic acid. -
Aldehydes of the Dihydric Alcohols.
Of these the only one of any importance is—
Glyoacal, or oa'alic aldehyde (COH)2, which may be prepared by
oxidizing alcohol with nitric acid. It forms, by oxidation, glyoacalic
acid, COH (COOH).
646 HANDBOOK OF MODERN CHEMISTRY.
CHAPTER XXVII.
THE KETONES.
Constitution—General Preparation—Properties and Reactions.
A ketone is a derivative of an aldehyde, in which the hydrogen
atom of the group COH is replaced by an alcohol radical. Thus:—
Acetic aldehyde, CH3COH, forms (CH3)2CO, acetone.
Propionic aldehyde, C.H.COH, forms (C.H.)2CO diethyl ketone.
The ketones may also be regarded, either as compounds of carbonic
oxide with monad alcoholic radicals, as (CH3)2.CO, or as compounds
of alcohol radicals with acid radicals, as CH3, C2H3O (acetone).
The following are the ketones best known. They correspond to the
aldehydes CAH2n + 1.COH, or to the fatty acids CAH2n+1COOH.
-
Boiling Point.
NAME. Formula.
• F. • C.
Dimethyl ketone (acetone). . . . CO } §:
3
Methyl ethyl ketone . . . . . . CO CH,
C.H.;
.# Methyl-isopropyl ketone . . . . CO #on, 199°4 93 -
# Methyl propyl ketone . . . . . . CO § 213.8 101
3 - CaFI,
T \Diethyl ketone (propione) . . . . CO §: 212° 0 100
2-5
3 (Methyl butyl ketone . . . . . . . CO º 260-6 | 127
#’ā; | §:
*" = ( Ethyl propyl ketone . . . . . . CO }; 262.4 || 128
t '3++7
, 9 (Methyl-isoamylketone. . . . . . . CO ºff, 311-0 155
§ { | #"
" H (Dipropyl ketone (butyrone) tº e CO {{# 291 - 2 144
3++7
- Acetone, the ketone of acetic acid, is the only one of these bodies
that has received particular attention. It is a colorless, limpid liquid,
having a specific gravity of 0.792, and a vapour density (air=1) of
2-022. It burns with a bright flame, and mixes with water, alcohol,
and ether in all proportions.
ECETONES. 647
We may here note the general preparation and reactions of the
ketones of the CO(CAH2n+1)2 group.
Preparation.—1. By the action of carbonic oxide on the sodium
organo-metallic compounds, such as sodium ethyle. Thus:-
2NaC2H, -- CO = Nag + CO(C2H5)2.
Sodium ethyle + Carbonic oxide = Sodium + Diethyl ketone.
2. By the action of the acid chlorides on the zinc organo-metallic
compounds. Thus:—
Zn(CHS), 4- 2COCH,Cl = ZnCl2 + 2CO(CH3)2].
Zincic methide + Acetic chloride = Zincic chloride + Acetone.
3. By the oxidation of the secondary monohydric alcohols. Thus:-
CH(CH3)2(OH) + O = H2O + CO(CH3)2
Isopropyl alcohol + Oxygen – Water + Acetone.
4. By the distillation of the baric or calcic salts of the fatty or other
monohydric acids, or mixtures thereof. Thus:–
(a.) Ca"(C2H5O2)2 = CaCOs + CO(CH3)2.
Calcic acetate ~ Calcic carbonate + Acetone.
fy A / { CH
(6.) Ca"(CºH,02)2 + Ca"(C.H.O.)a= 2CaCO3 + 2CO | Či,
Calcic valerate + Calcic acetate =Calcic carbonate + Methyl-butyl
ketone.
General properties and reactions.
Retones differ from aldehydes as follows:—
1. That, whereas aldehydes form acids by spontaneous oxidation,
ketones do not.
2. That whereas aldehydes, by reduction with nascent hydrogen,
furnish primary alcohols, ketones furnish secondary alcohols.
3. That, whereas aldehydes reduce ammoniacal solutions of argentic
oxide, ketones do not.
Retones resemble aldehydes by forming crystalline compounds with
hydric-sodic or hydric-potassic sulphite (bisulphites), from which
the ketone may be afterwards liberated by an alkali.
With hydrocyanic acid the ketones form cyanides, which, when
digested with hydrochloric acid and water, form acids of the lactic
series.
With ammonia the ketones, when heated, form basic compounds.
Thus acetone forms the base acetonine. Thus:—
3C3H60 + 2NH, == CoPIs N2 + 3H2O.
Acetone + Ammonia -: Acetonine + Water.
648 BIANDBOOK OF MODERN CHEMISTRY.
CHAPTER XXVIII.
THE ALECALOIDS.
The Natural Alkaloids, Vegetable and Animal—Constitution of the Alkaloids—The
Amines (Aniline)—Phosphines—Arsines–Stibines — Bismuthines — Kakodyl –
Organo-Boron and Organo-Silicon Compounds—Organo-Metallic Compounds—
Amides—Imides—Alkalamides —Nitriles-—Tests.
We shall examine the organic bases as follows:—
1. The natural organic alkalies, or alkaloids.
2. The artificial Organic bases.
ORGANIC ALKALIES; THE NATURAL ALKALOIDS.
Definition.—A group of organic bodies containing nitrogen, their
solutions having an alkaline reaction, and capable of combining with
salts to form acids.
History.—In 1803, Derosne discovered narcotine; in 1816, Serturner
discovered morphia; since which time numerous alkaloids have been
discovered by Pelletier, Robiquet, Caventou, etc.
Natural History.—They are found in all parts of the vegetable,
and constitute the active ingredients of plants. They exist in
combination with Organic acids, which are often as peculiar to the
family as the alkaloids, e.g., morphia, etc., with meconic acid; quinine,
etc., with kinic acid; Strychnia with igasuric acid ; atropine with
malic acid, etc.
A few alkaloids are found in the animal kingdom, such as urea,
kreatine, etc.
Preparation.—The ficed alkaloids are extracted from the plant, either
by water, or by dilute sulphuric or hydrochloric acid. From this
solution the alkaloid is precipitated by an alkali, or by an alkaline
earth, such as magnesia. The precipitate is then again dissolved in
a dilute acid, decolorized with animal charcoal (which must be used
very sparingly, owing to its great power of absorbing the alkaloids
and their salts), and reprecipitated from the solution with an alkali.
The precipitated alkaloid is then dissolved in boiling alcohol, the “
solution filtered, and the alkaloid crystallized from the solution.
The volatile alkaloids are prepared by distillation from the plant
with a very weak alkali. The distillate is always more or less am-
moniacal from the decomposition of a portion of the alkaloid. After
ORGANIC ALKALIES. 649
neutralization with oxalic or sulphuric acid, the distillate is evaporated
to dryness. The residue is now treated with alcohol, and the upper
layer of the mixture drawn off, filtered to separate extraneous matters,
and again evaporated. This is treated with a mixture of ether and
a potassic hydrate solution, the latter for the purpose of combining
with the acid, and the former to dissolve the alkaloid set free. The
ethereal layer is then decanted and evaporated.
Properties.—(a.) Sensible and Physical. All the alkaloids are solid,
except the three which contain no oxygen, viz., nicotine, conia, and
sparteine. They all crystallize easily from alcoholic solutions, except
quinia, which crystallizes with difficulty, and quinoidine, which is
not crystalline. None of them, except the three liquid alkaloids
mentioned, have any odor. Their taste is generally more or less
bitter. Their physiological action is very energetic. In treating
cases of poisoning by them we may say, generally, that the stomach-
pump and emetics are indicated, as well as astringent liquids, such
as strong tea, etc. Tannic acid precipitates most alkaloids from their
aqueous solution.
Action of Heat.—Conia, nicotine, sparteine, theine, and caffeine
sublime by heat unchanged : hyoscyamine, cinchonine, and some
others partially sublime; piperin, when heated, yields piperdin.
All the alkaloids are decomposed (ammoniacal compounds being
formed) if the heat applied be sufficient.
Action of Light.—The alkaloids generally have a powerful influence
on a polarized beam, some turning it to the right and some to the left.
Quinine solutions are remarkable for their fluorescence.
Action of Electricity.—The salts of the alkaloids (like other salts)
liberate the base at the platinode of the battery.
Action of Solvents.- Water. The alkaloids generally dissolve in
water very slightly, nicotine being one of the most soluble. Alcohol
dissolves them all, but in varying proportions; thus cinehonine may
be separated from quinine by the insolubility of the former in cold
alcohol. Ether dissolves them all except morphia, cinchonia, sabadilla.
strychnia, and brucia. Chloroform dissolves strychnia and most of
those soluble in ether.
(3.) Chemical. The solutions of the alkaloids have generally an
alkaline reaction. They act as bases, forming salts with acids.
Rreatine is a neutral alkaloid, and not basic.
Action of Acids.-(1.) Sulphuric acid, when concentrated, slowly de-
composes them, strychnia excepted; when dilute, it dissolves them and
forms salts. With papaverin it strikes a deep blue, thus distinguish-
ing it from all the other opium alkaloids. (2.) Nitric acid, sometimes
forms nitrates with the alkaloids, and sometimes colored compounds, as
in the case of morphia, etc. (3.) Hydrochloric acid, forms with many
of them additive compounds. With morphia, when heated in sealed
tubes, it forms apomorphia. Apocodeine is formed by the action of
650 EIANDBOOK OF MODERN CEIEMISTRY.
the acid and zinc chloride on codeine. (4.) Organic acids combine with
many of them, forming generally insoluble salts. For example:—(a.)
tannic acid precipitates the salts of morphia, narcotine, codeia, cin-
Chonine, quinine, Strychnine, brucia, conia, emetine, aconitine, atro-
pine, delphinia, and veratrine. (3) Carbazotic acid precipitates most
of the alkaloids.
Action of Alkalies.—Alkalies decompose most of the alkaloids when
heated with them with the evolution of ammonia.
Action of Haloids,-(1.) Chlorine usually decomposes them, forming
hydrochloric acid, which combines with the base itself or with some
substitution-compound produced by its action. It forms, (a.) with
Strychnia, a white precipitate; (6.) with brucia, cinchonine, and morphia,
yellow precipitates, which change to red, and then to yellow ; (y.) with
marcotine, a pale red precipitate, which becomes dark red, and then
brown; (6.) with quinine (on the addition of ammonia), an emerald-
green solution.
(2.) Bromine acts in most respects similarly to chlorine.
(3.) Iodine combines with most of the alkaloids to produce an in-
soluble yellow or brown compound of iodine and the alkaloid. This
was first noticed by Pelletier in the case of strychnine, and was
further investigated by Bouchardat. Herapath has pointed out that
the crystalline compound of iodo-sulphate of quinine (Herapathite)
CooHo, N.O.I. HaSO4(H2O)5 exerts a powerful polarizing action on
transmitted light.
Action of metallic salts.
(1.) Platinic chloride, forms crystalline compounds with the chlo-
rides of the alkaloids.
(2.) Mercuric chloride, forms double salts with the chlorides.
(3.) Auric chloride, in some cases, produces a characteristic colored
precipitate. Thus, with morphia, it produces a green; with strych-
nia, a yellow, etc.
(4.) Ferric chloride, forms a green compound with morphia.
Action of nascent oaygen.—Nascent oxygen decomposes many of the
alkaloids, new compounds being formed. With strychnia, morphia,
etc., it gives a characteristic series of tints. (See page 10.)
The vegetable alkaloids are extensively used in medicine. As an
antiperiodic, quinine is esteemed of great value. The ordinary
sulphate of quinine is a basic sulphate, and has the formula
(C20H24N2O2)2, H2SO4,8EI2O. It is very slightly soluble in water. On
adding a few drops of sulphuric acid to the basic sulphate suspended
in water, a neutral sulphate is formed (C20H24N2O2, H2SO4,7H2O),
which is freely soluble. The tincture of quinine (B.P.) is an alcoholic
solution of the basic sulphate. The tinctura quinae ammoniata (B.P.)
is an alcoholic solution of quinia precipitated by ammonia from a solu-
tion of a salt. The vinum quinae is a mixed solution of the neutral
sulphate and citrate.
ALKALOIDS.
651
(A.) Alkaloids of Vegetable Origin.
(1.) The volatile liquid alkaloids which do not contain oxygen:—
NAME. Formula. Source. Properties, etc.
Nicotine . . . . . Clo H.N., Tobacco (2–8 per A colorless oily liquid, boiling at
cent.) 464° F. (240° C.). Sp. Gr. 1-027.
Soluble in water, etc.
Conine (conia) CeBItsN Hemlock (conium | A colorless liquid, boiling at 413.6°
maculatum). F. (212° C.). Sp. Gr. 0-89. An
artificial conine has been prepared
by distilling dibaſtyraldine, a body
º formed by digesting normal butyric
aldehyde with an alcoholic solution
of ammonia. By oxidation comine
. yields butyric acid.
Sparteine .. CiołIsM2 Broom (spartium
scoparium).
(2.) The solid alkaloids containing oxygen, arranged according to
their Natural Orders:—
NAME. Formula. Source.
(a.) Cinchonaceae.
Quinine . . . . C.H.N.0, Cinchonas, especi-
, ally cinchona cor-
difolia.
Cinchonine . . . . . C. H.N.0 Cinchonas, especi-
ally cinchona con-
daminea.
Quinidine Isomeric c. Ditto.
quinine
Cinchonidine ... Isomeric c. Ditto.
cinchonine
Quinicine Isomeric c. Ditto.
quinine
Cinchonicine. . . . . Isomeric c. Ditto.
cinchonine
Quinoidine . . . . . Isomeric c. Ditto.
Aricine (cinchova-
tine) . . . . . .
Emetine tº e º e
quinine
º 3.
Uſ
30 *N. 8
Cusco, or arica bark.
Ipecacuanha root.
Properties, etc.
Quinine turns the plane of polariza-
tion to the left ; cinchonine to the
ºright. Quinine is less disposed to
crystallize, and is more soluble in
water than cinchonine. Quinine
( dissolves in cold water (1 in 350),
and in alcohol (1 in 2). Cinchonine
is insoluble in cold water, and dis-
solves in boiling alcohol (1 in 35).
gº melts at 221°F. (105°
Quinidine turns the plane of polariza-
tion to the right, and cinchonidine
to the left.
ſ Formed by the action of a tempera-
ture of 248-266° F. (120–130° C.)
for several hours on quinine and
cinchonine, or on quinidine and
3 cinchonidine. The action of these
bodies on a polarized ray resembles
that of quinidine and cinchonidine,
but to a very much less marked
U extent.
Called , chinoidine or amorphous
quinine. A brown mass, insoluble
in water, soluble in ether, alcohol,
and dilute acids. Prepared by the
action of heat on quinine.
652
EIANDBOOK OF MODERN CHEMISTRY.
tato shoots, etc.
NAME. Formula. Source. Properties, etc.
b.) Papaveraceae.
orphia (morphine) | Cr; Hign Oa | From opium, the Forms prismatic crystals; soluble in
inspissated juice water (1 in 1000); solution bitter
from the capsule and alkaline; soluble in alcohol
of the papaver (1 in 30); freely soluble in dilute
somniferum. acids and in excess of fixed alkaline
hydrates. Melts and burns in air,
leaving a small carbon residue.
(Apomorphia) Cr, H17NO2 Ditto. Prepared by heating morphia in a
sealed tube with hydrochloric acid
to 302° F. (150° C.). Very solu-
ble (unlike morphia) in alcohol,
ether, and chloroform. It is not
- a narcotic, but an emetic.
Codeine . . ClaRAINO, Ditto. Prepared from the mother liquor
from which the morphia has been
crystallised. Forms octahedral crys-
tals. Soluble in water (1 in 80 at
60° F., and 1 in 17 at 212° tº:
solution alkaline. Forms salts
with acids. It yields apomorphia
by prolonged heating with hydro-
chloric acid.
(Apocodeine). . CisłIgMO, Ditto. Prepared by heating codeine with
hydrochloric acid and chloride of
zinc. A mild emetic.
Narcotine C.H. NO; Ditto. Prepared from the insoluble portion
(marc) of opium by boiling acetic
acid, and precipitation with am-
monia. Nearly insoluble in water
(1 in 123 at 212° F.). Soluble in
acids, but its basic powers are very
feeble. With manganese dioxide
and H2SO4, it forms opianic acid.
(CoPſi,0s).
Thebaine (paramor- e e
g : J. Insoluble in water; soluble in alco-
phine) . . Clo Bai NO3 Ditto. hol and ether. It is strongly alka-
line and forms crystallizable salts
with acids. It is probably the
most active of the opium alkaloids.
Papaverine . . . . . Ǻm N9. Ditto.
Pseudo-morphine ... CºHº Q, Ditto.
Narceine ... C.II,NOo Ditto.
Codamine ... CºPI, N03 Ditto.
Lanthopine . . . . . Caſſº, Ditto.
Laudanine . . C. H.,N0s Ditto.
Meconidine . . C. H. NOA Ditto.
Opianine . . . Ditto.
Porphyroxine Ditto.
(c.) sº | H ige
-LVOSC amine 8,- yoscyamus niger.
Hº © a } Cls HaNO3 Datura stramonium. º º
Atropine Culi, NO, Atropa belladonna. Sparingly soluble in water. Soluble
Solanine C.H.I.N.O., |Various plants; po- in alcohol and ether.
ALFCALOID8. '653
NAME. Formula. Source. Properties, etc.
(d.) Ranunculaceae. g e
Delphinine C.H.NO, Delphinum staphi- The prepared seeds of stavesacre are
Sagria. S i. to kill tº:
& tº n NO. Aconitum napellus. oluble in water (1 ln lou at 10 U.;
Aconitine Csofia, NO, p 1 in 50 at 60° C.), in alcohol, and
in ether.
(e.) Melanthaceae. e gº; * º
Weratrine (veratria) || C.B.S.N,0s | Veratrum sabadilla A white powder, insoluble in water;
(white hellebore). soluble in alcohol, ether, and in
acids. Solutions alkaline.
Colchicine Colchicum autum-
male.
.) Strychnaceae. & tº tº
sº C.H.N.0, Nux vomica, false Both alkaloids are associated in the
angustura bark, etc. plant with igasuric acid. Strych-
wine crystallizes in octahedra ; is
slightly soluble in water (1 in
7,000); soluble in hot dilute al-
cohol (1 in 100); insoluble in abso-
lute alcohol, ether, or in alkaline
solutions. It forms with acids
crystallizable salts.
se so Ditto. I}rucia is readily soluble in alcohol
Brucine . . . . . . . C. HogN2O, (absolute or dilute) and in boiling
water (1 in 500).
(g.) Other orders. te º * * *
Harmaline . . C.H.I.N.O | Peganum harmala. It is soluble in alcohol and in dilute
(Russia). acids. By oxidation it forms har-
t mine, Cls HisN.O.
Caffeine Coffee berries, 1 per It forms needle crystals; very bitter.
Theine } C.H.I.N.O., cent. ; tea leaves, When heated it melts and sublimes.
2–4 per cent. ; by Soluble in water (1 in 100 at 60°
the action of me- F.); slightly soluble in alcohol;
thylic iodide on basic properties feeble. By its
theobromine, at oxidation, products are formed
100° C. closely allied to the uric acid deri-
vatives. With chlorine it yields
amalie acid, Cs(CHS),N,0,--aq.
With oxidizing agents it yields
cholestrophane (CsPIs N.O.).
Theobromine C, H.N.O., | Theobroma cacao. White crystals, soluble in a solu-
&º tion of ammonia; not very soluble
in pure water.
Berberine C, H, NO, Berberis vulgaris A feeble base; crystalline; soluble in
(calcumba radix). Water.
Cocaine . . . . . . C17H31NO, Coca leaves. e w
Piperine Cr. His SOs Pepper. Yellow crystals, insoluble in water,
* soluble in alcohol and acids. By
distillation it yields piperdine
(CSHuM), a colorless liquid boiling
at 222.8° F. (106° C.).
Capsicine Cayenne pepper. Forms crystallizable salts.
Picocarpine . . ? Jaborandi. tº § *
Asparagin CAHs N,0s Asparagus (marsh Metameric with malamide.
mallow.)
Physostigmia Caohai N,0, Calabar bean.
654
EIANDBOOK OF MODERN CHEMISTRY.
(B.) Alkaloids of Animal Origin.
NAME.
Formula.
Source.
Properties, etc.
Xanthine
• *
Hypoxanthine (Sar-
cine)
Guanine
Kreatine
Kreatinine
Sarcosine
|Urea
C.H.N.O.,
C.H.N.0
C.H.N.0
C.H.,N.30.2aq
C.H.N.0
C, H, NO,
CN.H.0
Urinary calculi,
guanine, urine,
all parts of body.
Formed by the
action of nitrous
acid on guanine.
Flesh of vertebrata,
also in blood,
liver, etc.
Guano, excrement
of spiders; pan-
creatic juice.
Flesh, urine, brain.
Ditto.
Ditto.
Urine.
A white amorphous body, soluble in
acids, forming salts; slightly soluble
in boiling water; soluble in alka-
line solutions. Dissolves in HNO,
without the evolution of any gas,
leaving a yellow residue which
turns red with ammonia. The hy-
drochloride is insoluble in water.
White crystals, soluble in boiling
(but not in cold) water, and in dilute
acids and alkalies. The hydro-
chloride is soluble in water.
Colorless crystals; insoluble in water,
alcohol, ether, and ammonia; Solu-
ble in acids and in a potash solu-
tion. Forms salts. By the action
of KC10, and HCl it forms para-
banate (CAH.,N2O3) and guanadin
(CH.N.).
Colorless crystals; soluble in boiling
water; sparingly soluble in cold
water (1 in 74); insoluble in alcohol
or ether. Solution bitter. Kreatine
is a neutral body, combining neither
with acids nor alkalies.
Prepared by the action of strong acids
on kreatine. It forms crystals, Solu-
ble in water (1 in 11 at 60° F.), the
solution being very alkaline. It
forms salts with acids. It evolves
methylia when heated with soda
lime. By boiling with an alkali it
forms kreatine.
Prepared by boiling kreatine with
baryta water.
Preparation.—(1.) From urine, by
precipitation with oxalic acid. (2.)
By heating a solution of ammonic
cyanate. (3.) By the decomposi-
tion of ammonic carbonate. Forms
four-sided crystals, soluble in water
and in alcohol; solution neutral.
When heated, it first melts and
then decomposes. The pure solu-
tion is permanent in the air, but it
decomposes rapidly in urine, owing
to the presence of putrefiable or-
ganic matter. (See Urea.)
Constitution of the Alkaloids.
(1.) Berzelius regarded the alkaloids as conjugate bodies of some
neutral substance with ammonia (to which latter compound he sup-
posed they owed their alkalinity), founding his theory on the universal
ALKALOIDS. 655
presence in these bodies of hydrogen and nitrogen. To this, objection
was made that it was impossible to detect the presence of ammonia in
them.
(2.) Liebig regarded them as ammonias, where one atom of hydrogen
was replaced by a compound radical; in other words, as compounds
of amidogen (NH2) with a compound radical capable of acting as a
hydrogen atom, and not destructive to the original alkalinity. Thus,
in aniline, NH2(C6H5), H was regarded as being replaced by phenyl
(C6H5). This view of the composition of aniline was further confirmed
by the circumstance that when ammonic phenate was heated, aniline
was obtained. Thus—
NHA.C6H50 (ammonic phenate)=NH2(C6H5) aniline + H2O.
Hence an amide was regarded as a body derived from an ammoniacal
salt by the loss of a water molecule.
(3.) Further investigation has shown that in organic bases—
(a.) One, two or three atoms of the hydrogen of ammonia may be
displaced by one, two or three molecules of a univalent compound
radical or their equivalent, and that—
(B.) The nitrogen of the ammonia may also be displaced by certain
elements, such as phosphorus, arsenic, antimony, etc.
It is important for us to consider here the method of investigation
pursued in these enquiries:—
(1.) If ammonia and ethylic iodide (C2H5T) be heated in sealed
tubes, the apparently conjugate body NH3, C.H.I is formed. When
this compound, however, is distilled with potassic hydrate, it yields
(not ammonia, but) potassic iodide and ethylamine, this latter body
being ammonia where one of hydrogen has been displaced by one
of the alcohol or hydrocarbon radical ethyl (C2H5). Thus—
NHS.C.H.I + KHO = NH. (C.H.) + KI + H2O.
+ Potassic = Ethyl-amine + Potassic + Water.
hydrate iodide
Nevertheless, ethylamine is a colorless alkaline liquid forming salts
with acids, boiling at 65-6°F. (18.7°C.), and Smelling of ammonia.
(2.) If ethylamine and ethylic iodide be again heated as before in
sealed tubes, the compound NH3(CH2)C.H.I will be formed. This,
on being distilled with potassic hydrate, furnishes potassic iodide and
diethylamine, this latter being an ammonia where two atoms of hydrogen
are replaced by two molecules of the alcohol radical ethyl (C2H5).
Thus—
NH3.C.H.C.H.I + KHO NH(C.H.). -- KI + H2O.
+ Potassic = Diethylamine + Potassic + Water.
hydrate iodide
Nevertheless, diethylamine is a colorless alkaline liquid, boiling at
134°6°F. (57.0°C.), and behaving chemically as ammonia.
(3.) Similarly, diethylamine, NH(C.H3)2, may be converted into
triethylamine, N(CH3)3, which is also a colorless alkaline liquid.
656 HANDYSOOR OF MODERN CHEMISTRY.
(4.) If triethylamine N(C.H.)a be similarly heated with ethylic
iodide, the conjugate compound N(C2H5)3.C.H.I is formed.
(5.) Just, however, as we regard the hydriodate of ammonia as an
iodide of the hypothetical metal ammonium (NHA), thus—
(NH4)HT (hydriodate of ammonia)=(NHA)I (iodide of ammonium),
so we may regard the compound (N(C.H.)3C.H.I.) as the iodide of
tetrethylammonium (N(C.H.),I), or, in other words, as a compound
where the four atoms of the hydrogen of the metal ammonium have
been replaced by four of ethyl.
(6.) On heating this body (N(C.H.),I) with potassic hydrate, it is
not decomposed. When its solution, however, is treated with argentic
oxide, an argentic iodide is precipitated, and a solution of tetrethylam-
monic hydrate is formed. Thus—
2[N(C.H.), Ij + AgaO + H2O = 2 N(C.H.), HO) + 2AgI.
Iodide of tetr- + Argentic -i- Water = Tetrethylammonic + Argentic
ethylammonium oxide hydrate iodide.
This hydrate, which may be obtained in a crystalline state by evapo-
ration “in vacuo,” is an alkaline, caustic, deliquescent body, freely
absorbing carbonic anhydride from the air, expelling ammonia from
its salts, forming salts with acids, forming soaps with fat, etc. That
is, we have a close correspondence, chemically, between this body and
potassic and ammonic hydrates. Thus—
ICHO ; (NH4)HO : (N(C.H.),)HO.
Potassic Ammonic Tetrethylammonic
hydrate ; hydrate ; hydrate.
(7.) Similarly, the experiments might be conducted on ammonia
with the iodides of other alcohol radicals, as methyl (whereby methyl-
amine would be produced); or amyl (forming amylamine, etc.); or
one hydrogen may be replaced by one radical, and one by another.
Thus, if we act on aniline or phenylamine (NH2C6H,), first, with iodide
of methyl (CHAI), and distil with potash, then with iodide of
ethyl (C.H.)I, and distil with potash, and lastly, heat the product
with iodide of amyl (C, Hu I), and distil, we obtain a compound
formed on the ammonium type, where each hydrogen atom is replaced
by a different compound alcohol radical. Thus we obtain—
N(C6H,) (CHA) (C.H.) (C.Hu)HO.
Hydrate of phenyl-methyl-ethyl-amyl ammonium.
(8.) From these experiments we learn—
(a.) That by heating ammonia with ethylic iodide, and distilling
the product with potassic hydrate, we obtain products where the
hydrogen is replaced successively by C.H. Thus we obtain—
First ; Ethylamine, NH2(C.H.) when H, is replaced by C.H.
Secondly; Diethylamine, NH(C2H5): ,, H, 3 * (C.H.).
Thirdly; Triethylamine, N(C.H.)s ,, H3 2 3 (C.H.).
*
ALKALOIDS. 657
*-.
(ſ3.) That by the further action of ethylic iodide on triethylamine,
a compound is formed containing another ethyl molecule, viz.,
N(C2H5),I, corresponding to the salt NHAI.
This product, unlike the previous compounds, is not decomposed
by the action of potassic hydrate, but may be made to yield a caustic
alkaline liquid N(C2H3)4(HO), closely corresponding to NH,(HO).
9. Adopting a similar method of investigation in examining the
constitution of the alkaloids to that above described in the case of
ammonia, we ask this question—
How many atoms of hydrogen in the alkaloid can be replaced by an
alcohol radical (such as ethyl), by the action upon the alkaloid of iodide
of ethyl 2
For example:—
Conine has the formula CsII,5N. We act upon it with ethylic
iodide, and distil the product with potassic hydrate, when we obtain—
CsPI (C2H5)N.
Thus we learn for certain that one atom of hydrogen can be
replaced by C. Hg.
We again act on the new body formed (CsIH, (C.H.S)N) with ethylic
iodide, and we obtain the product CsPI,4(C2H5). NI, where, although
the body has taken up a new molecule of C.H., nevertheless another
hydrogen atom has not been displaced ; and further, the new product
is not decomposed when treated with potassic hydrate, but is converted
by argentic oxide into a soluble base corresponding to (NH4)HO.
Hence our experiments prove that only one hydrogen atom of the
compound comine (CsPI,N) can be replaced by ethyl, and that there-
fore the group (CaFIL), supposing comine to be an ammonia, must
play the part of two hydrogen atoms. Therefore the formula
N | *) or NHC, H,).
represents the constitution of conine as an ammonia.
10. Again, morphia has the formula C7H16NO3. Heated with
ethylic iodide it forms Criſing(C.H.S)NOAI, i.e., it refuses to part
with any of its hydrogen under the action of ethylic iodide. Hence
the formula N(CHHig0s)" represents the constitution of morphia,
exhibiting it as an ammonia where the group C; HoOs plays the
part of three atoms of hydrogen. -
11. Some alkaloids containing two atoms of nitrogen are regarded
as being built up on the double ammonia type (N.H6); others, con-
taining three of nitrogen, on the treble ammonia type (NaHg), etc.
Thus:—
N.(Cooſ I.O...)"-Quinine; N.(Ce, Hog().)Yi-Strychnia.
Those bodies that are formed on the type of a single ammonia
molecule (NH3) are termed monamines; those on the double ammonia
TJ U
658 HANDBOOK OF MODERN CHIEMISTRY.
type (N2H6), as ethylene, N.H., (C.H.)", diamines; those on the treble
type (NaHo), as diethylene triamine, Ns|H3(C2H4)", triamines, etc.
12. Further, the nitrogen of the ammonias may be replaced by
phosphorus, arsenic, antimony, etc. In this way are formed the com-
pounds triethylarsina, As(C.H3)3 (which, however, is not a true
ammonia, inasmuch as it is incapable of forming true salts), and
triethylphosphine, P(C6H5)3, which latter compound is a true ammonia,
and forms true salts, such as P(C6H5)3S ; POC., H3)3FIO, etc.
Compound Ammonias.-The Amines.
We have now to consider a class of bases termed the Amines.
An amine is an ammonia in which one or more atoms of hydrogen
have been replaced by one or more alcohol radicals (that is, a radical
which, like CH3, does not contain oxygen). The amines may be
classified as follows:—
(A.) Monamines : bodies formed on the type of a single ammonia molecule
(NHS)
These are subdivided into three groups, viz.:-
(a.) Primary monamines, where H1 only is replaced (NHGR").
(6.) Secondary monamines, where H2 is replaced (NHR'2).
(y.) Tertiary monamines, where Hs is replaced (NR'2).
(B.) Diamines : bodies formed on the type of a double ammonia molecule
(N2H6). -
(C.) Thiamines : bodies formed on the type of a treble ammonia molecule
(NaHo). -
(D.) Tetramines : bodies formed on the type of a quadruple ammonia
molecule (NaH2).
(A.) Monamines.—Organic bases formed on the type of a single am-
monia molecule (NH3). The monamines may be primary, secondary,
or tertiary.
(a.) Primary monamines, that is, ammonias (NH3), where one hydrogen
atom is replaced by a compound alcohol or hydrocarbon radical. Evample:
NH2(C2H5), Ethylamine.
Preparation.—(1.) By the action of the caustic alkalies on cyanates
of the alcohol radicals:—
Ethylic + Potassic - Ethyl-amine + Potassic
cyanate hydrate carbonate.
2. By the action of the iodides or other haloid compounds of the
alcohol radicals on ammonia, and the subsequent decomposition of
the compound formed by potassic hydrate :-
(a.) C.H.I + NH3 = NH.(C.H.) HI.
Ethylic + Ammonia - Ethylammonic
iodide iodide.
THE AMINES. - 659
(6.) NH2(C.H.)HI + KHO = NH2(C.H.) + KI + H2O.
Ethylammonic + Potassic = Ethylamine + Potassic + Water.
iodide hydrate iodide
[This process is also available for the preparation of secondary
and tertiary monamines.]
3. By the action of reducing agents on certain nitro derivatives of
the hydrocarbons:—
C6H,(NO2) + 3H2 -: NH2(C6H,) + 2H2O.
Nitro-benzene + Hydrogen = Aniline + Water.
(6.) Secondary monamines, that is, ammonias (NH3), where two hy-
drogen atoms are replaced by two compound radicals, the same or different.
Eacample : Diethylamine, NH(C2H3)2.
Preparation.—By the action of a haloid compound of an alcohol
radical on a primary monamine (the alcohol radical being the same or
different to that contained in the monamine), and the subsequent action
on the product of potassic hydrate.
(C2H3)] + NH2(C.H.) = NH(C.H.)2 + HI.
Ethylic iodide + Ethylamine = Triethylamine + Hydriodic
acid.
(y.) Tertiary monamines, that is, ammonias (NHS), where three hydro-
gen atoms are replaced by three compound radicals, the same or different.
Fæample: Triethylamine, N(C2H5)3.
Preparation.—By acting in a similar manner to that described above
with ethylic iodide on a secondary monamine.
Ethylic iodide + Diethylamine = Triethylamine + Hydriodic
acid.
[NotE.—In practice, when we act on ammonia with ethylic iodide,
all these compounds are formed in varying proportions. They cannot
be separated by fractional distillation.]
Properties of the Amines.-A tertiary monamine may be known from
a primary or a secondary monamine by its forming with ethylic or
other like iodide, an iodide which is not decomposed by potassic
hydrate. The amines are, with few exceptions, basic compounds.
Ilike ammonia, they are alkaline, and form analogous salts with
acids. By the action of alkalies, these salts are decomposed with the
separation of the amine, just as with ammonium salts the evolution
of ammonia results.
The following is a list of the chief monamines:–
660
HANDBOOK OF MODERN CHEMISTRY.
...”
NAMEs.
}{
Formula.
#
i
Ethylamine tº º
\ , ,
Diethylamine . .
Triethylamine . .
Tetrethyl-ammo-
nic hydrate
Methylamine
Dimethylamine .
Trimethylamine -
Tetramethyl-am-
monic hydrate
Amylamine
Diamylamine . .
Triamylamine ..
Tetramyl-ammo-
nic hydrate
Butylamine ..
Dibutylamine ..
Tributylamine ..
Tetrabutyl-ammo-
nic hydrate
NH,C,E)
NH(C.H.),
N (C2H3)3
N(C.H.),(OH)
NH,(CH.)
NH(CH.),
N(CH.),
N(CH.),(OH).
N(CH),(OH)
NH,C,EI
§§
N(C.H.),
N(d. Hºffo)
Boiling Point.
o F.
o C.
Properties.
0-6964
88
ºt
C
1-08
|0.7503
at
189 C.
66-2
|
19-0
199°4
388-0
494-6
57-5
91 - 0
93-0
170-0
257-0
Specific gravity of vapor, 1:57.
Ammoniacal odor. Alkaline
reaction. Forms salts with
acids. Fumes with HCl.
Like ammonia, precipitates
metallic salts,dissolves AgCl,
and produces a blue. ppt.
with copper salts. Vaporin-
flammable. Decomposed by
HNO, into N and ethyl
nitrite. -
A colorless alkaline liquid,
soluble in water; forms
salts with acids.
A colorless alkaline liquid.
Forms crystalline salts with
acids. ‘. . .
Crystalline; the crystals de-
composed by heat into
methylamine, water, and
ethylene. The solution is
colorless, alkaline and bitter.
Closely related to potassic
hydrate. w
A gas, alkaline, and of ammo-
niacal odor. Liquefied at
–0-40 F. (–18° C.). One
vol. of water at 53-69
(12 o C.) dissolves 1,040
vols. of gas. Inflammable,
and burns with a yellow
flame. It occurs in herring
brine, and is a product of
the action of H on HCN.
A colorless gas, liquefying at
46.4°F. (8°C.). Smells of
NHa. -
A colorless gas, boiling at
48.7° F. (9.3 C.). Smells
of ammonia and fish brine.
When heated it yields tri-
methylamine and methyl
alcohol. * *
A colorless liquid, alkaline,
having an ammoniacal
smell.
An alkaline liquid. - w
A colorless liquid; the Salts
are sparingly soluble in
water. -
A solid crystalline body; when
heated it yields triamyla-
mine, amylene, and water.
It is not very soluble in
Water.

THE AMINES.
861
Properties.
###|Boiling Point.
NAMES. Formula. § 3.3
C-: *- F- -
2 & 3 || 9 F. o C.
Allylamine NH,(CH.)
Diallylamine NH(C.H.),
Triallylamine .. N(CH3),
Tetra-allyl-ammo- N(C.H.),(OH)
nic hydrate
Methyl - ethyla- NH(CH,)(C.H.)
mine
Methyl - ethyl- N(CH2)(C.H.)(CH.)
phenylamine
Ethyl-amylamine | NH(C.H.)(CŞH,1)
Benzylamine NH,(C, H,) 359-6 | 18.2-0
Dibenzylamine. . NH(C, H,),
Tribenzylamine . N(C.H.),
Xylylamine NH,(C.H.) 384-8 196-0
Dixylylamine .. NH(CºHo),
Trixylylamine . . N(CsIIs),
Cymylamine NH2(CoHº) 536-0 |280-0
Dicymylamine .. NII(CoHº), 572.0 300-0
Tricymylamine. . N(CoHis),
Naphthalidine . NH2(CoH,)
Aniline (phenyla- NH2(CSPIs) 1.028 359-6 182.0
mine)
Toluidine. . NH,(C.H.Me)
(tolylamine ; Or
amidotoluene) NH2(C.H.)
Conine NH(C.H.)”
Piperidine . . NH(C.H.)”
Pyrrol N(CHS) 1.077 271.4 || 133-0
Pyridine N(C.H.)” 242.6 || 117-0
Picoline (parani- N(CH.)” 0.955 271-4 133-0
line
Lºs tº ſº $ N(C.H.)” 309.2 1540
Collidine (xyli- N(0, Hu)" 419' 0 || 215 - 0
dine)

A colorless liquid. It absorbs
CO, and fumes with HCl.
Oily liquids, soluble in
alcohol and ether, insoluble
in water.
} Oily liquids.
A crystalline solid. Melts at
177.8°F. (81° C.).
A crystalline solid. Prepared
by the action of NHHS on
an alcoholic Solution of nitro-
naphthalene. Forms salts.
See page 663.
Exists in three forms; as para-
toluidine, a crystalline solid,
melting at 45° C. : ortho-
toluidine, a liquid, Sp. Gr.
0.998, boiling at 197° C.,
becoming rose colored on
exposure to air; and meta-
toluidine, a crystalline solid
melting at 57°C.
Prepared from animal oils. A
colorless liquid, turns a
piece of fir wood moistened
with HCl purple.
Prepared from coal tarnaphtha,
and by heating amyl nitrate
with phosphoric anhydride
C.HuMO,-3H,0=N(C.H.)
A liquid prepared from coal
tar naphtha.
Do.
Do.
662
HANDBOOK OF MODERN CHEMISTRY.
### Boiling Point.
NAMES. Formula. º ## Properties.
§§sſ, F.T. C.
Chinoline .. N(C.H.) 1:081 || 455-0 || 235-0 | By distilling quinine, etc., with
* a strong solution of potassic
hydrate. A colorless oily
liquid forming salts with
acids.
Parvoline (cumi- N(C.H.)” 370-4 1880 | A liquid prepared from coal
dine) tar naphtha.
Cymidine (cori- N(CoHis)” 482 - 0 || 250-0
dine)
Rubidine . . N(CuIII.)” 446-0 || 230' 0
Viridine 12 º 483 ‘8 || 251 - 0

(B.) Diamines.—Organic bases formed on the type of a double ammonia
molecule (N2H6).
Preparation.—By the action of a haloid salt of a diatomic alcohol
radical (as ethene (ethylene), C.H., etc.), on ammonia. Thus:–
2NEI, (C.H.)"Bra — N.H.,(C.B.)” + 2EIBr.
Ammonia Bthylene F. Ethylene + Hydrobromic
dibromide diamine acid.
That is, N2H4(C2H4)" represents a double ammonia molecule
(N2H6), where two atoms of hydrogen have been replaced by the
diatomic radical (C2H4)". •
Just as 2(NHA, HO) represents a double molecule of a hydrate of
ammonium (NH4), so (N.H., (C.H.)"., H2O.) represents a molecule of
the fixed alkaline base, hydrate of ethylene diammonium.
The following table represents some of the diamines —

- Boiling point.
Name. Formula. Properties.
• F. 9 C.
Ethylene diamine N.H.,(C.H.)" 242.6 117-0 |An oily liquid.
Urea . . * * , H,(CO)"
Sulphur-urea N.H (CS)”
Ithyl-urea | | N.H. (diſco)"
Sulpho-phenyl-urea. . . N.H. (CºHA)'(CS)"
(C.) Triamines.-Organic bases formed on the type of a treble am-
monia molecule (NaHg).
To this class belong many of the bases of the aniline colors, such
as rosaniline, etc.
There are certain other amines to which mere reference must suffice,
it being impossible to classify them.
ANILINE. 663
NAME. Formula. Sp. Gr. Properties.
Furfurine | Cls H.N.0, Prepared by boiling furfuramide, a body formed
by the action of ammonia on a solution of fur-
furol (C.H.O.) in potassic hydrate. A power-
ful base soluble in boiling water (1 in 135), in
alcohol and in ether. Solutions alkaline; salts
bitter.
Benzoline; C, His N., By the action of potassic hydrate on hydro-
(amarine) benzamide (C,EISO). A solid substance in-
soluble in water.
Thialdine C.H.I.N.S., 1.191 | Forms solid, highly refracting crystals. It is
volatile, and yields salts with acids.
Aniline (C6H1N=93).
Specific Gravity, 1.028; Freezing point, 17.6°F. (–8°C.); Boiling point,
359-6°F. (182°C.); Molecular volume, TT1 .
Origin of Name.—From the indigo plant, Indigofera anil.
Synonyms.-Phenylamine (regarding it as an ammonia derivative);
Phenylia ; Amido-benzene.
Constitution.—Aniline may be regarded either (1) as an ammonia
derivative, where Hı is displaced by one of phenyl (C6H5):—hence
called phenylamine, NH2(C6H5)"; or (2) as a derivative of benzoic acid,
hence called amido-benzene, C.H., (NH2).
For the following reasons we are led to regard aniline as an am-
monia:—
(a.) Its behaviour with ethylic iodide.—Thus it forms successively ethyl-
phenyl-, diethyl-phenyl-, and triethyl-phenyl-ammonic iodide, the two
former yielding
C5H7 | C6H1
Ethyl-phenyl amine C.H, ). N; and Diethyl-phenyl amine C.H. W. N.
Hiſ §
respectively, when treated with potassic hydrate; the last yielding
triethyl-phenylammonic hydrate when treated with water and argentic
oxide.
This reaction corresponds to ammonia, as already explained (page
655).
(3.) As potassic hydrate separates NH3 from ammonic salts, so it
separates aniline (NC5H7) from aniline salts.
(y.) By heating together phenic acid and ammonia in an hermetically
sealed tube, aniline is formed by the substitution of phenyl (C6H5) for
hydrogen.
(6.) The salts of aniline correspond to the salts of ammonia.
Preparation.—(1.) By distilling powdered indigo with a saturated
solution of potassic hydrate:—
CaFINO + 4.KHO + H2O = 2EI, + 2K.COs -- CŞH.N.
Indigo + Potash + Water = Hydro- + Potassic + Aniline.
gen carbonate
664 EIANDBOOK OF MODERN CHEMISTRY.
(2.) By heating together ammonia and phenol for two or three
weeks in sealed tubes. (Laurent.)
C6H,(OH) + NH3 = H.O + C6H,(NH2) [or C.H.N.I.
Phenol + Ammonia = Water + Aniline.
(3.) By the action of reducing agents on nitro-benzene; such as, L
(a.) Sulphuretted hydrogen (Zinin)—
C6H,(NO2) + 3H2S = 2 H2O + S., -i- C6H1N.
Nitro-benzene + Sulphuretted = Water + Sulphur + Aniline.
hydrogen
(3.) Ferrous acetate (Béchamp).
(y.) Dilute sulphuric acid and zinc (i.e. nascent hydrogen).
C6H2(NO2) + 3H2 = 2Eſ..O + Cº. H.N.
Nitro-benzene + Hydrogen = Water + Aniline.
[In the commercial manufacture of aniline, nitro-benzene is heated
in a retort with glacial acetic acid and iron filings, when the aniline
distils over, together with water, in which the aniline sinks. It is
then separated, any acetate present being decomposed with an alkali,
and redistilled. All the aniline of commerce contains toluidine, com-
mercial benzene always containing toluene.]
Aniline is found amongst the products of the distillation of coal
and other organic matters.
Properties.—(a.) Sensible. Aniline when pure has a slightly brown
tint, and is a thin oily liquid, having a faint odor and a burning taste.
It is an active poison.
(3) Physical.—Specific gravity, 1.028. It is very volatile. It
freezes at 17.6° F. (–8°C.), forming a crystalline mass. It boils at
359-6°F. (182°C.). It is slightly soluble in water (forming, possibly,
a hydrate), and is very soluble in alcohol and ether.
(y.) Chemical.—It is not alkaline to test-paper, but its vapor forms
white fumes with hydrochloric acid. By contact with air it be-
comes of a dark color and of resinous consistency. By the action
upon it of oxidizing agents the various aniline colors are formed.
With the haloids (but not by their direct union) it forms substitution
products, as chlor- or brom-aniline (C6H6CIN), dichlor- or dibrom-
aniline (C6H,Cl:N), and trichlor- or tribrom-aniline (C.H.Cl, N). The
first two of these haloid substitution compounds are bases, and form
salts; but the last compound, i.e. where the substitution is complete, is
neutral. Aniline is a powerful organic base, and with acids forms
crystalline salts.
Numerous other substitution products of aniline have been pre-
pared, as, e.g., nitraniline, C.H. (NO)N, a body existing in two modi-
fications; dinitraniline, C6H,(NO3)4N ; diphenylamine, NH(CoHº),
etc. With cyanogen it forms the compound cyan-aniline (C6H1N). Cya.
When nitrous acid is passed (a.) into aniline, plenol, nitrogen, and
ANILINE. 665
water are evolved; but when the acid is passed through (3.) an
alcoholic solution of aniline, azodiphenyl-diamine and water are formed.
(y.) If azodiphenyl-diamine be treated with nitrous acid, an explosive
body, diazo-diphenyldiamine, is produced.
These several reactions may be shown as follows:
(a.) CeBI.N. + HNO. - C.H.60 + H.O +- N2.
Aniline + Nitrous acid = Phenol + Water + Nitrogen.
(3) 20, H.N + HNO. = C, Huns + 2 H2O.
Aniline + Nitrous acid = Azodiphenyl- + Water.
diamine
(y.) C12HuN3 + NOs = Clefſe N1 + 2H.O.
Azodiphenyl- + Nitrous acid = Diazo-diphenyl- + Water.
diamine diamine
With an alkaline hypochlorite aniline forms a violet (mauve). With
chromic acid it gives a bluish-black precipitate.
Uses.—For the manufacture of dyes.
Homologous with aniline is the base,
Toluidine (C, HoN). It is found in three states—(1) as a solid
(paratoluidine), melting at 113°F (45° C.), and boiling at 401°F.
(205°C.); (2), as a liquid (orthotoluidine), boiling at 386-6°F. (197°C.);
specific gravity, 0.998°; and (3), as a second solid (metatoluidine),
melting at 134.6°F. (57°C.), and boiling at 464°F. (240° C.).
Coal-Tar Dyes: Aniline Colors.
Aniline Purple; Mauve.—Preparation.—By the action of sul-
phuric acid and potassic bichromate on aniline. The mauve is
extracted from the residue by hot alcohol.
Properties.—It is insoluble (or nearly so), in water, ether, etc., but is
freely soluble in alcohol, acetic acid, etc. The base of this compound
is a colorless body, called mauveine (C27He, NA). -
Aniline Red; Rosaniline.— Preparation.—By the action on aniline
of various reagents, such as stannic chloride, mercuric salts, arsenic
acid, and many other oxidizing agents. The base, rosaniline, is color-
less, and has the composition CookingNs. It is freely soluble in
alcohol, but is scarcely at all soluble in water. From rosaniline, by
the replacement of hydrogen by alcohol radicals, various other bases
forming coloring matters with acids, have been formed. By the action
upon it of ammonic sulphide, or of free hydrogen, leucaniline Cookie Ns
is formed, the hydrochlorate of which is white, but is converted by
oxidizing agents into rosaniline.
To obtain a red from aniline, it is said to be essential that the
aniline should contain toluidine, inasmuch as pure aniline (i. e., aniline
derived from benzoic acid) yields no red coloring bodies.
Aniline Blue; Triphenyl-rosaniline. (Collis(C6Hs);N3).--Pre-
666 HANDBOOK OF MODERN CHIEMISTRY.
paration.—By boiling rosaniline with an excess of aniline at from 300°
to 320°F. (150°-160°C.). w
Aniline Green. (a.)—Aldehyde green. — Preparation. — By adding
aldehyde to a solution of magenta and sulphuric acid, and treating
the product with sodic thiosulphate.
(3.) Iodine Green.—By the action of methyl- or ethyl- iodide on
aniline violets.
Aniline Yellow contains a well-defined base called chrysaniline
(Coofſ, N3). It is found amongst the secondary products of aniline
red. Its nitrate is insoluble in water.
Phosphines : Arsines: Stibines: Bismuthines,
Phosphorus, arsenic and antimony, like nitrogen, form compounds
with three atoms of hydrogen, viz., PH4, AsFIa, Sb PI3, which bodies
also form compounds analogous to the amines (termed phosphines,
arsines, &c.), excepting that in AsRIs and in SbH3, the replacement of
the hydrogen is always complete.
Properties.—They are mostly liquids, having a very strong odor.
Many of them are spontaneously inflammable. They have great
affinity for oxygen and for the haloids, forming compounds in which
the metal is quin-quivalent. Thus we have stibethyl oacide, Sb'(C2H5)30;
stibethyl chloride, Sb"(C2H5)3Cl2, etc. The tertiary compounds form,
with ethylic or methylic iodide, compounds from which argentic
oxide separates the hydrates; thus—
P(CH3), HO: P(C2H4),(HO); As(C.H.),(HO); Sb(C.H.m),(HO), etc.
Hydrate of Hydrate of Hydrate of IIydrate of
tetramethyl tetrethyl tetrethyl tetramyl
phosphine; phosphine ; arsine ; stibine.
Some of these compounds are stated in the following table :-
Boiling point.
Name. Formula. Sp. Gr. -- Properties.
F. C.
I’hosphines.
Methyl phosphine ... PHI,(CH3) 6'8 – 14'0
Dimethyl phosphine . . PH(CH3), 77.0 || 25-0
Trimethyl phosphine... P(CH3), 105.8 41-0 | A colorless oil, very vola-
tile.
Ethyl phosphine. . . . | PH2(C.H.) 77.0 25.0
Diethyl phosphine . . PH(C2H5), 185-0 || 85-0
Triethyl phosphine ...| P(CH3), 261'5 | 127-5 | Prepared by the action
of phosphorous chloride
(PC],) on zinc ethyl.
A colorless oil, oxidizes
in air, and explodes by
Arsines. heat.
Trimethyl arsine ...| As(CH3)3 248-0 | 120-0 | Prepared by the action of
methylic iodide on an
alloy of arsenic and
Sodium.
HAKODYL. 667

Boiling point.
Name. Formula. Sp. Gr. Properties.
o F. ° C.
Arsines (cont.).
Triethyl arsine . . . . . As(C.Hs), 284-0 || 140-0 | Prepared by the action of
ethylic iodide on an
alloy of arsenic and
sodium. A colorless
liquid, having a very
Stibines. disagreeable odor.
Trimethyl stibine ... Sb(CH.),
Triethyl stibine . . . . Sb(C.H.), 316.4 | 158-0 | Prepared by the action of
(Stibethyl) ethylic iodide on an
alloy of antimony and
potassium. Odor of
onions; combines
powerfully with oxy-
gen and the haloids.
Triamyl stibine . . . . Sb(C, Hu),
Bismuthime.
Triethyl bismuthine ... Bi(C.H.), 1.82 Prepared by the action of
ethylic iodide on an
alloy of bismuth and
potassium. A yellow
nauseous liquid.
Arsen-mono-methyl-Kakodyl.
It will be convenient to examine these bodies here, which, however,
it must be specially noted, are not formed on the ammonia type.
Arsen-mono-methyl; As(CH3). This radical is not known in the
free state. It forms compounds by combining with either two or four
atoms of a univalent element or compound radical, or their equivalent.
Thus it forms a dichloride As”(CH2)Cl., which is a heavy, very
poisonous liquid, and a tetrachloride, ASYOCHs)Clt, a stable crystal-
line solid; an oaside, As”(CH3)0, a bibasic acid, arsen-methyllic acid,
As"(CH3)O"(OH)2, a sulphide, As”(CH3)S, etc. -
Rakodyl (Cacodyl); Arsen-dimethyl (As".(CHS),), or As(CH3),
Boils at 338° F (170° C.). Freezes at 42.8°F. (6° C.).
Preparation.—(a.) By distilling together potassic acetate and arse-
nious oxide, a spontaneously inflammable liquid is formed, called
alkarsin (Cadet's fuming liquid).
4KC, H3O2 + As2O3 = As2(CHS),0 + 2K2CO, H- 200,
Potassic + Arsenious = Alkarsin + Potassic + Carbonic
acetate oxide carbonate anhydride.
(6.) This alkarsin combines with acids to form salts. Thus, by
acting upon it with hydrochloric acid it forms a chloride, thus—
As2(CH3),0 + 2 HCl = As,(CH3)4Cl2 + H2O.
Alkarsin + Hydrochloric = Chloride of + Water.
acid alkarsin
668 HANDBOOK OF MODERN CEIEMISTRY.
(y.) By distilling this chloride of alkarsin with zinc, kakodyl
[As,(CH3)4] is obtained, together with zincic chloride, which latter
product may be dissolved out with water.
Properties.—(a.) Physical. Kakodyl is a colorless, transparent, oily
liquid, having a most offensive odor (kákog bad). It is intensely
poisonous. It boils at 338° F. (170° C.). At a heat below redness it
resolves itself into arsenicum, methane, and ethene:—
As2(CH3), — Aso + C2H4 + 2CH4.
- Kakodyl = Arsenicum + Ethene (1 vol.) + Methane (2 vols.)
(3.) Chemical. Kakodyl catches fire spontaneously when poured
into oxygen, air, or chlorine, and it also combines directly with
sulphur. If the air in contact with it be limited, it forms kakodyl
oxide, As2(CH3)40, and in the presence of water, kakodylic acid. The
following are some of its compounds : — 4.
Name. Formula. Preparation, Properties, etc.
Kakodyl oxide ...|As,”(CH),0" Preparation. — By the slow oxidation of
kakodyl.
Properties.—A colorless, pungent, oily liquid.
Boils at 120° C. It explodes when heated
to 1904° F. (88° C.), but does not fire in
the air. It is insoluble in water, but is
tº a soluble in HCl, FIBr and HI.
Kakodyl dioxide ... AS,(CH3)40, Decomposed by water into kakodyl oxide and
Kakodylic acid, 2(As,CH,0)--H,0=As,
• * A / (CH),0+2As(CII),0(H0).
Kakodylic acid (al- |As"(CH3),0"(IIO) Preparation.—By the slow oxidation of kako-
kargen) - ºr dyl in the presence of moisture.
Properties.—Deliquescent crystals, soluble in
water and in alcohol: reaction acid. It is
very stable, and is not even affected by
boiling nitro-hydrochloric acid. It is de-
composed by dry HI. It combines with
IHCl. It is decomposed by PCls, forming
- a trichloride. It is not poisonous.
Kakodyl chloride ... As"(CH3)2Cl Preparation.—By distilling alkarsin with HCl.
(Arsen chloro- Properties.—A colorless liquid, volatile at
dimethide) ordinary temperatures. Soluble in alcohol;
insoluble in water or in ether. The vapor
inflammable, and has a specific gravity of
4:56°.
Kakodyl trichloride As"(CH3)2Cla Preparation.—By the action of PCls on Ka-
- kodylic acid.
Kakodyl iodide ... As(CH3). I Preparation.—By distilling alkarsin with a
- strong solution of HI.
Kakodyl cyanide ...|As(CH3)2Cy Preparation. — By distilling alkarsin with
HCy, or by the action of oxide of kako-
dy! on cyanide of mercury,
Properties.--Crystalline. Melts at 91.4° F.
(33° C.), and boils at 284°F. (140° C.).
The vapor is very poisonous. *
Kakodyl sulphide ...|As,(CIIA).S A liquid, boiling at about 248° F (120° C.).
Kakodyl disulphide |As,(CH),S, Preparation.—By the action of H.S on kako-
dylic acid.
Properties.—It yields salts of sulpho-kakody-
lic acid. Asy (CII),S.H. .
ORGANO-METALLIC BODIES. 669
Organo-Boron, -Silicon, and -Metallic Compounds.
Boron, silicon, and certain metals, also combine with alcohol radi-
cals, forming compounds built up on the ammonia type.
Organo-Boron Compounds.
These are compounds of boron with hydrocarbon radicals (as
methyl ; CH3), the boron being directly combined with the carbon—
Name. Formula. Preparations, Properties, etc.
Boric methide . . B(CH.), Preparation.—By adding an ethereal solution
of zinc methide to boracic ether 2|B(C,EIs),
O3] + 3(Zn(CH3)2]=2|B(CH3)2]+3(Zn(C.,
Properties.—A heavy pungent gas; specific
gravity 1-93; condenses at 50° F. (10° C.),
under a pressure of four atmospheres; in-
flames spontaneously in air; combines with
ammonia to form ammonia boric methide
(NH, B(CH.),).
º - Preparation.—By adding an ethereal solution
Boric ethid th 1) B(C.Hs), of zinc ethide to borºid ether.
(Triborethyl) Properties. – A colorless liquid; specific
gravity, 0-696; boils at 203° F (95° C.);
inflames spontaneously in air, burning
with a green flame. It combines with
ammonia to form ammonia boric ethide,
NH, B(C.H.)a.
Organo-Silicon Compounds.
Compounds of silicon with hydrocarbon radicals, the silicon being
directly combined with the carbon—

Boiling Pt.
• F. • C.
Silicic methide . . . Si(CH3), 86-9 || 30-5 | Preparation.—By the action of
* * * * - -> zinc methide on silicic chloride.
Silicic ethide ... Si(CAHs), 306'5 | 152-5 | Preparation.—By the action of
zinc ethide on silicic chloride.
IJerivatives.
Silicic methylate . . . Si(CHA),0, 249.8 121-0
Silicic ethylate ... Si(C.Hs),0, 331-7 | 166.5
Organo-Metallic Bodies.
These are compounds of a metal and an alcohol radical, the metal
being directly combined with the carbon of the radical. Thus zinc
670 IIANDBOOK OF MODERN CHEMISTRY.
ethyl, Zn(C2H5)2 is an organo-metallic body, and may be represented
thus—
H H H H
| | | |
H–C–C–Zn–C–C–H
| | | |
H H H. H.
Whilst zinc ethylate Zn(C2H3)2O, is not an organo-metallic body (for
the metal is not directly connected with the carbon of the radical), but
is simply an organic body containing zinc, and may be represented
thus—
H H H. H.
| | | |
H–C–C–O—Zn—O—C–C–H
h # # h
Preparation.—(1.) By the action of a metal on an iodide of the
monad positive radical under the influence of heat, or sometimes
of light—
2(C.H.)I + Zn2 = Zn(C.H.)2 + ZnT3.
Ethylic iodide + Zinc = Zincic ethyle + Zincic iodide.
(2.) By the action of alloys of the metals with K or Na, on an
iodide of the monad positive radicals—
2 ( C.H. 8) I + H gNag — Hg"( C2H, )2 + 2NaI.
Ethylic iodide + Sodium and = Mercuric ethide + Sodic iodide.
mercury alloy
(3.) By the action of haloid salts of the metals (as Sn"C1,), on the
zinc organo-metallic compounds—
SnCl4 + 2CZn(C2H5)2] = Sn(C.H.). -- 22ncl.
Stannic chloride + Zinc ethyle = Stannic ethyle + Zincic chloride.
(4.) By the displacement of one metal in an organo-metallic com-
pound, by a second and more positive metal—
Hg(C, Hu), + Zn — Zn(C, Hin), + Hg.
Mercuric amylide + Zinc F Zincic amylide + Mercury.
Some of these organo-metallic compounds are represented in the
following table:– -
Name. Formula.
Sodic ethide . . . . . . } º Corresponding to .
Zincic ethide. . . . . . Il ( U ol. } } n\jl,
... mºiáč . . . Zºff. 3 y ZnCl,
,, amylide . . . . Zn(C5H11), }} ZnCl,
Mercuric methide. . . . Hg(CH3), 3 * HgCl,
,, ethide . . . . Hºfſ. } } HgCl,
Stamnous ethide . . . . Sn(C.H.), 5 * Sn"Cl,
Stannic ethide . . . . #. 5 x Smivol
Plumbic ethide . . . . Pb(C.H.), 5 y PbO,
Aluminic methide. . . . Al2(CH3)6 3 2 Al,Cls
AMIDES, IMIDES, ALKALAMIDES, NITRILES. 671
For further details as to the properties of these organo-metallic
bodies, see Frankland's Lecture Notes, Vol. ii., p. 227.
Amides; Imides; Alkalamides; Nitriles.
An amide is a compound of amidogen (NH2) and an acid radical.
We may regard the amides either as:—
(1.) Derivatives of ammonia; or as
(2.) Derivatives of organic acids.
1. As derivatives of ammonia; that is, an amide may be regarded as
an ammonia where one or more atoms of hydrogen are replaced by
an acid radical, i.e., a radical containing oxygen (such as C2H3O, the
radical of acetic acid).
[N.B.-An amine is regarded as an ammonia where one or more
atoms of hydrogen are replaced by an alcohol or hydrocarbon radical,
i. e., a radical containing no oxygen (as CH3, methyle, etc.)].
Thus the amides may be obtained from their ammonic salts by the
abstraction of water, and may be converted into their ammonic salts
by the assimilation of water.
Thus by driving off water by heat from ammonic acetate or am-
monic oxalate we obtain acetamide and oxamide respectively. Thus:—
NH,(C.H.,0) — H.0 = NH,(C.H.,0); (NHA).(C.O.) — (H,0), – (NH),C,0,.
Ammonic —Water = Acetamide ; Ammonic — Water = 0xamide.
acetate oxalate
and conversely, by heating acetamide and oxamide with water, we
reproduce from them ammonic acetate and ammonic oxalate.
2. As derivatives of acids ; that is, an amide may be regarded as
an acid where the group (HO) is replaced by amidogen (NH2).
Thus, by acting with ammonia on a chlor-acid, as acetylic chloride
(which is acetic acid, C2H8O(HO), where Cl has replaced the group
(HO)), we obtain acetamide. Thus:–
C.H.O.Cl + NHS = C.H.O(NHS)-- HC1.
Acetylic chloride + Ammonia = Acetamide + Hydrochloric acid.
Thus it would appear that we may formulate the amides in two
ways. For example : acetamide and oxamide.
(1.) As ammonia derivatives they may be stated as follows:–
TI Ho
(C2H5O) lö.o.) 3)2(CAOs)
Acetamide : 0xamide.
(2.) As acid derivatives (of acetic acid, CH3CO(HO), and of oxalic
acid, CaO2(HO), respectively), as follows:–
C.H.O(NH.), Ol' C.O.(NH2)3.
Acetamide Ol' Oxamide.
672 HANDBOOK OF MODERN CHEMISTRY.
An imide is an ammonia derivative where two of the three hydro-
gen atoms are replaced by one molecule of a bivalent acid radical.
An imide, therefore, is a compound of imidogen (NH)", and a bivalent
acid radical. Thus:–
(NH)"(C, H,0.)"—Succinimide.
An alkalamide may be regarded as an ammonia derivative where
the hydrogen is partly replaced by an alcohol (positive) radical, and
partly by an acid radical : e.g.—
Ethyl acetamide=NH (C.H.) (C.H.,0).
There are no primary alkalamides, inasmuch as two atoms of hy-
drogen in every case must be substituted.
We append tables of the chief amides of monatomic, diatomic,
and triatomic acids.
I.—Amides of Monatomic Acids.
Name. Formula. g º
{. which derived
Properties.
Acetamide NII,(C.H.,0)
Primary monamides. .
Benzamide NH,(C, H,0)
* Diacetamide NH(C.H.,0),
Secondary monamides | }s. Niño. Hojº
Secondary monamides Ethyl acetamide NH(C,EIs)(C, H,0)
or secondary alkala-
mides . . . . . .
Tertiary monamides, or Ethyl diacetamide ||N(C.H.)(C.H.,0),
tertiary alkalamides
II.-Amides of Diatomic Acids.
These are of three kinds—
A white solid; melts at
172.4° F. (78° C.),
and boils at 429.8° F.
(221° C.)
A crystalline body;
melts at 239° F,
(115°C.), and volati-
lizes unchanged at
546.8° F (286° C.)
These containing tri-
valent acid radicals,
are called imides,
(a.) An acid amide or amic acid, prepared from an acid ammonic
salt by the abstraction of one water molecule, e.g. :—
(NH,)C.H.0, (acid ammonic succinate)—H,0=(C,EI,0)” (NH2)(OH)(succinamic acid)
(6.) A neutral monamide or imide, prepared from an acid ammonic
salt by the abstraction of two water molecules; e.g. :—
(NH,)0,H.0, (acid ammonic succinate) — (H,0);=(C, H,0)” (NH)" (succinimide)
AMIDES OF DIATOMIC AND TBIATOMIC ACIDS.
673'
(y.) A neutral diamide prepared from a neutral ammonic salt, by the
abstraction of two water
molecules; e.g.:—
(NHA),C,EI,0, (neutral ammonic succinate) = (C.H.O.)"(NH,), (succinamide) + 2.H.0.
es-ºs-
Name. Formula. Properties.
Oxamic acid, ... (C,0.)”(NH,)(OH) | White crystals; forms salts. If NH,
Ammonia salts | º be replaced by ethyl, an acid
f oxalic acid oxamic ether is formed, but if the
§ 0,(H0) r (OH) be replaced by ethyl, a neu-
20,0EIO)2 Oximide (?) . . (?) tral ether results.
Oxamide .. (C.O.)”(NH2)2 Formed also by the action of HCN
on H,02. Decomposed by heat
into HCN and urea C,02(NH2)3–
C0+CO,--NH2+CyFI-FCN.H.0
Ammonia salts ( Succinamic acid (C.H.O.)”(NH2)(OH)
of succinic acid & Succinimide .. C.H.O.)"(NH)”
C.H.02(OH)2 Succinamide .. §§ H2)2
Carbamic acid.. (CO)"(NH2)(OH) | Not known in a free state, but as an
| ammonia salt, which when heated
Ammonia salts forms ammonic carbonate and
of carbonic acid urea. It forms acid and neutral
CO(OH), ethers.
Carbimide (CO)"(NH)” Corresponds to cyanic acid.
Carbamide (CO)”(NH.), Corresponds to urea.
III.-Amides of the Triatomic Acids.
Ammonia salts (Malamic acid ... (CAH,02)” (NH2)(OH), Not known in the free state.
of malic acid | Malimide (?) . . … f
(C.H.O.)”(OH)s ( Malamide ... (C.H.O.)”(NH2)2(OH)| Metameric with asparagin.
Ammonia salts ( Citramic acid .. (?
of citric acid & Citrimide. , (?),
(C.H.O.)”(HO), ( Citramide (C.H.,0)” (NH.),
A nitrile is an ammonia derivative, where the three hydrogen
atoms are replaced by a trivalent radical.
Thus the cyanides of univalent alcohol radicals may also be regarded
as nitriles; for example:–
Hydrocyanic acid CHN
Methylic cyanide CHs.CN
Ethylic cyanide
Phenyl cyanide C6H,CN
= (CH)N formonitrile.
= (C2H3)"N acetonitrile.
C.H.CN = (CSPI)"N propionitrile.
= (C.H.)”N benzonitrile.
The term “nitrile ” is applied to all bodies similar to those obtained
by the abstraction of two molecules of water from ammoniacal salts,
and which are capable of being again reconverted into the ammonia
salt. Thus, if ammonic benzoate be distilled with anhydrous phos-
phoric acid, it furnishes benzonitrile,
(NHA)C.H.0
(C.H.)"N
Ammonic benzoate
* Benzonitrile
*
+
-H
2H2O.
Water.
Y X
674 - BIANDBOOK OF MODERN CHEMISTRY.
whilst ammonic benzoate is re-formed on boiling benzonitrile with
dilute acids or alkalies.
By the action of fuming sulphuric acid, the nitriles yield sulpho-
acids. Thus benzonitrile yields sulphobenzoic acid—
(CºH (HSO4)CO2H).
By the action of potassic hydrate, the nitriles yield ammonia and a
salt of the corresponding acid containing the same number of car-
bon atoms. Thus:—
(C.H.)”N + KHO + H2O = NH, -- KC, H.O.,
Benzo-nitrile + Potassic + Water = Ammonia + Potassic
hydrate benzoate.
This last reaction is important, inasmuch as certain cyanides or
nitriles have been obtained, which, under the influence of hydrating
agents, yield, instead of ammonia and the corresponding acid, an
amine (or alcoholic ammonia) and formic acid. These are known as
isocyanides and carbamines. For example: by the action of chloro-
form on aniline we obtain phenyl isocyanide, a body isomeric with
benzonitrile. Thus:—
C6H1N + CHCl, = 3HCl + C.H.N.
Aniline + Chloroform = Hydrochloric acid + Phenyl isocyanide.
(a.) But phenyl isocyanide, when boiled with a dilute acid, yields
formic acid and aniline. Thus:–
C.H.N + 2H2O +. (CGII.)"N + CH2O2
Phenyl isocyanide + Water F. Aniline + Formic acid.
(3.) Whereas benzonitrile yields benzoic acid and ammonia. Thus:—
Benzo-nitrile + Water º-º: Ammonia + Benzoic acid.
The isocyanides are unaffected by alkalies, whilst the nitriles are
easily decomposed.
=
TESTs For CERTAIN OF THE ALKALOIDs.
I. Alkaloids of Wegetable Origin.
Nicotine,—1. Tobacco odor. Turns brown by exposure.
2. Solubility. Soluble in water, alcohol, ether, and in the fixed oils.
3. Heat. Wolatile.
4. Auric and platinic chlorides give precipitates.
Does not coagulate albumen.
Conine,—1. Odor of mice.
2. Solubility. Soluble in ether and alcohol; almost insoluble in
water.
3. Heat. Wolatile.
4. Auric chloride (but not PtCl4) gives a precipitate.
Coagulates albumen.
REACTIONS OF THE ALKALOIDS. 675
Quinine,—1. Crystals; tufts of needles. Solutions of quinine salts
are fluorescent.
2. Solubility. Soluble in alcohol, ether, etc.; slightly soluble in
Water.
3. Heat. (1.). Entirely dissipated and decomposed when heated on
platinum foil. (2.) Gives a violet-red sublimate, with quinoline odor,
when heated in a test-tube.
4. Sulphuric acid dissolves it. The color produced is a faint yellow.
(Salicine gives a red.)
Witric acid dissolves it; no color, but turns yellow when heated.
Chlorine water and ammonia; a bright green solution.
Chlorine water, potassic ferrocyanide, and ammonia; a deep evanescent
red solution.
5. Turns the plane of polarization to the left.
Cinchonine,—1. Crystals; four-sided prisms. Solutions of cincho-
nine salts are not fluorescent.
2. Solubility. Soluble in alcohol; very slightly soluble in water ;
insoluble in ether.
3. Heat. Similar to quinine.
4. Chlorine water and ammonia; a yellowish white precipitate.
5. Turns the plane of polarization to the right.
Morphia.-1. Crystals; four-sided prisms. Taste, bitter.
2. Solubility. Soluble in water and alcohol; insoluble in ether.
3. Heat. Melts, inflames like resin, leaving a little charcoal, which
soon burns away. -
4. Nitric acid turns it red; color destroyed by SnCl2 and (NH4)2S.
(See Brucia.)
Sulphuric acid dissolves it; solution colorless.
Ferric chloride (Fe2Cls neutral); colors it blue.
Narcotine,—1. Crystals; rhombic prisms.
2. Solubility. Insoluble in water; soluble in alcohol and ether.
3. Heat. Fuses and is finally dissipated.
4. Sulphuric acid. A red color when heated.
Chlorine water and ammonia; a yellowish-red liquid.
Atropine,—1. Crystals; silky needles.
2. Solubility. Slightly soluble in water and ether; soluble in
alcohol and chloroform.
3. Heat. Fuses at 194°F., decomposes and partially sublimes.
4. Auric chloride; a yellow precipitate.
Aconitine,—1. Crystals not well marked. When a minute particle
is placed on the tongue, it produces tingling and numbness.
2. Solubility. Slightly soluble in cold water, soluble in alcohol and
ether.
3. Phosphoric acid; a violet tint.
Sulphuric acid turns it yellow, changing to a dirty violet.
676 HANDBOOK OF MODERN CHEMISTRY.
Strychnine,—1. Crystals; octahedra. Taste intensely bitter.
2. Solubility. Soluble in chloroform and methylic alcohol; slightly
soluble in water and dilute alcohol; insoluble in absolute alcohol or
ether.
3. Heat. Slightly volatile.
4. Sulphuric acid dissolves it without change of color; on adding
MnO2 or PbO2, etc., to the acid solution, a play of color from purple
violet to red is obtained.
5. The physiological test on a frog is infinitely the most delicate.
Brucia.-1. Crystals; needles arranged in stars.
2. Solubility. Soluble in water and alcohol; insoluble in ether.
3. Nitric acid. A bright red; becoming yellow by heat; violet by
SnCl2 or (NH4)2S. (See Morphia.)
4. Chlorine water. A red solution, becoming yellow with ammonia.
Caffeine,—1. Crystals; silky needles. Taste very bitter.
2. Solubility. Soluble in water, alcohol and ether.
3. Heat. Melts and sublimes.
4. Nitric acid. Solution red when evaporated to dryness; turns
purple on adding ammonia.
II. Alkaloid of Animal Origin.
Urea.—1. Crystals; four-sided prisms permanent in air.
2. Solubility. Soluble in water and alcohol; insoluble in ether.
3. Heat. Evolves NH3 ; partially sublimes.
4. Nitric acid. Forms crystals of nitrate of urea.
Potassic hydrate and heat; evolves ammonia.
Oaxalic acid; deposits tabular crystals.
III. Artificial Alkaloid.
Aniline,—1. Liquid, with fragrant odor, becoming brown on
exposure.
2. Solubility. Slightly soluble in water; very soluble in alcohol
and ether.
3. Heat. Wolatile.
4. Alkaline hypochlorite (chloride of lime); a purple color. .
Heated with mercuric chloride, and the residue dissolved in alcohol
forms a magenta solution. A Solution in dilute sulphuric acid sub-
mitted to electrolysis turns blue (changing to violet) at the positive
pole by the action of the nascent oxygen.
- 677
CHAPTER XXIX.
COLORING MATTERS.
Natural History—General Preparation and Properties—Yellows–Reds—Blues-
Browns—Blacks.
SUPPLEMENTARY CHAPTER : Dyeing and Calico Printing.
Natural History.—A few coloring bodies are found (1) in the animal
kingdom, such as cochineal and sepia, but they occur almost entirely
(2) in the vegetable kingdom.
Preparation.—(1.) By solution in water, spirit, ether, or oils.
(2.) By fermentation (e.g., indigo, madder, archil, and litmus).
Preparation of Indigo.—The leaves of plants of the species indigofera,
are placed in water and allowed to ferment. A yellow soluble sub-
stance is first formed, which in time turns blue, and becomes insoluble.
This constitutes, when dried, the indigo of commerce. The change of
color is due to the oxidation of a body existing in the plant, called
&ndican. -
Preparation of Madder.—Madder is prepared by a similar method of
fermentation, whereby a yellow substance present in the plant, called
rubian (C28H3,015), becomes converted into alizarine (C4HsO4). -
Preparation of Archil and Cudbear.—The plants are first digested
with lime and water, and the clear filtered solution neutralized with
hydrochloric acid. The white precipitate thus produced, consisting
of one or more acids, such as erythric, evernic, and lecanoric acid,
is dissolved in hot alcohol. This solution is then boiled with lime,
by which means the acids are decomposed. The clear solution from
which the excess of base has been removed, yields on evaporation
and extraction with boiling alcohol, the colorless body called orcine
(C.H.O.), which by the action of air and ammonia forms the red
coloring matter orcéine (C7H7NOs).
In practice, the archil and the cudbear are mixed with lime and
urine (the latter to furnish ammonia), and exposed to the air for some
weeks. In the case of litmus, ammonic and potassic carbonates are
used instead of lime and urine. The red color produced in the case
of litmus is azolitmine (C7H16NO5), which differs from oreeine in its
insolubility in alcohol.
(3.) By artificial processes, such as indigo-blue, which is prepared
from aceto-phenone, alizarin from anthracene, etc.
678 HANDROOK OF MODERN CHEMISTRY.
Properties. – (General). — The organic coloring matters are solid
bodies. Some of them are crystalline, such as alizarin, moritannic
acid, haematoxylin, etc.
Their colors are bright; they have but little taste or odor.
Heat decomposes most of them. A few are volatile (e.g., indigo,
alizarine).
Light bleaches most of them, especially if the coloring matter be
moistened with water.
They are mostly soluble in water, but are insoluble in alcohol or
ether.
Strong acids generally decompose them, sulphuric acid charring,
and nitric acid oxidizing them, Weak acids change the blues to
reds. Cyanine, for example, is the blue coloring matter of certain
flowers, and the flower is blue if its juice be neutral, but red if it be acid.
They are all bleached by chlorine, by sulphurous acid, by re-
ducing agents, and generally also by the action of nascent oxygen.
Alkalies change the reds to greens or blues, and the yellows to
browns.
The metallic oxides combine with many of them to form permanent
compounds (as, e.g., the lakes). Thus alumina, ferric oxide, and
stannic oxide are used as mordants. Charcoal generally both absorbs
and destroys the colors,
I. The Yellows.
1. Annatto (seeds of Bixa Orellana).-The coloring matter “bixine”
is soluble in alkalies.
2. Chrysammic Acid.—Prepared by the action of nitric acid on
aloes.
3. Gamboge (Hebradendron Gambogioides).—A gum resin, the
coloring matter being soluble in water.
4. Homatoacylin. (Logwood ; Haematoxylon Campechianum).-It
forms the red ha'matein (C15H12O6) in contact with oxygen and alkalies,
and a black by the action of potassic chromate.
5. Luteoline or Weld (Reseda Luteola).-Soluble in water.
6. Morindin (Morinda Citrifolia) (Soranjee).
7. Moritannic Acid (Morus Tinctoria or Fustic).--Soluble in water.
8. Orypicrio Acid.—Prepared by the action of nitric acidon assafoetida.
9. Phylloxanthin.—Phylloxanthin is precipitated by boiling chloro-
phyll in an alcoholic solution of potash, and adding hydrochloric
acid to the solution.
10. Picric Acid is a derivative of phenol, and also a product of
the action of nitric acid on indigo.
11. Purree or Indian Yellow (origin º).-A compound of magnesia
and purreic or euxanthic acid.
COLORING MATTERS. 679
12. Quercitrin (Quercus Tinctoria).
13. Rubian (See Madder).
14. Saffron (Yellow Anthers of Crocus Sativus).--A glucoside.
15. Turmeric (Curcuma Longa).-The coloring matter curcumine is
soluble in alcohol, but insoluble in water.
16. Xanthin and Xantheine.—The yellow coloring matter of flowers
and of yellow leaves.
II. The Reds.
1. Alizarin (See Madder).
2. Braziline.—C2.ÉI2007, obtained from Brazil wood.
3. Carmine; Cochineal; (from insects of coccus tribe).-Cochineal
is extracted by water and alcohol. The coloring body is carminic acid
(C14H140g), which combines with alumina to form lakes.
4. Draconine (Dracoena Draco).
5. Hametein (See Haematoxylin).
6. Madder Red (Rubia Tinctorum).—By the fermentation of the
yellow coloring matter rubian (Cash;10,s), whereby alizarin is formed
(C4H8O.).
7. Orceine (C7H8O.).
8. Safflower (petals of Carthamus Tinctorius).-The coloring matter
carthamine (C14H1607) is soluble in alkalies and is reprecipitated by
acids.
9. Santaline (Pterocarpus Santalinus).
III. The Blues,
1. Cyamine.—This constitutes the blue colouring matter of flowers
and also the colouring matter of grapes.
2. Indigo (various species of indigofera) (See General Preparation,
page 677).-By the action of deoxidizing agents and an alkali, indigo
becomes soluble and colorless (indigo white), changing to blue on
exposure to air. Traces of indigo have been found in the urine.
Blue indigo ... gº tº ºf ... CigHo N2O2.
White indigo... g is tº ... Cl6H16N2O2.
By oxidation, indigo forms isatin (CeBioN.O.), from which, by the
action of chlorine, chlorisatin is derived (CsIHaCl.N.O.).
3. Litmus, Archil and Cudbear (from various lichens, as Roccella
Tinctoria (litmus), Lecanora Tartarea (cudbear)). These colors are
developed by fermentation, whereby orceine (C7H7NO3) is formed.
(See General Preparation.) -
4. Phyllocyanine.—From chlorophyll. This coloring matter remains
in solution after the phylloxanthin has been precipitated.
680 HANDBOOK OF MODERN CHEMISTRY.
IV. The Greens.
1. Chlorophyll.—A resinoid body present in plants. It is soluble
in ether, and consists of phylloxanthin (a yellow) and phyllocyanine
(a blue).
W. Brown.
Sepia, from the cuttle fish.
WI. Black.
See Haematoxylin.
Pigmentum Nigrum.
681
SUPPLEMENTARY CELAPTER.
DYEING AND CALICO-PRINTING.
Dyeing.—To obtain uniformity of color it is necessary that
the coloring matter should be applied to the fabric in solution; but
it is also essential, in order that the color should not be discharged
when the fabric is washed, that it should be rendered insoluble in
the fibre.
Sometimes the fibre itself forms an insoluble compound with the
coloring matter. Thus, animal fabrics (such as silk and wool) com-
bine with coloring matters; but if this does not happen, as in the
case of cotton, other systems have to be adopted, such as the follow-
ing —(a.) The fibre is sometimes impregnated with a material called
a mordant, such mordant being capable of forming an insoluble com-
pound with the coloring matter (e.g., alumina and cochineal). (3.) In
the case of a color formed by the admixture of solutions, the fabric
is first Saturated with one solution and then dipped into the second,
so that the insoluble coloring matter may be formed in the fabric
itself. (Thus, a blue dye is formed from ferric chloride and potassic
ferrocyanide.)
The red dyes used are madder and brazil wood, alum and bitartrate
of potash being the mordants employed. Lac or cochineal are used
for dyeing wool, stannic chloride and bitartrate of potash being used
as mordants. The aniline colors are also employed, albumen being
required as a mordant in dyeing cotton, no mordant being necessary
for wool or silk.
The blues used in dyeing are usually indigo, the aniline blues, or
prussian blue, the latter being formed by the admixture of solutions
of ferric chloride and potassic ferrocyanide.
The yellows employed are weld, quercitron, fustic, annatto (alumi-
nous mordants being used for each of these dyes), lead chromate
(formed by the admixture of acetate of lead and potassic chromate),
and carbazotic acid.
Browns and blacks are formed by a mixture of tannin and a salt
of iron, different shades depending on the relative proportions of
each, on the admixture of indigo, etc.
Calico printing.—This consists in the production of a pattern on the
fabric. This is effected in different ways. (1.) By printing the
pattern on the fabric with the mordant mixed with gum. By the
action of water containing cow-dung (dunging) any excess of mor-
682 HANDBOOK OF MODERN CHEMISTRY.
dant is removed. The fabric is then dipped in the dye-bath, and any
color except that on the mordanted pattern can be washed out with
water. (2.) Sometimes a resist is used, that is, a substance, like citric
or tartaric acid, which prevents the fabric taking the color on those
parts to which the resist has been applied. (3.) Sometimes a discharge
is used. The color from a uniformly printed fabric dyed with indigo,
madder, etc., may be removed wherever desired by the application
of an acid mixed with gum, and afterwards passing the fabric
through a solution of chloride of lime. By this means the color
will be discharged wherever the acid has been placed. Different
eolors may also be produced at the same time, by combining the
acid with different reagents. -
683
CHAPTER XXX.
WEGETABLE CHEMISTRY.
Tissues of Vegetable—Cellulin—Vegetable Parchment—Gun Cotton—Woody and
Corky Tissue—The Life of a Plant.
The organised structures of plants are made up of three kinds of
material :—
(1.) Cellulin (lignin) (C5H10O3), which is the growing part of the
plant, such as the cambium layer, etc.
(2.) Woody matter (sclerogen), such as the duramen or alburnum.
(3.) Corky matter, or the outer layer of the plant.
In the first of these three bodies, the hydrogen and oxygen are pre-
sent in the proportion to form water, but in woody tissue and in
corky matter the proportions are different.
I. Cellulin (lignin; cellulose) (C5H10O.). This constitutes the
growing and the active part of the plant. It forms the basis of cells
and the true cell-wall. In its purest form it is met with in the extre-
mities of the roots and buds, in the pith or medulla, in the medullary
rays, in the cambium or under layer of the bark, and in certain hairs
or filaments about the seeds, such as cotton. Fungi and the substance
called vegetable ivory are said to consist of nearly pure cellulin.
Preparation.—The adhesion of encrusting woody tissue to the cellulin
is so great, that it is scarcely possible to prepare it in a state of absolute
purity. By the consecutive action upon it of various solvents, such as
water, alcohol, ether, dilute alkalies, and dilute acids, its comparative
purity may be effected.
Properties.—(a.) Physical. A tasteless, colorless, and perfectly innu-
tritious substance; specific gravity, 1:9. Its appearance varies. It is
spongy in the shoots of germinating seeds; porous and elastic in the pith
of the rush and elder; flexible and tenacious in the fibres of the hemp
and flax; compact in the branches of growing trees; hard and dense in
the shells of the filbert, etc. Cellulin possesses the power of depo-
larizing a ray of polarized light.
(6.) Chemical. Cellulin is insoluble either in hot or cold water, in
alcohol, in ether, or in oils. It is soluble in an ammoniacal solution
of cupric oxide, from which it may be precipitated by acids. It is not
acted on by iodine. It is capable of fermentation, as shown in the
ripening of fruits.
Concentrated alkaline solutions dissolve it slightly, converting it first
into starch, and finally into gum —hence fabrics are injured by being
boiled in soda, Heated with alkalies it forms oxalic acid.
684 HANDBOOK OF MODERN CHEMISTRY.
Action of Acids.--Dilute mineral and organic acids have very
little action upon it. Hydrochloric acid dissolves it when heated
with it, the cellulin being precipitated on the addition of water.
Sulphuric acid dissolves it, converting it first into dextrin, and finally,
when boiled in a quantity of water, into glucose. Nitric acid (specific
gravity, 1:2) has no action upon it unless heated, when it forms
Oxalic acid.
Vegetable Parchment.—Preparation. By immersing blotting-
paper in a mixture of 2 parts of oil of vitriol and 1 part of water,
with subsequent washing.
Properties.—Tough, waterproof, and transparent. It neither gains
in weight nor alters in composition by the action of the acid, the
change being purely molecular.
Gun-Cotton (Pyroxylin; cellulo-nitrin).--Preparation. By soaking
cotton wool in a mixture of fuming nitric acid (1-5 specific gravity)
and sulphuric acid.
C6H10O. + 3HNO, - C6H1(NO2)3O. + 3H2O.
Cellulin + Nitric acid = Trinitro cellulin + Water.
Constitution.—Cellulin has been regarded as a trihydric alcohol,
CºEI702(OH)3, and pyroxylin as a nitric ether, C.H.O.(NO3)3; the
relationship existing between glycerin, C3H3(OH)3 and nitro-glycerin
CŞH3(NO3)4, or between ethylic alcohol, C2H3(OH) and ethylic
nitrate C.H3(NO3) being of a similar nature. Its more rational
formula, however, seems to be CºHz(NO2)3O, i. e., regarding it as a
substitution product of cellulin, C6H10O3, where H3 has been replaced
by (NO2)3.
Properties.—(a.) Physical. The form and appearance of the cel-
lulin remains unaltered by the action of the acid, nevertheless, it will
be found to have increased 82 per cent. in weight, and to have lost
its power of depolarizing a ray of light. It will be found, moreover,
to have become hygroscopic and highly electrical when rubbed or
pulled out briskly. It is insoluble in alcohol, water, ether and in dilute
acids, but is soluble in acetic ether, in methylic acetate, and in a
mixture of ether, ammonia, and potash.
(6.) Chemical. Its composition varies according to the strength of
the acid used.
Thus, by using a less concentrated acid, less highly nitrated com-
pounds may be produced, such as CSPI,(NO2)0, and CºEſs(NO2)2O,
the latter constituting the dinitro-cellulin used for collodion.
It inflames at or about 400°F. (204-5°C.).
By the action of reducing agents, such as nascent hydrogen, gun-
cotton may be reconverted into cellulin.
The products of its combustion are CO, CO., N, HNO3, and CN.
Collodion is a solution of dinitro-cellulin in a mixture of alcohol and
ether.
Uses of Cellulin.—In nature its use is essentially vital, performing
VEGETABLE CHEMISTRY. 685
the functions of the plant, and elaborating the various products from
the juice.
In the arts it is used in the manufacture of paper, cotton fabrics,
gun-cotton, collodion, etc.
II. Woody Matter (incrusting matter; Sclerogen). This is the
deposit found either within the cell, or encrusting the cell wall. It is
difficult to obtain it pure on account of the rapidity with which it
becomes oxidized. It is insoluble in water, alcohol, and ether.
Unlike cellulin, it is soluble in alkalies. Exposed to the air, and
more especially under the influence of parasitic plants, it becomes
pulverulent, constituting “dry rot.” Sulphuric acid does not, as in
the case of cellulin, convert it into sugar; nitric acid tinges it yellow,
forming with it gelatinous compounds; hydrochloric acid renders it
brown and black. Iodine and sulphuric acid change it blue. The
products of its destructive distillation have been already described
(page 501).
Uses.—In mature it gives support to the plant. In the arts its uses
are numberless.
III. Corky Matter is also an incrusting matter, and is always
found outside the cell wall. The entire plant—leaf, fruit, flower,
and indeed every cell, is covered with it.
Properties.—It is lighter than and impermeable to water, and is
insoluble in water, alcohol and ether. It is soluble in alkalies. It is
insoluble in strong sulphuric acid except by heat, or after a long period
of action, but it is soluble in nitric acid (specific gravity, 1-2), which
changes it to suberic acid. It is dissolved by chlorine. It is turned
brown (not blue) by iodine and sulphuric acid. It will not take a
dye. These reactions show—
1. Why potatoes and fruits do not dry, viz., owing to the imper-
meability of the corky matter to water.
2. Why cotton must be first bleached with chlorine before being
dyed, viz., to remove the corky matter present on the cells.
Uses in nature.—To bind the cells together, and also to prevent
the moisture in the cells from evaporating.
The Life of a Plant.
The seed is placed in the ground.
The soil is formed by the combined action of air, and of rain con-
taining carbonic acid in solution, upon, say, a granite rock. The water
in the rock expanding in the act of freezing, assists in breaking down
the rock upon which the rain and the air have previously acted. Thus
the soil derives its mineral ingredients. Spores of the lower orders of
plants, such as the lichens, find in this soil a resting-place, grow, live,
and die; their remains supply the soil with the organic portion neces-
sary for the growth of plants of a higher order.
686 HANDBOOK OF MOIDERN CHEMISTRY.
The seed is placed in this soil. Under the influence of warmth and
moisture the insoluble starch of the seed, by the action upon it of a
nitrogenized ferment (diastase), is converted into soluble sugar, capable
of serving as the first food of the plant, until it is able to shift for
itself. The germ shoots, that is, it sends forth leaves and roots.
These are its two means of obtaining food, the former acting as lungs
and the latter as mouths.
The food of the plant is entirely inorganic. One thing, however, is
essential, viz., that the food supplied to the plant should be soluble.
The chemical action of the plant is an action of reduction or deoxida-
tion.
The leaves inhale ammonia and water vapor, and also more particu-
larly carbonic anhydride. Under the action of light they fix the
carbon of the carbonic anhydride, and exhale pure oxygen.
The roots also take up—carbon as CO2, derived from decaying
organic matter, nitrogen from the ammonia carried down by the rain
or the product of putrefaction, or derived from the nitrates and
nitrites the results of nitrification, together with sulphur, phosphorus,
and chlorine derived from the sulphates, phosphates, and chlorides of
the soil.
Thus the plant grows. The tips of the buds and the extremities of
the rootlets are the active points of growth. Here no starch is to be
found, for all the starch in these parts is converted into sugar to aid
the growth.
The culminating point in the life of the plant is the formation of its
fruit. The unripe fruit contains an insoluble body called pectose, to
which the hardness of unripe fruits is due, together with cellulin and
an acid, such as citric, tartaric, malic, etc., to which their sour, rough
and astringent taste is to be attributed. By the action of warmth,
the acid and a peculiar ferment present in the fruit (pectase) react on
the insoluble pectose, and change it into the soluble pectin of ripe fruits,
which, as ripening proceeds, becomes transformed into pectic and
pectosic acids. These impart to the juice its power of gelatinizing
(that is, forming a jelly) when boiled. Further, the fruit as it ripens
absorbs oxygen, and evolves carbonic acid. Thus the tartaric or other
acids by oxidation are converted into fruit sugar. Thus—
3C4H606 + Og = CsPI,206 + 3H2O + 6CO2.
Tartaric + Oxygen = Fruit sugar + Water + Carbonic
acid anhydride.
whilst a similar change results in the case of the cellulin and of the
starch by the assimilation of water.
Thus the ripe fruit becomes sweet and loses its sour taste.
The ripening action being complete, oxidation still continues, but it
now induces the changes of decay and putrefaction.
Finally, the plant dies and decays. Its carbon is dissipated as CO2,
its hydrogen as H2O, its nitrogen as NH3. Thus the dead plant
LIFE OF A PLANT. 687
becomes the gaseous food for other and living plants, to be absorbed
by their leaves. Its mineral constituents are washed into the soil,
whilst its woody tissue rots and forms humus, which also serves as a
source of food for vegetation.
The soil needs constant renewal in order to restore its exhausted
fertility. This is effected by manuring ; phosphorus, sulphur, nitrogen
and silica, together with lime, magnesia, and the alkalies, are supplied
by gypsum (which, as well as supplying lime and sulphur, serves to
retain the carbonate of ammonia by converting it into sulphate), by
bone-ash, by superphosphate, by sodic chloride (which may be con-
verted into carbonate, silicate, or other salts of soda), by sodic nitrate,
by the alkaline silicates (soluble silicates being needed more especi-
ally by the cereals), and by ammonic sulphate.
Further, dead plants, the ashes of plants, urine, solid animal
excrement, guano (i.e., the dung of carnivorous sea birds, which
contains a large quantity of urate of ammonia), and soot which con-
tains ammonia, are all employed as sources of food for the vegetable.
Sometimes the ground is allowed to lie fallow, chemical changes
occurring by the action of air and moisture, whereby it becomes en-
riched.
The use of lime depends on its power of promoting the decay of
organic, and the decomposition of mineral matters, whereby they are
converted into soluble forms.
Lastly, it must be remembered that different plants, like different
animals, need different foods. Hence the principle of “the rotation
of crops.” s -
688 HANDBOOK OF MODERN CHEMISTRY.
CHAPTER XXXI.
ANIMAL CHEMISTRY.
ALBUMINOIDs: I. Animal Solids — II. Nutrient Fluids — III. Digestion, and the
Fluids concerned in it—IV. Excrementitious Products.
ALBUMINOIDS OR PROTEIDS,
These bodies form the chief part of the solid constituents of animal
organs. They are also found in small quantities in vegetables.
The formula C12Huania02a S represents their composition approxi-
mately. They are all amorphous, and turn the plane of polarization
to the left. They are insoluble in alcohol and in ether, but are soluble
in water, in acetic and the mineral acids, and in the alkalies. They
may be known by forming a yellow solution with nitric acid (xantho-
proteic acid) which becomes orange-red when treated with ammonia.
The caustic alkalies decompose them. They are precipitated from
their solutions by acetic acid and by mercuric nitrate (Millon's
reagent), leaving, in the latter case, a red supernatant solution.
According to Hoppe-Seyler, the albuminoids may be arranged as
follows:—
Class I. Albumens.
(Soluble in water.)
Name. Source. Properties.
—-am-º.
Ser-albumen...] Blood serum | A yellow elastic transparent body. Its aqueous solution is preci.
pitated by alcohol. It is not precipitated by a small quantity of
very dilute acid, but is precipitated by the addition of acids in
large quantity. The precipitate is soluble in excess of strong
HCl, and in strong HNO,. When injected into the veins, it does
not, like ov-albumen, pass into the urine.
Ow-albumen .. Egg Coagulated by ether and turpentine. . It is insoluble in strong
HNO3. When injected into the veins, it passes into the uring
unchanged.
Veget-albumen Like ov-albumen.
ALBUMINOIDS OR PROTEIDS. 689
Class II. Globulins.
(Insoluble in water, but soluble in dilute acids and alkalies, and also
in dilute solutions of NaCl or other neutral salts.)
Name.
Source.
º Properties.
Myosin . .
Globulin (para-
globulin).
Fibrinogen
Witellin . .
. Yelk of egg.
Muscle
Prepared from
Blood serum,
by passing
CO2 through
a dilute solu-
tion.
Aqueous hu-
77?07/7”.
Crystalline
dens.
Pericardial
fluid.
Hydrocele
fluid, etc.
Coagulable by heat and by alcohol. It is soluble in very dilute
HCl, rapidly becoming acid-albumen.
The globulin from blood serum is fibrino-plastic, i. e., it can form
fibrin in contact with certain fluids (paraglobulin). In this
respect it differs from the globulin of the crystalline lens (glo-
bulin).
Precipitated by CO, or by very dilute acids from its solution in
NaCl. Soluble in water saturated with oxygen, and in very
dilute alkaline solutions; but if the solution contains 1 per cent. of
alkali it dissolves as an albuminate, and not in a free state. It is
converted into acid-albumen by dilute acids. It coagulates at
158° F (70° C.).
Produces fibrin when mixed with fibrino-plastic globulin (fibrino-
genous). It is more difficult to precipitate by CO2, and less
difficult to precipitate by a mixture of alcohol and ether, than
globulin.
Witellin is the residue left after treating the yelk with ether. It is
a white granular body, insoluble in water, and soluble in solutions
of neutral salts. It is neither fibrino-plastic nor fibrinogenous.
It is converted into acid albumen by dilute acids, and is soluble in
dilute alkalis as an albuminate.
Class III. Derived Albumens.
(Insoluble in water and in dilute NaCl solutions; soluble in dilute.
acids and alkalies.)
Acid albumen
Alkali albumen
or albuminate
Casein
If the albumens of Class I. be acted on with a small quantity of
dilute acid (HCl or acetic), the coagulation of the albumen does
not occur at 70° C., and its levo-rotatory action on a polarized
ray is largely increased (acid albumen). On neutralizing the acid
solution, a white precipitate of albumen is thrown down, which
will now be found to be insoluble in water and in a NaCl solution,
but soluble in an excess of alkali or of alkaline carbonates. Coagu-
lates at 70° C. The albumens of Class II. are soluble in dilute
acids as acid-albumen. The solution yields a precipitate when
neutralized, which is not soluble in neutral saline solutions.
Alkalies, like acids, prevent the coagulation of albumen (albu-
minates), the albumen being precipitated on neutralizing the
solution.
Casein is closely allied to the artificial albuminates.
Class IV. Fibrin.
(Insoluble in water, and but slightly soluble in neutral saline
solutions or in dilute acids and alkalies.)
Fibrin ..
chyle.
..|Blood; lymph; Believed to be formed by the contact of fibrino-plastic and fibrogenous
substances (see Blood, page 699). Fibrin is very elastie and pos-
sesses a filamentous structure. It is insoluble in water, except
at very high temperatures, or after a very lengthened action. It
swells up when acted on with dilute acids and alkalis, and after
their prolonged action, aided by heat, dissolves slightly.
Y Y
690 HANDBOOK OF MODERN CHEMISTRY.
Class W. Coagulated Proteid.
(Insoluble either in dilute or strong acids, except acetic acid; soluble
in the gastric fluid (pepsin) which converts it first into syntonin
and finally into peptone.)
Name. Source. Properties.
This body is produced by the action of heat or of alcohol on neutral
solutions of albumen, fibrin, myosin, etc. Strong HCl and also
ether convert ov-albumen into a coagulated form. Heat similarly
converts the albuminates into a coagulated form, but the preci-
pitate may be reconverted into the albuminate by potassic hydrate,
Class VI. Peptones.
(Bodies formed by the action of the gastric juice on albuminoids;
soluble in water, insoluble in alcohol and ether.)
Peptones. ||Stomach and | These bodies are highly diffusible. They are not precipitated by
small intes- acids or alkalies.
times only.
REACTIONS OF TIIE PROTEIDS.
The following Table taken from Fownes' (Watt's) exhibits the
reactions of the several proteids before named :—
Soluble in water :
Aqueous solutions not coagulated by boiling, PEPTONES.
Aqueous solutions coagulated by boiling . ALBUMENS.
Insoluble in water :
Soluble in a 1 p. c. solution of sodic chloride, GLOBULINs.
Insoluble : 27 3 y
Soluble in hydrochloric acid (0.1 p. c.) in
the cold :
Soluble in hot spirit . & e . ALKALI-ALBUMEN.
Insoluble in hot spirit . * wº . ACID-ALBUMEN.
Insoluble in hydrochloric acid (0:1 p. c.) in
the cold :
Soluble in hydrochloric acid (0.1 p. c.)
at 60° C. ſº FIBRIN.
Insoluble in hydrochloric acid (0.1 p. c.)
at 60° C.; insoluble in strong acids:
tº | CoAGULATED
uble in gastric iuice
Soluble in gastric juic ALBUMEN.
Insoluble in gastric juice . tº . AMYLoïD.
ANIMAL SOLIDS.
691
A.—ANIMAL SOLIDS.
Bones, TEETH, SHELLs, ETC. FLESH, GELATIN, CHONDRIN, HAIR, SILK,
ERAIN AND NERVE TISSUE.
Bones from a child aet. 13 months.
TABLE I.
Composition of the healthy human bones of a child and an adult :-
Cause of death bronchitis.
Bone, Teeth, Shells.


Bones from a male aet. 40 years.
Cause of death bronchitis.

- a; - a;
$– - - F3 2 H is c; P tº -
5 || 3 || 3 || 5 | E | 3 || = | 3 | # | 5 || 5 || 3
à || 3 || 3 | # | 3 || 5 || 5 | # | 3 || 3 || 3 | #
Prº E- P- E. p: P P- F. H ſ:
Calcic
º: 49-6 || 47.5 47.6 50.6 45.1 49.2 || 60.2 57.9 57-4 61.8 57.4 58-2
fluoride.
Calcic w º K. * . - tº 8 & * . * . * * . º
ºt. 6'0 6-0 5.9 7-1 5-0 6'4 8-0 7-8 7' 5 8:8 7-3 7-8
Magnesic \ º º & & º & sº 1. g * , * e
º: ; 10 || 08 || 08 || 10 | 10 || 0-3 | 1.4 14 | 1.3 | 1.4 | 1.3 tº
Animal * I tºº & - º & º º te tº * * a & º
matterS. } 43°4 || 45.7 45-7 || 41-3 48-9 || 43-6 || 30°4 32.9 || 33-8 28-0 34-0 || 32-4
TABLE II.
Composition of the bones of different mammals, birds, fishes, and reptiles:–

Birds (Femur
Fishes
;
i
Mammals (Femur of). of). (Vertebrae of.)
fl & P+_2 º cº) § º º > tº 5 s:
㺠#| | | | #. à || 5 || 3 | # É | 3 | # #3
## |##| = |##| 5 || > | = | 5 | # | * | 3 ||3:
ſº B: ask R
Calcic -
phosphate. | 58.0
55.9 54.1 || 54-4 58-9 || 57.9 57.5 58-6 || 59.5 || 57.6 36-6 || 59.5
Calcio || 2.2
fluoride. \ | * *
Calcic - - * A & - - tº º s e * º
carbonate. | 8-0 | 12:2 12*7 | 12-0 || 9-0 || 11.1 4.8 5-1 8-9 || 4-9 1-0 || 2-2
Magnesic - º tº . - " * { e * & * *
i. 1°4 || 1-0 | 1.4 || 1:9 || 1:2 1-1 || 1-0 || 0-8 1-0 || 2–3 || 0-7 || 1-0
Oth -
i. | . . . 0-5 0-8 || 0-7 || 0-9 1-0 || 0-7 0-8 0-9 || 1-0 || 0-8 1.8
Animal 4. * jºr
Imatters. | 30°4 || 30-4 || 31-0 || 31-0 || 30-0 || 28:9 || 36-0 || 34-7 || 29-7 || 34-2 || 60-9 || 35-5

692 HANDBOOK OF MODERN CETEMISTRY.
TABLE III.
Composition of certain diseased bones, of teeth, and of various
shells :-
Diseased Bone. Enamel * O Hen’s Fish
Tooth. of Crab s stºr | Egg Scales
Rachitis. Caries. Tooth. Shell. hell. Sheil. (Perch).
Tibia. | Femur.
Calcic phosphate . . * & e g * tº g *.
Calcic fluoride . . . . }26.9 38-4 64-3 || 88.5 6-0 1.2 10 sis
Calcic carbonate . . 4 - 9 5 4 5-3 8-0 62.8 98.3 97-0 3-0
Magnesic phosphate 0.8 1 - 1 1 - 0 1.5 1 - 0 tº º & g 0.9
Other salts . . . . . . 1 - 1 0.9 1 - 4 tº gº 1 : 6 tº ſº * & & ſº
Animal matter ..., | 66-3 54 - 2 28.0 2-0 28-6 0.5 2 : 0 57-4


Omitting the periosteum or external membrane of the bone and
the internal membranes, marrow, etc., we may say that bone con-
sists of a mixture of an organic substance, called ossein, with inorganic
compounds. It has been stated that iron has been found in bone,
but if present, it is probably due to the retention of blood in the
bone.
We would note that :—
(1.) There is a close resemblance in the chemical composition of the
bones of the higher mammalia. (Table II.)
(2.) The bones of the young contain more animal matter, and less
earthy matter than the bones of adults. There is, however, no well-
marked gradation in the proportions. (Table I.)
(3.) The composition of bone is influenced by certain diseases.
(Table III.) The alteration generally consists in a diminution of the
earthy constituents.
(4.) The composition of bone varies slightly with the part from
which it is derived. Thus the femur and humerus contain more
earthy matter than the tibia and fibula or the radius and ulna, whilst
the scapula, the sternum and the vertebrae contain less earthy matter
than the long bones. (See Table I.)
(5.) It would seem that the bones of males contain slightly more
earthy matter than the bones of females.
(6.) Of other animal substances closely allied to bone we note—
(a.) Teeth (Table III.). The substance of the teeth is (excepting
the enamel) very like bone in its composition. The enamel (i.e. the
covering of the tooth external to the gum), is remarkable for con-
taining very little organic matter and a large excess of inorganic
constituents.
(3.) The Shells of the crustaceae, and of the mollusca, and also
birds' eggs, contain generally but little phosphate and a considerable
excess of carbonate of lime.
- FLESH. 693
(y.) In Fish Scales the phosphate of lime is less, and the animal
matter more, than in bone.
Properties of bone.
(a.) Action of heat in open vessels. The organic matter burns away,
leaving a white “bone-ash ’’ (Ca3P.Os). This residue is used in the
manufacture of phosphorus (see page 124), and also as a manure, in
the form principally of Superphosphate.
(3.) Action of heat in closed vessels (destructive distillation).
Ammonia and tarry matters (Bone-oil or Dippel's oil) are given off,
the residue in the retort constituting “Animal Charcoal ’’ or “Bone
black.” This consists of a mixture of phosphate of lime and finely
divided carbon. Animal charcoal is largely used by the sugar re-
finers. When its decolorizing power has been exhausted, it is burnt
for the purpose of recovering the bone ash.
(y.) Action of water. When bones are boiled in water at 212° F.
(100° C.) all that occurs is the separation of the grease present in the
bone. This floats on the surface of the water, the ossein of the
bone being insoluble. If the bone, however, be digested in water at
a temperature of 300°F., as in a Papin’s digester, the organic matter
is rapidly converted into gelatin, which is soluble in water. This
converted ossein is used for glue.
(3.) Action of acids. When dilute hydrochloric acid is added to
bone, effervescence first occurs by its action on the lime carbonate.
In time the dilute acid dissolves out the whole of the earthy phos-
phates, etc., leaving only the ossein (the organic constituent of the
bone), a semi-transparent horn-like body, which by the action of
heat under pressure is converted into gelatin.
(e.) Action of burial. After long burial the organic matter of bone
disappears, leaving only the inorganic constituents.
Flesh.
Composition of Flesh—
Water tº º 'º © tº gº tº º ºs e º 'º ... 78-0
Fibrin (with nerve tissue, blood-vessels, etc.). 17:0
Albumen ... º º ſº & © tº tº º ſº tº e C. 2.5
Other constituents of the juice ... tº tº a 2.5
100-0
Muscle contains about three-fourths its weight of water, one part
of which is due to the blood present, and a second part to the “juice
of flesh,” as it is called, i.e., an acid liquid containing kreatin, inosite,
and certain salts, together with phosphoric, lactic, and butyric
acids. -
694 HANDBOOK OF MODERN CHEMISTRY.
Freatine (C.H.N.O.aq), when boiled in an acid, loses water and be-
comes kreatinine (C.H.N.30), a minute trace of which is found in urine.
When boiled with alkalies, kreatin gains water and yields urea
(CH4N2O) and sarcosin (C, H, NO.).
Inosite or muscle sugar (C6H12O6.2aq), a body similar in composition,
but dissimilar in properties, to grape sugar, may be obtained from
the concentrated extract of flesh. It may also be obtained from
green kidney-beans.
As soda is the chief alkali of the blood, its alkalinity being Sup-
posed to be due to phosphate of soda (Na2HPO,), so potash is the
chief alkali of the juice of flesh, its acidity being supposed to be due
to the acid phosphate of potash (KH2PO4).
Gelatin and Chondrin do not pre-exist in the animal kingdom,
but result from the action of boiling water on gelatinous tissues
(such as skin, tendons and bones), * or on chondrin-producing tissues
(such as the cartilages of the ribs and joints).
Ultimate Composition of Gelatin and Chondrin.
Gelatin, Chondrin.
Carbon ... ... ... 50-0 49 - 1
Hydrogen ... • * * e tº e 6' 6 . 7.1
Nitrogen ... * * * tº is tº 18:3 14 4
Oxygen 9 tº º tº e ºs ... 25.1 29' 4
100.0 100.0
In addition to the above, earthy phosphates are always present.
Gelatin is found in a pure state as isinglass (the dried swimming-
bladder of the sturgeon), and in a less pure state as calf's-foot jelly,
glue, and size. It is soluble in hot water, but insoluble either in cold
water, in alcohol, or in ether. It shrinks greatly in bulk when ex-
posed to dry air. When perfectly dry, gelatin may be preserved
indefinitely, but when moist it rapidly becomes acid, and putrefies.
A gelatin solution is precipitated as tanno-gelatin by tannic acidf
(the only acid known that possesses the power of precipitating it),
by alcohol, by mercuric chloride, by mercurous and mercuric nitrates,
and by chlorine (forming a chlorite of gelatine). It is neither pre-
cipitated by alum nor by basic or neutral lead acetate.
Boiled with strong alkaline solutions, it is converted into leucine,
or amido caproic acid (C6H13NO2), and glycocol (glycocine) or amido-
acetic acid (C2H5NO2), with the evolution of ammonia.
* The gelatin from bone is called ossein.
# Leather consists of a combination of a gelatinous tissue (as skin) with tannin
(see page 637).
NUTRIENT ANIMAL FLUIDS. 695
A one per cent. Solution sets on cooling. Repeated boiling destroys
this property of gelatin. -
Chondrin is the gelatin obtained by the action of boiling water on
the cartilages of the ribs and joints.
It is not so soluble as gelatin in boiling water. It is precipitated
by acids. In the case of acetic acid the precipitate is insoluble in
an excess of acid, but in the case of the other acids the least excess of
acid effects the solution of the precipitate. Its solution is precipitated
by alum and by lead acetate. It forms glucose when boiled with
hydrochloric acid.
Uses.—Size is the gelatinized solution produced by boiling clippings
of hides, parchment, etc., in water.
Glue is manufactured by boiling the parings of hides, etc., in water.
The hides are first carefully cleansed from hair and blood by lime.
This done, the lime is carbonated by free exposure, after which
the hides are boiled in water. The liquid is then kept warm
for a time so as to allow the impurities to subside. The Solution is then
cooled, the gelatinized mass being cut into slices and dried on nets in
the air. The temperature at which the drying process is effected is
important, for a summer heat would melt the glue, whilst a winter
cold would split it.
Hair contains 3 to 5 per cent. Of Sulphur.
Silk.--This is said to consist of three layers, the outer one being
gelatin, and soluble in water; the centre one albumen, and soluble in
boiling acetic acid; the winer one sericin, and insoluble either in water
or in acetic acid.
Brain and Nerve Tissue.—The watery extract (75 to 80 per cent.)
contains kreatin, uric acid, Xanthin, sarcine, inosite and lactic acid;
the solid undissolved matter consisting of protagen, cholesterin and
albumen. The ash (3 to 4 per cent.) consists mainly of salts (especi-
ally potassium salts) of sulphuric and phosphoric acids.
B.—NUTRIENT ANIMAL FLUIDS.
BLOOD, CHYLE, LYMPH, MILK.
Blood.
Composition.—This can be only stated very generally, although it
is to be remarked that the composition of blood is singularly uniform,
considering the work it has to perform in supplying the materials for
the replenishment of worn-out tissue, and the carrying away some of
the products arising from their destruction.
696
EIANDBOOK OF MODERN CHEMISTRY.
Average Composition per 1,000 parts of Human Blood (Becquerel and
Rodier).
The quantities are stated in parts per 1,000 Male. Female.
of blood.
Specific Gravity of defibrinated blood .. 1060-0 1057-5
Do. of serum tº º 1028.0 1027-4
Water 779-00 791-10
Fibrin tº º tº º is p 2-20 2-20
Saponified fat 1.00 1-04
Fatty Phosphorized fat 1.60 ) 9.4% 1.61 ) 0.4%
matters. Cholesterin . . 0-09 0.09
Serolin O-02 0.02
Albumen .. e e º, tº 69-40 70.50
Blood corpuscles . . e tº 141 - 10 127.20
Extractive matters and salts 6-80 7'40
1,000:10 1,000-01
Sodic chloride . . º g e 3- 10 3.90
Salts Earthy phosphates .. * * 5.93 | 0.33 7:15 ( 0-35
Soluble salts other than NaC 2:50 2.90
Iron tº a tº e - - e tº 0.57 6'54
It may be noted that arterial blood contains more fibrin and less
fat and albumen than venous blood.
The gases present in blood have been estimated by Magnus and
Meyer.
Free gases present in 100 vols. of blood taken from the carotid of a dog.
(Corrected to 0°C. and 760 mm.)
Oxygen (free or combined with haemoglobin)
Nitrogen is tº • *
Free carbonic anhydride
Exp. 1.
12:43
2-83
6-62
20-88
Exp. 2.
14:29
5-04
6-17
25-50
The combined carbonic acid was found to be, in the first experiment,
28-61 volumes in 100 volumes of blood, and in the second experi-
ment, 28:58 volumes.
This would give a total of 49-49 and 54-08
volumes of gas, free and combined, in 100 volumes of blood. Relatively,
venous blood contains more carbonic acid and less oxygen than ar-
terial; but absolutely, the carbonic acid, in both arterial and venous
blood, is always in excess of the oxygen.
Constitution.—Fresh blood, as revealed by the microscope, consists
of numerous red globules (blood corpuscles) and a few colorless cor-
puscles, floating in a colorless liquid. This colorless liquid, termed
THE BLOOD. 697
the liquor sanguinis, consists of what is called the serum of blood,
holding the fibrin in solution. The composition of the blood cor-
puscles and of the liquor sanguinis respectively, are stated in the fol-
lowing table :-
Average Composition per 1000 parts of Blood Corpuscles and of Liquor
Sanguinis (Serum and Fibrin).
Blood Corpuscles [Sp. Gr. 1088:5]. Liquor Sanguinis [Sp. Gr. 1028].
Water . . . . . . . . . . 688:00 Water . . . . . . . . . . 902-90
Solid constituents . . . . . 312:00 Solid constituents . . . . 97-10
Consisting of-
Globulin and cell mem- sº a #3 a.
brane, or stroma. . . . 282-22 Consisting of-
Haematin (with iron). Albumen . . . . . . . . 78-84
[This body is a deriva- Fibrin 4-05
tive of haemoglobin.] 16.75 F tº it iſ tº J
Fat . . . . . . . . . . 2-31 at . . . . . . . . . . . . 1-72
Extractive matters. . . . 2' 60 Extractive matters. . . . 3-94
Mineral matter (without Mineral matter . . . . 8-55
iron) . . . . . . . . 8-12
Consisting of- Consisting of-
Chlorine . . . . . . 1-686 Chlorine . . . . . . 3-644
Sulphuric acid . . . . () - 066 Sulphuric acid . . . . 0-1 l 5
Phosphoric acid . . . . 1 : 134 Phosphoric acid . . . . 0 - 191
Phosphate of line .. 0 - 114 Phosphate of lime . . 0-3] I
3 y magnesia 0-073 y 5 magnesia 0.222
Potassium . . . . . . 3° 328 Potassium . . . . . . 0-323
Sodium . . . . . . 1'052 Sodium . . . . . . 3-341
Oxygen . . . . . . O'667 Oxygen . . . . . . 0-403
I.—The Blood considered generally.
Properties.—(a.) Sensible and Physical. The blood is a viscid red
fluid. As regards its color, we have already noted that this is de-
pendent on the presence of red corpuscles, and not upon any coloring
Imatter actually existing in a state of solution in the liquid portion or
liquor sanguinis. The exact color of the blood varies:—
(1.) It differs according to its source. Thus: the blood in the arteries
is florid red, that in the veins being dull purple. This difference of
color was at one time supposed to be physical, and due to alterations
in the capacity (dependent on change of shape) of the red corpuscles
for reflecting and transmitting light. It is, no doubt, true that
the more spherical the globules, or, in other words, the more swollen
the corpuscles are with water, the darker colored is the blood.
Hence it was taught that carbonic acid effected the expansion of the
cells, thereby rendering them bi-convex, and the blood dark colored;
whilst oxygen effected the contraction of the cells, thereby rendering
them bi-concave, and the blood bright red. It is, however, tolerably
evident that the color change is not simply physical but chemical,
698 HANDBOOK OF MODERN CHEMISTRY.
and dependent on the state of oxidation of the haemoglobin, or blood-
coloring matter. Thus, in arterial blood the haemoglobin is oxidized,
and of a scarlet color; whilst in venous blood a part of the haemo-
globin is deoxidized, and of a purple color. Possibly, the physical
condition of the corpuscles, and also the presence of carbonic acid,
may be elements in the case; nevertheless, there can be but little
doubt that the change of color is primarily, if not entirely, due to
the oxidation and deoxidation of the haemoglobin.
(2.) The quantity of haemoglobin in the corpuscles, as well as the
proportion of corpuscles to serum, influences the color of the blood.
(3.) The form of the corpuscles (see above). Thus the more spherical
the corpuscles, the darker the blood appears.
(4.) The thickness of the cell-wall of the corpuscles. Mulder sup-
posed this to be the cause of the different colors of venous and
arterial blood. He pointed out that potassic nitrate and iodide, and
also sodic phosphate and carbonate, thicken the external membrane
of the corpuscles, and render the blood of a lighter color.
(5.) Any reagents, like the caustic alkalis and certain organic acids,
that burst the corpuscles, render the blood brownish-red.
The odor of blood is more marked when warm than when cold. By
treating the blood with sulphuric acid, the odor becomes so apparent
that it is often possible to say the animal from which the blood so
treated was derived. (Barruel.) The odor is more intense and well
marked in the blood of males than in that of females. It is supposed
that this odor is due to a volatile fatty acid.
Specific Gravity. Normal blood has a specific gravity varying
from 1052-0 to 1057-0. It is less in women, and especially in preg-
nant women, than in men, and least of all in children. The specific
gravity of venous blood is always somewhat higher than that of
arterial. The blood from various animals, so far as its specific gravity
is concerned varies very little. The blood of the bullock (four ex-
periments) was found to have a mean specific gravity of 1060-0, and
that of the sheep (seven experiments), 1053-0. [Tidy.]
The temperature of the blood is usually 100°F. (37.8°C.), but the
blood on the left side of the heart is said to be 1° to 2°F. (.55° to
1.1° C.) higher than the blood on the right side, whilst the blood is
warmed by passing through the liver, and cooled by passing through
the superficial capillaries.
(6.) Chemical. The blood has invariably a slightly alkaline reac-
tion when first drawn from the body, but it becomes acid after a
short time, owing, it is supposed, to the conversion of the sugar into
lactic acid. Menstrual blood is said to be acid, but this is probably
due to its intermixture with acid uterine or vaginal mucus.
Coagulation.—In from two to five minutes after the blood is drawn
from the body it coagulates, and in seven to fourteen minutes the whole
mass becomes gelatinous. This coagulation is due to the fibrin pre-
TEIE BLOOD. 699
sent in a soluble state in living blood, becoming insoluble in the dead
blood. The cause of this change is not understood. It has been
suggested that it is due to the contact of foreign matter with
the blood when drawn from the body. (Lister.) Others suppose
that the inherent tendency of the fibrin to coagulate, is prevented
during life by some inhibitory power resident in the walls of the
containing vessels. Others suppose that coagulation of the fibrin
does take place in the body, but that the tissue needing it absorbs
the coagulated mass as soon as formed. Others believe coagulation
to be due to the escape of ammonia and carbonic acid when the blood
is withdrawn from the body; whilst others hold (Schmidt and Bu-
chanan) that fibrin is not present at all in living blood, but that
coagulation results when the blood is drawn, from the actual forma-
tion of fibrin by the union of two substances existing separately in
the fluid and living blood. The solid mass now gradually contracts,
forcing out a watery fluid. This stage of contraction, [or the separa-
tion of the clot or crassamentum, which consists of fibrin with the blood
corpuscles entangled in its meshes (the blood corpuscles Inot having
had time to subside before coagulation) from the serum, which is the
liquor sanguinis minus the fibrin and in which the clot floats, is
usually complete in from twelve to forty hours.
If, from any cause the fibrin contracts less rapidly than usual (as
happens in inflammatory blood), or the red corpuscles sink more
rapidly than usual, owing either to a greater tendency of the blood
corpuscles to form rouleaux as in inflammation, Ör to a great relative
deficiency of red corpuscles, as in chlorosis, a white layer collects
on the surface of the clot, consisting either of fibrin only, or of a
mixture of fibrin and white corpuscles. This constitutes what is
called the “buffy coat,” or the “inflammatory crust” of blood. This
buffy coat contracts more rapidly than the rest of the clot. Hence a
cupped depression on the surface of the clot becomes apparent after
a short time.
Coagulation is influenced by a variety of circumstances : —
(1.) The Origin of the Blood.—Women's blood coagulates more
rapidly than the blood of men, but the clot is less firm. Embryonic
blood coagulates imperfectly. Arterial blood coagulates more rapidly
than venous.
(2.) A warmth of 100° to 120° F (37.8 ° to 48.9° C.) promotes
coagulation. A higher temperature than this retards it, whilst a
temperature of 200°F. (93.3°C.) stops coagulation altogether, even
after the blood has been cooled. Conversely, a cold of 40° F.
(4°5° C.) entirely stops coagulation; but coagulation will, under
these circumstances, take place as well as ever after the normal
temperature of the blood has been restored.
(3.) Motion retards coagulation, but rest promotes it.
(4.) The multiplication of points of contact promotes coagulation.
700 HANDBOOK OF MODERN CHEMISTRY.
Thus we whip blood with a bundle of twigs to coagulate the fibrin.
Or, again, the blood coagulates more rapidly in the rough cavities of
the heart than in the smooth veins and arteries.
(5.) Contact with living tissue retards coagulation, whilst contact
with foreign or dead tissue favours it. Thus we pass a thread
through an aneurism to form a nucleus for coagulation, and to assist
the cure.
(6.) The addition of two parts of water to one of blood promotes
coagulation, but the admixture of a greater quantity of water retards it.
(7.) Free access of air promotes, whilst exclusion of air retards
coagulation.
(8.) Coagulation is either retarded, or entirely prevented, by the
alkaline hydrates, carbonates, and acetates; also by dilute acids;
also by potassic or calcic nitrates, by ammonic chloride, etc.
(9.) Coagulation is influenced by the mode of death. Thus in
death by asphyxia, where the blood is imperfectly aerated, coagula-
tion is retarded. According to Hunter, the same result occurs in
death from lightning, blows on the stomach, over-exertion, fits of
anger, etc.
(10.) The consistency of the clot depends chiefly on the quantity of
fibrin present in the blood. -
The blood consists, as we have said, of corpuscles and serum,
in the following proportion, according to Schmidt, per 1,000 parts:—
Man. Woman. Dog.
Moist corpuscles .. * & 513:02 396-24 543-56
Serum • * e - tº º 486-98 * 603-76 456'44
II.-The Blood Corpuscles.
The composition of the blood corpuscles has been already stated
(page 967). These corpuscles are of two kinds, red and white.
1. The White Corpuscles.—These are present in blood in the pro-
portion, in health, of 1 white to 400 or 500 red. This proportion,
however, is greatly influenced, (a.) by food, the quantity of white cor-
puscles being decreased by fasting, increasing in number half an hour
after food has been taken, the increase continuing, on an average, for
two hours. (6.) Their proportion again is influenced by disease, the
quantity being increased in pneumonia, tuberculosis, and more espe-
cially in leucocythemia. (y.) Moreover, in the blood of certain
portions of the body, as in splenic blood, their relative proportion is
greater.
The white corpuscles are circular and nearly spherical. They have
the power of assuming various irregular forms, known as their
THE BLOOD. 701
“amaeboid movements.” They are about gºrm of an inch in diameter.
They are specifically lighter than the red corpuscles. They contain
neither fat nor haemoglobin.
2. The Red Corpuscles.—These are red, circular, flattened discs,
having an average diameter of roºm of an inch, and an average
thickness of Tºrº of an inch. To these corpuscles the red color
of the blood is due, their relative proportion to the liquor sanguinis
varying greatly under different circumstances. They are relatively
fewer in women's blood than in men's, and fewer in the blood of the
old and young of all animals than in that of the middle-aged. More-
over, their proportions vary in the blood of different animals; e.g.,
there are relatively a greater number in the blood of birds than in the
blood of carnivorous and herbivorous mammalia, whilst the pro-
portion is smallest in the blood of cold-blooded animals. Lastly,
the proportions vary in the blood of different vessels. Thus there
are fewer in arterial than in venous blood, fewer in the portal vein
than in the jugular, whilst they are most abundant of all in the
hepatic. The quantity, moreover, in the blood is diminished by want
of food, by repeated bleedings, and in certain diseases, such as
diarrhoea, intermittent fever, chlorosis, affections of the brain, etc.
The quantity is increased by a fat diet, and in such diseases as cholera,
spinal irritation, the early stages of heart-disease, general plethora,
etc.
Constitution and Properties of the Red Corpuscles.—The corpuscle is
a non-nucleated body. It is not a cell, in the sense of a sac. It con-
sists of a tough, elastic, transparent framework, or stroma (that is,
not merely a cell-wall), infiltrated with a fluid containing globulin
(an albuminous body), and a red coloring matter, called haemoglobin.
A little fatty matter, iron, and other mineral constituents are also
present. The central light or dark spot seen with the microscope
depends on the unequal refraction of the transmitted light.
The red corpuscles have an average specific gravity of 1:088, but
this is influenced materially by disease. In a case of cholera, the
corpuscles were found to have a specific gravity of 1:102. Inasmuch
as the specific gravity of water is less than that of the fluid contents
of the corpuscle, it follows that it will, when mixed with the corpuscles,
pass by osmosis into the cell, thereby swelling, and finally, if the
action be allowed to continue long enough, bursting it.
We now consider the chemistry of some of the constituents of the
corpuscle.
1. Globulin is a substance similar in composition to, and in its
properties closely resembling, albumen. It is found in large quantity
(10 to 14 per cent.) in the crystalline lens, and for this reason is
sometimes called crystallin.
702 HANDBOOK OF MODERN CHEMISTRY.
2. Haemoglobin (hamato-globulin ; haemato-crystallin).-This is the
true, and the only coloring matter of the blood of vertebrate animals.
Its percentage composition is stated as–
Carbon .. & © © tº º e tº º 54 - 2
Hydrogen. . tº º ë e • * tº º 7.2
Nitrogen . . tº º tº ºn • * ' ' s 16:0
Oxygen . . tº º e is © tº * - 21 - 5
Sulphur . . tº tº tº e e - - * 0-7
Iron * - - - tº 9 • & - tº 0-4 = 100-00
Preparation.—(1.) By the action of cold water, in which the haemo-
globin is soluble, on the corpuscles.
(2.) If a drop of blood, placed on a glass slide, be diluted with
water, alcohol, or ether, and after a short exposure to air covered
over with a thin glass slip, crystals of haemoglobin will be apparent
under the microscope. (Funke.)
Properties.—Haemoglobin may be obtained from blood, with more
or less ease, in a crystalline form (Haemato-crystallin of Funke).
The forms of the crystals vary in different animals. Thus they
8. I’6– -
(a.) Prismatic in the blood of fish, in human blood, and in the
blood of most mammals.
(3.) Tetrahedral in the blood of the rat, mouse, and guinea-pig.
(y.) Hexagonal in the blood of the squirrel.
The formation of haemoglobin crystals is promoted by light, and by
the chemical action of oxygen and carbonic acid on the corpuscles. It is
specially to be noted that the crystals are not the result of the evapo-
ration of the water of the blood, inasmuch as they are formed more
readily when the blood is diluted with twice its volume of water than
when only mixed with one-half its volume.
Haemoglobin is soluble in cold water, but not in hot. The pris-
matic 'crystals are soluble in 94 parts of cold water, the solution
coagulating at 147.2° F (64°C.), while the tetrahedral crystals are
soluble in 600 parts of cold water, the solution coagulating at
145.4°F. (63°C.) This coagulation consists not only in the coagu-
lation of the albumen, but in the formation of haematin. The red solu-
tion is decolorized by chlorine, with the precipitation of white flakes
(the chlorhamatin of Mulder), and is changed to a brownish-red color
by carbonic oxide, and to a brown color by nitrogen. It may be
said generally, that whatever precipitates haemoglobin, destroys it.
The feeblest acids (even CO.) decompose it.
The remarkable property possessed by hamoglobin of combining
with and delivering up oxygen has been already referred to (see
page 65).
Carbonic oxide displaces the oxygen of oxy-haemoglobin to form a
more stable compound with the haemoglobin.
A body called hamatoidin (methomoglobin or methamatin) (C4H16N2O3,
TELE BLOOD. 703
Robin), is said to occur in blood after extravasation in the tissues of
living animals, in the brown fluids of hydrocele, ovarian cysts,
etc. It seems to be a body intermediate between haemoglobin and
haematin.
Haºmatin.-By the action of heat, or of mineral and other acids,
and also of alkalies, etc., haemoglobin is converted into homatin
(hamatosin) [Cºe Hyone Fe2Ou, Hoppe]. This body, which contains 12-8
per cent. of iron oxide, and was once supposed to be a constituent,
and the true coloring matter of the red corpuscles, is now proved to
be merely a product of the decomposition of the haemoglobin.
Haematin is an amorphous, blackish-brown substance, without
taste or odor. It is insoluble in water, alcohol, ether, acetic ether, in all
oils, or even in the concentrated mineral acids; whilst it is soluble in
alcohol acidulated with either sulphuric or hydrochloric acid, and in
aqueous or alcoholic solutions of the alkalies or of their carbonates.
The brown acid alcoholic solution, when treated with an alkali,
appears red by reflected, and green by transmitted light. It is a
body easy of reduction, but very difficult of oxidation. It is decom-
posed by chlorine, and by boiling with nitric acid.
Haematin Hydrochloride; Teichmann's Haemin Crystals; Blood
Crystals.
Preparation.—By acting on haemoglobin with common salt and
glacial acetic acid.
Properties.—Rhombic dichroic crystals, insoluble in water, alcohol,
and ether, and soluble in acids and alkalies, but in acetic and hydro-
chloric acids only without decomposition.
III.-The Liquor Sanguinis.
The composition of the liquor sanguinis has been already stated
(page 967). By the term “serum ” is meant the liquor sanguinis,
minus the fibrin. -
Properties.—A straw-colored fluid in health, becoming, in certain
diseases, such as icterus and pneumonia, of an intensely yellow color.
Its average specific gravity is 1:028, and, in this respect, is singularly
uniform. Its reaction is alkaline, the alkalinity being due to the
presence of carbonate and phosphate of soda.
[NotE.—Serum is also straw-colored and alkaline. It coagulates at
170° F (76.1° C).]
1. Water.—The quantity of water in blood varies. Thus there is
more in the blood of women (especially during pregnancy) than in
that of men, and more in those of advanced age than in the young.
The proportion present is influenced by disease. Thus there is a
great diminution in the quantity of water in the blood in cholera.
And further, arterial blood contains more water than venous blood,
whilst in both venous and arterial blood the actual proportion of
704 HANDBOOK OF MODERN CEIEMISTRY.
water varies hourly with the food, exercise, and atmospheric
changes. Nevertheless, a remarkable uniformity is noticeable, for
that which lessens the water excites thirst; whilst, if an excess of
water be added to the blood, the urine and sweat get rid of it.
2, Albumen (C12HugNiaSOzo). This varies from 60 to 70 parts
per 1,000 of blood. It is the cause of the coagulation of the serum
by heat. It may be obtained in a soluble state by evaporating the
serum below 120° F. (48.9°C.), whilst, if the serum be evaporated at
a higher temperature, the albumen becomes insoluble in water at
ordinary pressures. -
Hoppe considers that the albumen is not present in blood in a state
of solution, but merely in a state of fine subdivision. Others believe
it to be present as an albuminate of soda, whilst Enderlin believes it
to be held in solution by the sodic phosphate. The blood of women
contains more albumen than the blood of men, whilst arterial blood
contains less albumen than venous. The quantity of albumen in the
blood is decreased in such diseases as Bright’s disease, scurvy, puer-
peral fever, etc., whilst it is increased in cholera, intermittent fever, etc.
A body called vegetable albumen is found in vegetable juices.
3. Fibrin, The proportion of fibrin in blood varies between 2
and 3 parts in 1000. It is usually increased in inflammatory
affections, as rheumatism, pneumonia, etc., and decreased in anaemic
diseases, as typhus, chlorosis, etc. Its spontaneous and speedy coagu-
lation distinguishes it from all analogous substances.
All muscular tissue consists of fibrin. The gluten of flour is often
called vegetable fibrin, and bears a close resemblance to animal
fibrin.
[For remarks on coagulation, see page 698.]
4. Fatty Matters.-The proportion of fat in blood is about 1.6
parts in 1000. The quantity is not increased beyond this amount by
a fat diet, but is decreased by a want of fat food. Arterial blood
contains less fat than venous, and the portal vein more fat than the
jugular. The quantity of fat (and especially of cholesterin) is in-
creased at the commencement of every acute disease, and also in some
chronic diseases.
Most of the fatty matter present in the blood is in a saponified
form. It would appear that the fats peculiar to various organs exist
ready formed in the blood, as e.g. cholesterin (the fat of bile), cerebrin
and the phosphorized fat of the brain, together with oleic, margaric
and stearic acids, chiefly saponified, but also in a free state.
These fatty matters of the blood not only supply fat where it is
needed, but serve by their oxidation to maintain the temperature of
the body.
5. Extractive Matter.—This term includes Kreatin and Kreatinine,
glucose, urea, uric acid, hippuric and lactic acids, and certain other
bodies.
CHYLE AND LYMPEI. 705
Alcohol is said to be always present in blood in minute quantity,
and is supposed to be formed by the fermentation of the sugar. (Ford.
Jahresb., 1861, page 792.) -
6. Mineral Matters.--The percentage composition of the ash of
the serum may be thus stated —
Sodic chloride -.. tº dº ſº * * * tº º tº 61:08
IPotassic chloride ... tº º is tº º is tº gº & 4:08
Sodic carbonate (Na2CO3) § & © tº º 28-87
EIydric sodic phosphate (Na2HPO,) ... 3-19
Potassic sulphate... tº tº º © tº is 2.78 = 100'00
The proportion of mineral ingredients is greater in the blood of
adults than in that of the young, greater in arterial than in venous
blood, and greater in the serum of the portal vein than in that of the
jugular. The quantity is influenced by diet and by disease. There
is a larger quantity present in the blood of the cat, goat, and sheep
than in the blood of men, birds, and pigs, whilst a smaller quantity is
found in the blood of dogs and rabbits than in other animals.
The iron (a never failing constituent of blood) belongs exclusively
to the red corpuscles,
[For many details connected with blood, such as the measurements
of the corpuscles, tests, etc., see the Author’s and Dr. Woodman's
“Handybook of Forensic Medicine.”]
Chyle and Lymph.
Chyle is the fluid of the lacteals, the lymphatics of the intestines.
It is transparent during fasting, but milk-like during digestion. This
milkiness is due to the presence of minute fatty particles termed the
molecular base of the chyle.
Lymph is the fluid of the lymphatics. It is a clear, colorless,
faintly alkaline, albuminous liquid, having no fatty particles such as
occur in chyle in suspension.
In both lymph and chyle the presence of certain corpuscles may be
perceived under the microscope.
Percentage Composition of Lymph and Chyle (Owen Rees).
- Lymph. Chyle.
Water tº dº & tº e ºs 90. 237 & 4 tº 96.536
Albumen ... a & © 3 516 * - “ 1:200
Fibrin tº ºn tº & ſº º 0.370 tº º º 0-120
Animal extractive ... 1 : 565 * * * 1'559
Fatty matter tº ſº º 3. 601 * * * A trace
Salts ... z dº ſº * * * 0.7.11 tº º e 0-585
100'000 100'000
We remark — (1.) That lymph and chyle are substantially
alike, except that chyle contains fat, and lymph none or nearly none.
Z Z
706 HANDBOOK OF MODERN CHEMISTRY.
(2) Lymph and chyle are substantially like blood, the difference
being only one of degree. In fact these liquids probably are rudi-
mental blood, containing corpuscles in process of development into red
corpuscles. The difference between the lymph and chyle and the blood
becomes less and less as the two former pass through the thoracic .
duct, or in other words as they approach the place where they are to be
mingled with the blood.
(3.) Blood, lymph and chyle agree, in that they contain fibrin, and
coagulate spontaneously, although the clot of lymph and chyle is
softer than that of blood. Moreover in this property of spontaneous
coagulation they differ from all other animal fluids.
Milk.
Milk is a liquid secreted by the female mammary gland after par-
turition. Microscopically it consists of fat globules, surrounded by an
albuminous envelope, having a diameter of 0-0014 in., floating in
a perfectly transparent liquid.
Composition per 100 parts of human milk compared with that of the cow.
(Tidy).
Woman’s Milk. Cow’s Milk,
Max. Min. Average. Average.
Casein 4 - 36 2.97 3-52 3:64
Butter * 5- 18 4:45 4' 02 3'55
Sugar of milk 4'43 3.29 4-27 4. 70
Warious salts 0-23 0° 38 0-28 0 - S1
Total solids .. - - 14:20 11:09 12:09 12.70
Water . . 4 tº tº e 85-80 88-91 87.91 87:30
Total tº º * * 100.00 100' 00 100.00 100'00

Milk is a model diet. The casein is its azotized portion, whilst fat,
sugar, and the mineral ingredients of food (of which the chief is
phosphate of lime) are duly represented.
An increased yield of milk is promoted up to a point by an increase
in the quantity of albuminous and fatty elements taken as food, and
vice versa. A very fat diet increases the proportion of all the ingre-
dients and not of the fat only.
Milk is a yellowish, sweet liquid. The cream after a short time
collects on the surface, the lower part or the skimmed milk increasing
at the same time in specific gravity. If the cream be well agitated
the albuminous envelopes burst, and the fat globules coalesce to form
butter.
The reaction of fresh milk is variously stated. It is probably nearly
neutral or very slightly alkaline, owing to the soda holding the casein
DIGESTIVE FLUIDS. 707
in solution (albuminate). After a time the milk becomes acid and
then coagulates. This action is rapid if the weather be warm and
the air electrical. It is occasioned by the conversion of the milk-sugar
into lactic acid, under the influence of the nitrogenized body casein,
which acid effects the precipitation of the casein (lactic fermentation).
This latter, containing the milk globules in mechanical admixture,
constitutes “curds,” and the clear liquid “whey.”
Normal milk contains no albumen, but colostrum (that is, the first
milk secreted after pregnancy) usually abounds in it.
Human milk has an average specific gravity of 1030.
C.—DIGESTION AND TELE FLUIDS CONCERNED IN IT.
Saliva, Gastric Juice; Pancreatic Fluid, Bâle, Intestinal Juice.
Digestion is a process of Solution, i.e., of rinsing or drenching the
food with various secretions so as to extract from it the nutritious
portions, and convey them into the circulation.
To carry out this rinsing process perfectly, the food is first, in most
cases, cooked, and then chewed. In this way a perfect admixture of
the materials with the various solutive agents is effected.
The following diagram represents the amount of the digestive fluids
secreted daily, and the proportions of their chief constituents.

Quantity Solid e * tº
Secreted. Matters. Active Principles.
Saliva . . . . . tº wº 3:53 lbs. 231 grs. 116 grs. of ptyalin.
Gastric juice . . . . . 14'1 1 , , 2,963 , 1,482 , , of pepsin.
Pancreatic fluid tº sº 0.44 , , 309 , 39 , of pancreatin.
Bile . . ; tº is * * 3’53 , , 1,234 , , 1,058 , , of organic ferment.
Intestinal mucus * g. 0.44 ,, 46 , , 28 ,, }} 5 y
Total tº º ... 22:05 lbs. 4,783 grs. 2,723 grs. of special solvents.
Saliva.
Saliva is a fluid secreted by various glands, such as the parotid, the
submaxillary, the sublingual, etc. Two to three pints in the 24 hours
may be taken as the average quantity secreted. The exact amount,
however, varies considerably. The quantity is decreased by fasting,
and increased by the stimulus of food in the mouth, or by the mere
mental impression connected with the sight or even the thought of
food.
Composition per 1000 parts of Saliva (Frerichs).
Water ... ... 994 - 1
| * * tº s | Organic ... ... 3-61
Solids ... & ſº 5'9 U Inorganic ... ... 2:29
708 BIANDBOOK OF MODERN CHEMISTRY.
The Organic constituents of saliva consist of an albuminoid substance
called ptyalin (Tràu, to spit) (which constitutes about one-fourth of the
total Solid matter of the saliva), together with fat, epithelium, etc.
The ptyalin is said to be contained more largely in the saliva secreted
by the submaxillary than by the other salivary glands. The inorganic
constituents consist of the phosphates of lime, magnesia, and soda (the
deposition of the earthy phosphates on the teeth by the action of the
ammonia of the breath constituting what is called “tartar,”) of alkaline
chlorides and a small but an ever present quantity of potassic sulpho-
cyanide, said to be increased when sulphur is taken internally.
Properties, &c.—Saliva is a clear, feebly alkaline fluid. Its specific
gravity varies from 1002 to 1009. The alkalinity of the secretion
from the parotid is said to be more marked than that from the other
salivary glands. During digestion, moreover, its alkalinity is in-
creased. In certain diseased conditions the saliva becomes distinctly
acid.
The action of the saliva is twofold—
(a.) As a mechanical agent it acts as a lubricator, assisting mastication
and deglutition.
(3.) As a chemical agent its action depends on the presence of the
ferment body ‘ptyalin,’ by which the insoluble starch is transformed
into soluble dextrin and glucose. This conversion of the starch is
retarded rather than promoted by the gastric juice. The saliva may
also, being an alkaline fluid, assist in emulsifying the fat.
Gastric Juice.
The gastric juice is a fluid secreted from the glands of the stomach,
under the influence of disturbing causes, such as the introduction of
food and other mechanical irritants, and more especially by soluble
irritants, such as salt, etc. The quantity secreted in the twenty-four
hours is variously stated at from 10 to 20 pints.
Composition of Iſuman Gastric Juice per 1,000 parts.
Water ... ... 994 '4
Solid constituents ... 5-6 | Organic (pepsin) ... 33
Inorganic 2-4
The salts present in the gastric fluid consist of calcic, sodic, and
potassic chlorides, and earthy phosphates.
The two important constituents of the gastric fluid are the free acid
and the pepsin.
(a.) As regards the free acid, some investigators maintain it to be
lactic acid, and others hydrochloric acid. M. Werneuil states that he
has found both acids present in a free state, the hydrochloric acid
being 1:7 parts in 1,000, and the lactic acid in the proportion of 1 part
of lactic to 9 parts of hydrochloric acid. The quantity of acid is
DIGESTIVE FLUIDS. 709
increased by taking alcohol, and decreased by taking Sugar. (See
“Med. Examiner,” Vol. i., p. 783, and Vol. ii., p. 254.)
The fact probably is, that both acids are usually present, the
hydrochloric, as a rule, largely predominating. In some cases, more-
over, the presence of acetic, phosphoric, and butyric acids has been
clearly demonstrated.
(3.) Pepsin is an albuminoid body, soluble in water, and insoluble
in alcohol. Its solution is precipitated by corrosive sublimate, by solu-
tions of tannic acid and of lead salts, and by alcohol. When a solution
of pepsin is boiled, its action as a solvent of albuminoid matter is
destroyed.
Properties, etc.—The gastric juice is a clear, acid, odorless fluid. It
has a specific gravity varying from 1002-2 to 1002-4. It is miscible
with water. It coagulates albumen. Its action is powerfully anti-
septic. Its solution does not become turbid on boiling.
The action of the gastric juice as a solvent of albuminoid matters,
such as fibrin, coagulated albumen, etc., depends on the joint pre-
sence of the acid and of the albuminoid ferment-body pepsin. A
certain temperature (100°F.), and a perfect admixture of the fluid
and food, as, e.g., by mastication of the food, by the muscular action of
the stomach, etc., are also necessary conditions. Thus, after a time
varying from two to six hours, complete chymification of the food is
effected, the fibrinous and albuminous constituents being converted
into different peptones or soluble forms of albumen, such as albumino-
peptones, fibrino-peptones, gelatino-peptones, etc., all of which differ
from common albumen, besides their solubility, in being neither
coagulated by heat, acid, nor spirit, and in their capability of being
dialysed (albuminose of Mialhe). The composition of the chyme de-
pends, of course, largely on the food, but it has the general appearance
of a thick fluid, consisting of a solid, undigested portion, suspended
in a liquid of a more or less yellow color, and of a more or less
disagreeable odor.
The gastric juice has no action on starch or fat.
The Pancreatic Fluid.
This fluid, which in many respects is like the saliva (but unlike it
in containing no sulphocyanides), is the secretion of the pancreas, a
gland closely resembling the salivary glands.
Composition of Pancreatic Fluid per 1,000 parts (Schmidt).
Water ... ... 980:45
rami i 2.7
Solids ... ... 19' 55 | Organic (pancreatin)... 12-71
Inorganic ... ... 6'84
Properties.—A colorless fluid; specific gravity, 1008 to 1009. Its
reaction is usually stated as alkaline, but this, so far as the fresh
710 HANDBOOK OF MODERN OBIEMISTRY.
fluid is concerned, is doubtful. Its action depends on the presence
of an organic principle, called pancreatin, an albuminoid ferment-
body, constituting two-thirds of its total solids. Its action is
two-fold: (1) it emulsifies fat, converting it into a milky liquid,
thereby rendering it capable of absorption by the lacteals; and
(2.) it converts starch into glucose, and so effects its solution.
(Dobell.)
The Bile.
The bile is the fluid secreted from yenous blood by the cells of the
liver.
Average Composition per 1,000 parts (Frerichs).
Water ... 859.2
Biliary acids combined with alkalies
(Bilin) tº tº e • * º ... 91-5
e Fat ... tº e º tº e 9-2
Solids ..., 140-8 º * - e. º
Cholesterin ... * * * º º º 2.6
Mucus and coloring matters ... 29.8
Salts ... 9 * * tº º o & © tº 7.7
The quantity of solid matter is greater in the bile of the young
than in that of the old, and is in excess in such diseases as cholera,
heart-disease impeding the circulation, etc., whilst it is less than
normal in severe inflammations, diabetes, etc.
Bile consists essentially of (1) a resinoid matter, and (2) a coloring
matter.
(1.) Resinoid matter (bilin). This consists of the soda or potash
salts of two, or of one of two, acids, one of which contains sulphur
and the other none—
(a.) Salts of taurocholic acid (C26H5NSO.), which, by the action of
alkalies, forms taurine (C.H.NSOs) and a non-nitrogenous acid, called
cholic acid (C23H40O3). Thus:–
C26H4...NSO, + H2O = C.H.NSO3 + Co., H.100.
Taurocholic acid + Water = Taurine + Cholic acid.
Taurine may be prepared artificially by passing olefiant gas over
sulphuric anhydride, neutralising the product dissolved in water with
ammonia, evaporating to dryness, and heating the residue (isethionate
of ammonia, NH3.H2O.C.H.SOs), so as to expel a molecule of water.
(3.) Salts of glycocholic acid (C26H13NO6), which, by the action of
alkalies, forms glycocine (C2H5NO2) and cholic acid (C-4Eſto05).
Thus:–
C26H43NO6 + H.O C.H.N.O. + CelTao Os.
Glycocholic acid + Water = Glycocine + Cholic acid.
[Glycocholic acid gives, on adding sugar and H2SO4, a purple red
(Pettenkofer's test).]
=
DIGESTIVE FLUIDS. 711
In the dog, sodic taurocholate only is present; in the pig, sodic
glycocholate only is present; in man, sheep, etc., the taurocholates
are in excess over the glycocholates; whilst in the ox and in most
fish, the glycocholates are in excess over the taurocholates.
Pig's bile also contains hyocholic acid (C23H40O2), and goose bile
chenotaurocholic acid (C26H19NSO6).
(2.) The coloring matter of the bile is termed cholochrome. This is
a mixture of a green pigment, insoluble in chloroform, called biliverdin
(C16HzoN2O5), and a brown pigment, soluble in chloroform, called
cholophaein. Of this latter there are two modifications; viz., the red
bilirubin (CeBIGNO2), and the brown biliphaein.
A blue coloring matter has also been described.
Properties.—Bile is a viscid, greenish-yellow, bitter fluid, without
odor when fresh, but very offensive after it has become putrid. It
has a specific gravity of 1020. It does not readily mix with
Water.
Its reaction is slightly alkaline. It putrefies rapidly, becoming acid,
owing to the presence of mucus derived from the gall-bladder, the
hepatic ducts, etc.
The action of the bile is involved in much obscurity: it does not
convert starch into sugar like the saliva and pancreatic fluid (doubted
by Wittich); it does not dissolve fibrin like the gastric juice; it
does not emulsify fat, or at any rate to the same extent, as the secre-
tion from the pancreas. Some regard the function of the bile as the
medium, by direct excretion, for the separation of an excess of carbon
and hydrogen from the blood, thereby effecting its purification. This
is manifestly its purpose in intra-uterine life. Nevertheless, that it
is more than a mere excrementitious fluid, and plays an actual part
in digestion, there can be but little doubt. Some have suggested
that its function is to emulsify fat; others, that it assists the absorp-
tion of fat by moistening the intestinal mucous membrane; others,
that it neutralises the acid peptones from the stomach; others, that
its antiseptic power prevents the decomposition of the food as it
passes through the bowels; others, that it acts as a natural purgative
by its stimulating effect on the intestines. As yet, however, our
knowledge on these points is very imperfect.
Gall-stones consist sometimes of cholochrome, held together by
mucus (oriental bezoar stones), but most often of cholesterin around a
nucleus of cholochrome. Moreover, earthy carbonates and phos-
phates are generally present.
The Intestinal Juice.
The fluid secreted along the whole course of the small intestines
has an alkaline reaction, and contains 3 to 4 per cent. of solid
matter. It has a powerful action in assisting digestion, combining
712 HANDBOOK OF MODERN CHEMISTRY.
the activity and digestive power of all the other secretions. Starch,
fat, and albuminous substances are thus equally affected by it.
D.—EXCREMENTITIOUS PRODUCTS.
Urine; Urinary Calculi ; Faces; Sweat; Mucus; Pus.
Urine.
The urine in all animals is the vehicle through and by which the
body rids itself of used-up solid matter, and of the excess of water
present in the blood. It is in short the great outlet for the nitrogen
of effete azotized tissue.
About 60 ozs. may be taken as the average quantity of urine
secreted by an adult male in 24 hours, but this is subject to great
variation, depending on such causes as the quantity of fluid taken,
the season of the year, and the relative activity of the skin, lungs,
and alimentary canal.
Average Composition of Normal Urine, and average quantity of the various
Constituents eaccreted in 24 hours (Kirkes).
Constituents per Average quantity excreted
1,000 parts. in 24 hours (adult male).
Water to º tº p tº e 967'000 * * 52-0 ozs.
Urea. . e tº * - * g. 14:230 * * 512-4 grains
Uric acid .. * * & º 0.468 tº 4 8'5 ,,
Extractives, Pigment, Mucus 10-167 e e 1610 , ,
Salts . . s tº & 9 & Cº 8- 135 is tº y 423° 0 ,,
Silica. , p º * 9 º º traces & 4 traces.
100'000
*-------
(1.) The composition and character of the urine of different animals
varies. Thus, in the carnivora, the urine is usually clear and acid,
containing much urea, and but little uric acid. In the herbivora, it
is usually turbid and alkaline, containing urea like the carnivora,
together with a great excess of hippuric acid, but no uric acid; it
also contains an abundance of the earthy carbonates (hence its tur-
bidity), and but very little of the earthy phosphates, these latter
being proportionately abundant in the faeces.
Carnivorous birds excrete urea in small quantities, but uric acid in
abundance, whilst granivorous birds excrete uric acid in abundance,
but no urea. Serpents and other land carnivorous reptiles secrete uric
acid almost entirely, whilst frogs and other amphibious reptiles secrete
urea, and mere traces only of uric acid. Even the insecta excrete
uric acid.
Thus it would seem that in the animals that drink freely, the
nitrogen is excreted as urea, whilst in those that drink but little, it
is excreted as uric acid. It must be noted, however, that these differ-
- URINE. 713
ences are differences for the most part of diet simply. For if a car-
nivorous animal (as a dog) be fed on a purely vegetable diet, or a
herbivorous animal (as a rabbit) on a purely animal diet, a corre-
sponding change in the urine results.
(2.) The composition of the urine varies greatly in disease. Thus
the quantity of uric acid is increased in gout, etc.; albumen occurs in
Bright's disease, etc.; sugar in diabetes, etc.
(3.) The composition varies hour by hour. The morning urine
(urina sanguinis) consists chiefly of the products of tissue decomposi-
tion. Hence, our choice of this for analysis. The day and the evening
urine is greatly influenced by the quantity and the character of the
food ingested (urina cibi and urina pottis).
And here may be noted the changes that bodies undergo from the
period of ingestion to that of urinary excretion—
(a.) The kidneys secrete certain bodies from the blood in an
unaltered state, e.g., many metals (such as As, Sb, Bi, Cu, Cr, Au,
Fe, Li, Pb, Hg, Ag, Sn, Zn), free organic acids, alcohol (?), numerous
salts, many of the alkaloids, such as morphia, Strychnia, atropine, etc.
(3.) In other cases, the products secreted are oxidized products, or
are otherwise changed. Thus, ammonia salts are converted into
nitrates; Sulphur, alkaline sulphides and sulphites, become sul-
phates; tannic becomes gallic acid. Or, again, the neutral salts of
Organic acids become carbonates; free iodine is excreted as an alka-
line iodide ; ferrocyanides become ferricyanides; indigo blue becomes
indigo white; benzoic, cinnamic, and other acids are found in the urine
as hippuric acid, etc.
Properties.—(a.) Physical. A clear yellow fluid, having a mean
specific gravity in health of 1020. Its color, however, may vary even
in health from a colorless liquid to a deep orange. In its specific
gravity, variations occur in health ranging from 1015 to 1025,
depending on the season of the year, diet, exercise, etc. In disease
the variation is much greater, being sometimes as low as 1004, as in
albuminuria, or as high as 1060, as in diabetes. Of its relative
clearness it is to be noted that in health it often becomes turbid on
cooling, due to the deposition of phosphates. The cause of its peculiar
odor has not been well made out. The odoriferous principle, what-
ever it may be, undergoes speedy change.
(3.) Chemical. Healthy urine is generally acid. The acidity of the
60 oz. voided in the 24 hours may be taken as equivalent to about
the acidity of 30 grains of Oxalic acid. This acidity, which is
less during digestion (and, indeed, after a meal the urine may even
be alkaline) and most marked during fasting, is due to the acid
phosphate of Sodium, and according to some observers, to certain
free acids, such as lactic acid (?).
After a certain time, varying from a few days to two weeks, the
71.4 IHANDBOOK OF MODERN CEIEMISTRY.
urine becomes alkaline. This alkalinity is due to the urea becoming
converted into carbonate of ammonia, crystals of triple phosphate,
confervoid growths and vibriones occurring simultaneously in the
urine. Indeed, this change may be so rapid that under certain
morbid conditions, as in cases of retention, it takes place in the
bladder itself, thus rendering the urine turbid and alkaline when
voided. The urine may, however, under certain other conditions,
be alkaline when secreted. This occurs when neutral alkaline salts
of the vegetable acids have been administered in excess, the acid
being destroyed in the process of respiration, whilst the alkali ap-
pears in the urine as a carbonate.
We now consider in detail the various constituents of the urine:—
1. Water.—This varies according to season, exercise, drink, con-
dition of nervous system, etc. Thus it is increased in diabetes
(especially in D. insipidus), and decreased in albuminuria, in febrile
affections, and, in short, in any disease increasing the secretion of
water by other channels.
2. Urea.—Carbamide [CHN2O, or CO(NH3)2], (see page 514).-
TJrea constitutes nearly one-half of the total solid matter of the urine.
It is the principal outlet for the effete or the excessive nitrogen from
the system. The quantity excreted is greatest with an animal diet,
and least with a vegetable, greater in males than in females, and
greater in middle age than in youth or old age.
Constitution.—The molecular formula for urea is CH4N2O. It is
commonly regarded as the amide of carbonic acid—that is, just as
oxamide (C2H4N2O.) is derived from ammonic oxalate [(NH4)2C2O4] by
the abstraction of two water molecules, so urea (CH4N2O) is derived
from ammonic carbonate [(NH4)2CO3].
Preparation.—(A.) Preparation from urine. (1.) Evaporate the
urine to a syrup, and mix the concentrated liquid with an equal bulk
of nitric acid. In this way a quantity of nitrate of urea will be
formed (CO(NH2).HNO3). Dissolve this compound in boiling water,
and treat the solution with baric carbonate, when pure urea remains
in solution. Thus—
2(CO(NH.).HNO3)4-BaCO3=CO(NH2).--Ba(NO.). -- CO., + H.O.
Nitrate of Urea + Baric = Urea + Baric + Carbonic -j- Water.
Carbonate nitrate anhydride
The clear filtrate is then to be evaporated to dryness, and the urea
separated from the baric nitrate by hot alcohol.
(2.) It may also be prepared by forming an oxalate of urea by the
action of oxalic acid on the concentrated urine. On adding chalk to a
solution of this oxalate in boiling water, calcic oxalate is precipitated,
and a solution of urea results, which may be purified by crystallisation.
(B.) By the action of heat on ammonic cyanate.
(C.) By the decomposition of ammonium carbamate.
(D.) Urea was the first organic body prepared artificially, as follows.
URIC ACID. 715
A mixture of potassic ferrocyanide (56 parts) and manganic peroxide
(28 parts) is heated to redness, when the following changes occur:—
K. FeCy -- O = 4KCyO + 2CO2 + N2 + Fe0
Potassic + Oxygen = Potassic + Carbonic + Nitrogen + Ferrous
ferrocyanide cyanate anhydride oxide.
The residue is now treated with cold water, and the clear filtrate
containing the potassic cyanate is mixed with ammonic sulphate (41
parts). The solution is then evaporated to dryness, and the urea
separated from the potassic sulphate by solution in hot alcohol —
2KCyO + (NHA):S0, R.S.O., + 2CO(NH2)2
Potassic + Ammonic = Potassic + Urea.
cyanate sulphate sulphate
Properties.—A colorless, inodorous body, crystallizing in long-flat-
tened prisms. It is soluble in spirit (1 in 5 at 50°F.), and very
soluble in water (1 in 1 at 60°F.), the solution being neutral and per-
manent. Its rapid decomposition in the urine into ammonic carbonate,
(to which the ammoniacal odor of putrid urine is due), depends on the
mucus present in the urine. When heated it melts, and finally
decomposes, evolving ammonia and ammonic cyanate, and leaving a
residue of cyanuric acid. It forms salts with acids, such as the nitrate
of urea [CO(NH2)3.HNOs), an important compound, an account of its
difficult solubility in nitric acid. When boiled with solutions of
caustic alkalies (cold solutions being without action upon it), it is
resolved into ammonia and an alkaline carbonate—a similar result
occurring when urea is fused with the alkaline hydrates, or heated
with water in a sealed tube. It combines with metallic oxides ; thus
the compound CO(NH2)2,2HgC) is produced when mercuric oxide is
added to a solution of urea in a potassic hydrate solution. Urea is
decomposed by nitrous acid and by chlorine.
Compound wreas are formed by the replacement of the hydrogen of
the urea by hydrocarbon groups. In sulpho-urea, sulphur takes the
place of oxygen [CS(NH3)2].
3. Uric Acid ; Lithic Acid (CEN, H,0s).--This is present in the
urine in combination with soda and ammonia, and is probably derived
from the disintegrated elements of albuminous tissues. These salts
of uric acid, being more soluble in warm than in cold water, are
frequently deposited as the urine cools, a reaction occurring in cer-
tain deranged states where an excess of uric acid is present.
The quantity of uric acid in human urine is increased by an animal,
and decreased by a vegetable diet. It is increased in certain morbid
states of the system. It varies greatly in different animals. In the
feline tribe uric acid is often entirely replaced by urea. In birds and
serpents the urea is often entirely replaced by uric acid. This suggests
the notion that although urea and uric acid may have different
origins and different offices, nevertheless that each may do the work
of the other.
716 LIANDBOOK OF MODERN CEIEMISTRY.
Urate of soda constitutes the chief constituent of the gouty concre-
tions called “chalk-stones.” :
Preparation.—It has never been prepared artificially.
A. From urine.—By adding HCl to the concentrated urine. The
uric acid is precipitated in the form of hard red grains.
B. From the excrement of serpents.--This consists of acid ammonic
urate. Dissolve the excrement by boiling in a solution of potassic
hydrate; filter, and add hydrochloric acid to the filtrate, when the
uric acid is precipitated as a white crystalline powder. “Guano" is
an impure uric acid, and is formed by the partial decomposition of the
excrement of sea birds.
Properties.—Uric acid is a tasteless, inodorous, and sparingly
soluble body (1 in 10,000). It is insoluble in alcohol and ether, but
is soluble in strong sulphuric acid. When heated in a retort, a
black residue remains, cyanic acid, hydrocyanic acid, carbonic anhy-
dride, and ammonic carbonate being evolved.
TJric acid is a dibasic acid. Fused with an alkaline hydrate, it
yields an alkaline carbonate, cyanate, and cyanide. Mixed with
nitric acid, it effervesces, and if the resulting solution be evaporated
nearly to dryness, and after dilution, mixed with a slight excess of
ammonia, the characteristic deep red tint of murexide (CaM6HsO6)
is immediately produced.
With hydriodic acid and heat, it is resolved into glycocin, carbonic
anhydride, and ammonia.
Some Products of the Oa’idation of Uric Acid.
Name.
Formula.
Preparation and Properties.
Allantoin
Alloxan
Alloxantin
CAN, HSOs
C.N.H.,04aq
C.N.H.O.3aq
Preparation.—(1.) From the allantoic fluid of foetal calf. (2.) By
boiling uric acid with water and peroxide of lead,
Properties. – Transparent colorless crystals; soluble in 160 parts
of cold water. Decomposed by boiling with mineral acids and
caustic alkalies.
Preparation.—By the action of strong nitric acid on uric acid in the
cold.
Properties.—White crystals; very soluble in water; crystals become
anhydrous at 150° C.; solution acid, and stains the skin red;
decomposed by both oxidizing and reducing agents. Forms a
deep blue compound when acted on with an alkali and a ferrous
salt. Alloxan appears to be the intermediate stage in the con-
version, by oxidation, of uric acid into urea. When alloxan is
boiled with peroxide of lead, urea is formed—
(C.N.H,0,--2PbO,-i-H,0=CHN,0+300,--2PbO).
Alloxan forms alloxantin by the action of sulphuretted hydrogen.
Preparation.—(1.) By the action of hot dilute nitric acid on uric
acid. (2.) By the action of reducing agents (as H.S) on alloxan.
Properties.—Colorless crystals. Soluble with difficulty in cold
water, more soluble in hot. Becomes anhydrous at 150° C.
Solution acid. Gives a violet precipitate with baryta water, and
a black precipitate with AgNO3 –Converted by oxidizing agents
into alloxan. Boiled in water with peroxide of lead, it forms urea
and plumbic carbonate. Decomposed by the prolonged action of
H.S into dialuric acid.
- UBIC ACID. 717
Name.
_--—-
Alloxanic
acid
Mesoxalic
acid
Parabanic
acid
Thionuric
acid
Uramil
Murexide
Purpurate
of ammo-
nia)
Dialuric
acid
Oxaluric
acid
Formula.
Preparation and Properties.
C.N.H,0s
C,0(OH),
C.N.H.O.,
C.N.H.S0s
C.N.H.0,
CANs|H,0s-Haq
C.N.H.0,
C.N.H.0,
Preparation.—By the action of baryta water on a solution of alloxan.
The Ba is to be separated by H.S.04.
Properties.—A crystalline bibasic acid. The solution is acid, and
decomposes carbonates. It dissolves Zn with the disengage-
ment of hydrogen. The silver alloxanate is insoluble. On boil-
ing in water alloxanic acid forms urea and mesoxalic acid
(C,0,0H)). º •º - *
Preparation.—(1.) By heating a solution of baric alloxanate to boil-
ing. (2.) By adding a solution of alloxan to lead acetate, and
decomposing the lead mesoxalate with Hss. Urea is formed
at the same time.
Properties.—A crystalline acid.
oxalate is insoluble.
Preparation.—By the action of moderately strong nitric acid on uric
acid, or alloxan, with the aid of heat.
Properties.—A crystalline acid. The solution neutralised with am-
monia and boiled, yields an ammonium salt of oxaluric acid.
Preparation.—By the action of a sulphurous acid solution on a cold
solution of alloxan, and afterwards boiling the mixture with
ammonia and ammonic carbonate. The ammonic thionurate
formed is to be converted into a lead salt, which is then de-
composed with sulphuretted hydrogen.
Properties.—By boiling the solution it is resolved into sulphuric
acid and uramil.
Preparation.— By boiling a solution of ammonic thionurate with a
slight excess of hydrochloric acid.
Properties.—A white crystalline body. Its ammoniacal solution
turns purple in air. It is decomposed into alloxan and ammonic
nitrate by nitric acid, and forms pseudo-uric acid by the action of
potassic cyanate. -
Preparation.—(1.) By heating dry alloxantin with ammonia. (2.)
By boiling uramil and mercuric oxide in a weak solution of
ammonia. +
Properties.—The crystals appear green by reflected, and purple red
by transmitted light. It is insoluble in alcohol and ether. It is
soluble in hot, but not very soluble in cold water. It is decom-
posed by mineral acids, a white body (murexan) being precipi-
tated. It is soluble in KHO, the solution being purple red, and
disappearing on boiling.
Preparation.—By the long continued action of H.S on a boiling
solution of alloxan. It is the final product of the action of
reducing agents on alloxan.
It resists heat. The silver mes-
4. Hippuric Acid (CoHoNOs); Benzamidacetic acid (C.H.INH
(C, H,0)].O.); Benzoyl glycocol (C.H. (CºH3O)NO.).-This acid is found
in large quantities in the urine of herbivorous animals, but it also
occurs in small quantities in the urine of man.
It is derived partly
from certain constituents of vegetable diet, and partly from the natural
disintegration of tissue.
The relationship between hippuric acid and benzoic acid is to be
noted.
The urine of a cow or horse when at rest yields, by the
action of hydrochloric acid, hippuric acid; but if the animals are being
actively worked, their urine yields benzoic acid, and not hippuric acid.
718 HANDBOOK OF MODERN CHEMISTRY.
Moreover, the fresh urine only yields hippuric acid, the same urine
when stale yielding benzoic acid. If benzoic acid be administered to
an animal, hippuric acid is found in the urine.
The urine of children is said sometimes to contain benzoic acid.
Preparation.—(1.) Evaporate cows' urine to a thick syrup, and add
to the concentrated urine an excess of hydrochloric acid. Hippuric
acid will be deposited on standing.
(2.) By the action of benzoyl chloride on zinc glycocoll:—
Zn”(C,EI.N.O.). + 2C, H2OCl - ZnCl2 + 2CoPHoNOs.
Zinc glycocoll –H Benzoyl = Zincic + Hippuric
chloride chloride acid.
Properties.—Rhombic prisms soluble in hot alcohol and in cold
water (1 in 400). Solution acid. Forms crystallizable salts. The
acid is monobasic. When heated it yields benzoic acid, benzoate of
ammonia and benzonitrile, a coaly residue remaining in the vessel. It
is converted into benzoic acid by sulphuric acid, and into benzoic acid
and glycocine (C2H5NO2) by hydrochloric acid. Nitrous acid converts
it into benzoglycollic acid (CoHaO.) which by the action of boiling
water is converted into benzoic (C, H5O2) and glycollic acids (C.H,0s).
It is to be remarked that hippuric acid is soluble in an aqueous
solution of sodic phosphate, which probably explains the acid reaction
of the urine.
5. Salts.-These consist essentially of Sulphuric, phosphoric, and
hydrochloric acids, combined with soda and potash, and with lime
and magnesia. The ash also contains a trace of iron.
The quantity of saline matter in normal urine varies between 8 and
9 grains in 1000 of urine, but the quantity is largely influenced by
diet (an animal diet increasing the quantity of sulphates), by mental
energy, etc.
6. Extractive Matter.—This includes kreatin, kreatinin (derived
from the metamorphosis of muscular tissue), Xanthin, and other bodies,
such as indican, glucose, etc.
7. Pigments.-The pigments of the urine are not well understood.
They are probably altered haemoglobin. A body called urohaematin
has been mentioned by Harley, and one called urochrome by Thudi-
chum. Other pigments variously named purpurin, rosacic acid, and
uroerythrin have also been described.
Schunck considers that all urinary pigments are products of two
coloring matters always present, the one being soluble in ether,
having the composition C, H31NO26, and the other insoluble in ether,
having the composition C9H27NO.4.
In jaundice the urine is colored by bile pigment.
8. Free Gases.—It was found that 100 c.c. of urine yielded at nor-
mal temperature and pressure the following gases:–
TJRINARY CALCULI. 719
Nitrogen ... tº ſº ſº & Cº. # * † tº tº º º 0.87
Oxygen tº tº e $ tº º tº § {} e º º tº º ſº 0-06
Carbonic anhydride, free ... e tº tº * * * * 4°54
3 y 2 3 combined ... tº e tº 2-07
It is to be noted that the composition of the urine is largely in-
fluenced by disease. Thus albumen appears in Bright's disease, and
glucose in diabetes.
Urinary Calculi.
A few general analytical remarks are all that is necessary here.
On heating a very small piece of the calculus on platinum foil, one
of two results may occur –
A. It may be entirely, or very nearly entirely, dissipated.
If this occurs, it is probably uric acid, but it may be urate of am-
monia, cystine, or xanthin.

Calculus. Physical Action of Water, Action of Acids, etc.
Characters. Alkalies, etc.
Uric acid, Brownish red; smooth Insol. in water; sol. Y
C; N.H.O3. or tuberculated; con- by heat in solution of
centric lamina (com- || KHO, without the ge-
mon). neration of ammonia. Dissolves with efferves-
A ppt. of uric acid oc- cence in HNO,. The
curs when an acid is residue on evaporation
added to the alkaline X is red, becoming purple
solution. red on the addition of
ammonia (purple red
Urate of Clay colored; smooth; Sol. in water; sol. by murexide).
ammonia. fine concentric lami- || heat in solution of
nae (rare). RHO, ammonia fumes
being evolved. J
Cystine Brownish yellow ; Insol. in water, in al- || Odor of CS, when heated.
(CAH,NS0.). semi - transparent ; cohol, or in ether; sol. Sol. in a solution of
- crystalline (very in ammonia, when the KHO. If acetate of lead
rare). solution is evaporated be added to a boiling solu-
spontaneously, it leaves | tion, a black ppt. of PbS
hexagonal plates. The results.
ammonia solution is
precipitated by an acid.
Xanthin Pale brown; polished | Sol. in alkaline solu- Sol, in HNO, without
(CSHAN.O.). appearance (very tions. effervescence; residue on
rare). evaporation a deep yellow
color. Sol. in boiling
HCl,
B. It may not be dissipated by heat.
It is probably oxalate of lime or fusible calculus, but it may be
phosphate of lime or ammonio-phosphate of magnesia.
720
CEIEMISTRY.
HANDROOK OF MODERN
Calculus.
Physical
Characters.
Action of Ammonia
on Solutions.
Action of Acids, Blow pipe,
etc.
Oxalate of lime
(mulberry
calculus).
Deep brown; rough;
very hard ; layers
thick (common).
The solution in HCl
gives a white amor-
phous ppt. with alm-
monia.
Sol. in HCl without effer-
Vescence; insol. in acetic
acid. When heated it
becomes CaCO, when it
dissolves in HCl with
effervescence, but on being
heated more strongly Caſ)
only remains, which is
alkaline to turmeric.
Phosphate of lime
Pale brown
The solution in HCl
Sol. insol.
color; in HCl ; in
(bone earth laminae regular gives a white amor- | acetic acid. Infusible
calculus). (rare). phous gelatinous ppt. before the blow pipe.
with ammonia. The residue on being
strongly heated is not
alkaline.
Ammonio-phos- | White, brittle, and | The solution in acids | Sol. in HCl and in acetic
phate of magnesia
(triple phosphate).
crystalline ; surface
uneven ; seldom la-
minated (rare).
gives a white crystal-
line ppt. With ammo-
nia.
acid. Fusible before
blow-pipe with difficulty,
evolving NH3. Residue
insol. in water and not
alkaline.
Mixed phosphate
of lime and
ammonio-phos-
phate of mag-
nesia (fusible
calculus).
White;
large ;
rarely
(common).
often very
fusible and
laminated
The solution in IIC1
or acetic acid gives a
white ppt. with am-
monia (phosphate of
magnesia) and a white
ppt. with oxalate of
ammonia (lime).
Sol. in acetic acid ; insol.
in KHO. Very fusible
by blow pipe, residue
being insol. in water, but
sol. in acids. Residue not
alkaline.
Faces.
These constitute the excrementitious portions of food. The che-
mical composition of the solid matter of the excrement varies with
the food taken. The feces consist (on an average) of about 25 per
cent. of Solid matter and the rest water. The solid portion is made up of
biliary matter, alimentary débris, and salts, these latter being mainly
phosphates of lime and magnesia, with small quantities of iron, soda,
lime, and silica. The offensive odor of faecal matter is due to certain
intermediate products of oxidation, and becomes more offensive as the
quantity of bile secreted diminishes.
Eaccretin (CaRI156SO2), a body melting at 204.8°F. (96°C.), soluble
in water and hot alcohol, and insoluble in cold alcohol, has been dis-
covered by Marcet in the alcoholic extract of faecal matter.
Eaccretolic acid (Marcet) consists of a mixture of fatty acids, pre-
cipitated by the action of lime on the alcoholic extract of faecal
matter.
Sweat is the watery excretion from the sudoriparous glands of
the skin. Its reaction is usually acid, from the presence of free lactic
and formic acids, etc. It contains from 0-5 to 2:00 per cent. of solid
SWEAT. 721
matter, the quantity varying with the temperature of the day, the
liquids taken, the amount of exercise, etc. The chief part of the
solid matter consists of sodic chloride, but traces of phosphate of
lime, and of lactates, butyrates, and acetates are also present.
A trace of urea is said to be constant. A peculiar azotized and
easily decomposed body and an odorous principle are present in
varying quantity. Carbonic acid and nitrogen are also given off by
the skin.
Mucus is a viscid matter secreted by the mucous membranes. It
is always, more or less largely, mixed with epithelium cells. Its
glairy consistence is due to the presence of a nitrogenized body called
mucin, the per-centage composition of which is said to be carbon
52:2, hydrogen 7-0, nitrogen 12-6, and oxygen 28:2.
Mucin swells up, but is not soluble in water. It is turned yellow
by nitric acid. It is neither precipitated by mercuric chloride, nor by
acetic acid, plumbic acetate, or potassic ferrocyanide, but is coagu-
lated by alcohol and by heat.
Pus is a creamy-white fluid, having a neutral or slightly alkaline
reaction. It appears under the microscope to consist of minute globules
floating in a transparent serum. The pus globules are only imper-
fectly dissolved by alkalies. They contain fat (2 to 6 per cent.) and
cholesterin (1 per cent.). Dilute acids distend them. The serum
contains albumin, leucin, and the albuminoid body called “pyin.”
Pyin is soluble in water. It is precipitated by acetic acid. Unlike
mucin it is precipitated both by mercuric chloride and by lead acetate.
Cholesterin C26H13OH is a fat-like body, soluble in ether, in boiling
alcohol, and in chloroform. It is the chief constituent of biliary
calculi.
The solid residue of pus contains 12 per cent, of saline matter,
phosphoric acid and potash being the principal acid and base present.
A P P E N DIX.
Liquefaction of Oxygen, Etc.—Since the chapter on oxygen was
printed, M. Raoul Pictet of Geneva has effected the liquefaction of
oxygen under a pressure of 300 atmospheres, and at the temperature
produced by the evaporation of liquid carbonic dioxide in a vacuum.
On removing the pressure a jet of liquid oxygen escaped from the
tube. By a double circulation of SO2 and CO2, the liquefaction of
the CO2 was effected at a temperature of —85° F (–65°C.) and at a
pressure of 4 to 6 atmospheres. This liquid carbonic anhydride
was then passed along a tube about 4 meters long, communicating
with two air-pumps. By forming a vacuum with the pumps the
CO2 solidifies. Through the interior of this tube a second and
smaller tube passes, through which a current of oxygen set free in a
strong vessel can be passed.
The apparatus will stand a pressure of 800 atmospheres.—“Che-
mical News,” Vol. xxxvi., p. 281.)
M. Pictet has also lately made the experiment of liquefying and
solidifying hydrogen. The process consisted in the decomposition
of potassic formate by potassic hydrate, by which means pure hydrogen
is generated. Thirty-five minutes after the commencement of the
experiment, a pressure of 650 atmospheres was reached, at which
point it remained for some minutes. The tap of the apparatus being
now opened, a bluish jet escaped with a crackling sound, like that pro-
duced by the contact of water and red-hot iron. The jet then Sud-
denly ceased; and it appeared as if a hail of solid bodies was thrown
violently with a rattling noise on the ground. The tap having been
again closed, the pressure fell from 370 atmospheres to 320, at which
it stood for a few minutes, then rising to 325. When the tap was
once more turned, a jet again escaped, which underwent interruptions,
showing that beyond doubt crystallisation had taken place in the
interior of the tube. This was proved by the escape of the fluid
hydrogen when the temperature was raised. *
Mendeleeff’s Law of Periodicity. — According to Mendeleeff
(“Journal de la Soc. Chimique Russe,” Tome i., p. 60), “The
724
HANDROOK OF MODERN CHEMISTRY.
properties of simple bodies, the constitution of their combinations, as well as
the properties of the latter, are periodic functions of the atomic weights of
the elements.”
of their atomic weight as follows:–
In accordance with this law the elements are arranged in the order

§ 1st 2nd 3rd 4th 5th 6th 7th 8th
'#' | Group. Group. Group. Group. Group. Group. Group. Group.
UD
- - © - • - RH, RH, RH, REI (R.H.)
#9 RO R2O3 RO, R20s R0, R20. (R0)
2 Li→7 Be=9 B=11 C=12 N=14 O=16 F-19 º e
Cu-63
3 Na=23 Mg=24 || Al=27 Si-28 P=31 S—32 Cl–35 | Fe=56
4 K=39 Ca-40 | ? E=44 Ti-48 W=51 Cr=52 Mn=55 | Co-59
Ni=59
Ru-104
5 (Cu-63) Zn=65 P 68 ? 72 As=75 | Se—78 Br-80 | Rh=104
6 || Rb-85 || Sr-87 Yt=88 Tri-90 Nb-94 || Mo-96 || ? 100 Pd=106
Ag=108
- Os=195
7 | (Ag=108)|Cd=112| In=113 | Sn=118 Sb=122 ||Fe=125 | I=127 Ir=197
8 Cs=133 Ba-137 Di-138 (?) Ce=140 gº º • * tº º Ph-198
Au-199
9 • * - - - - tº & * tº
10 Er=1.78 || La-180 P | Ta-182 W-184 || ? 190
11 (199–Au) 200 Hg Tl=204 || Pb=207 | Bi-208 ..
12 * * - - * - Th:=231 tº º |U-250
The chief use of this law at present appears to be in predicting the
Mendeleeff's Foundations of Chemistry.
discovery of new metals and the properties of their compounds.
will be noticed that several gaps occur in this classification, which
gaps Mendeleeff considers will be filled either by new metals or by
the corrected atomic weights of known elements. The newly discovered
metal, Gallium (see page 434), is, according to Mendeleeff, his eka-
aluminium, El, Group 3, Series 5, At. Wt. = 68. (Real At. Wt. 69.9).
For further information on this subject see—
It
Liebig's Annalen, Supplement, Band viii., page 133 (1871).
“Chemical News.”
“Quarterly Journal of Science,” No. xlix., January, 1876.
Page 32 et seq.
December 24th, 1875.
In order that certain elements may fit into those places which
APPENDIX.
725
Mendeleeff assigns to them, he proposes the following changes in the
atomic weights of certain elements.
Numbers received. Numbers proposed.
Element. . Remarks.
At. Wt. Oxide. At. Wt. Oxide.
Specific heat as deter-
Indium 75 || In O I 13 In,0s | tº: §:
this change.
M.M. Ramelsburg and
Uranium ... | 120 U,0s 240 UO, | Roscoe accept the pro-
posed change.
Cerium 92 CeO 138 Ce,0s "...º º:
Ce3O4 CeO2 tory.
MM. , Chydemius and
Thorinum ... 116 Th() || 232 ThO, º:º
Y , change.
ttrium 60 YO 90 Y.O - ---
Erbium . . . 141 Erſ) 171 Ejo, | Mººre the
Di ? or La P 92 RO 138 R,0s OTDI Lll32.
From the Chemical News, December 24, 1875.
726 FIANDBOOK OF MODERN CHEMISTRY.
TABLE I.
Table showing the Specific Gravities and percentage strengths of various
solutions of Nitric Anhydride (N205) and Nitric Acid (HNO3).

Specific r Specific -r
č. HNO3=63. N,0–108. §. HNO3=63. N.O. =108.
I 5000 92-983 79. 700 1 - 2047 46.299 39' 685
1° 4980 92° 0.53 78-903 l: 2887 45' 562 39-0.53
1 - 4960 91 - 124 78. 106 1 - 28.26 44' 632 38-256
1 : 4940 90-194 77.309 1:2765 43’ 702 37 ° 459
1 - 491 () 89 - 264 76. 512 1 - 27 05 42.772 36' 662
1 : 4880 88° 334 75-715 1 2644 41 - 842 35° S65
1 4850 87° 404 74. 918 1 - 2583 40° 9 3 35' 068
1 48.20 86°484 74. 121 1 - 2523 39 - 98.3 34-27 |
1 - 4790 85' 545 73° 324 1 2462 39 ():53 33°474
I-4760 84' 615 72. 527 1 - 2402 38: 123 32’677
1 - 4730 83-680 71-730 1 2341 37 - 190 3 l SS0
1 - 4700 82.755 70-933 1-2277 36 - 263 31 ()S3
1-4670 81 - 825 70° 136 1 - 22 12 35' 334 30 2S6
I 4640 80.895 69 - 339 1 - 2148 34 404 30.’ j S9
1 - 4600 79-966 68: 542 1 2084 33'47.4 2S' 602
1'4570 79 036 67-745 1 - 2019 32° 544 27.895
1 ° 45.30 78- 106 66-948 1 - 1958 31 614 27' 098
1 ° 4500 77: 181 66 - 155 1 - I S95 30' 684 26' 301
I 4460 76° 246 65' 354 1 - 1833 29.755 25-504
1° 4424 75' 316 64' 557 1. 1770 28' 825 24. 707
1-4385 74° 386 63-760 1 - 1709 27 - 890 23.910
1 4 346 73° 457 62.963 1 : 1 (348 26'965 23: 113
} - 4306 72. 527 (2° 166 1 - 1587 26' 035 22.316
1 - 4269 71 ° 587 61 - 369 1 - 1526 25 1 ().5 21 : 519
1 4228 70. 667 6(): 572 1 - 1465 24 - 176 20. 732
1-42 B. P. 70-000 6() ()00 1 - 1403 23° 2,46 19-925
1 - 4 189 69: 737 59.775 1 : 1345 22° 316 19' 128
1-4147 68-807 5S'978 1 - 12S6 21: 386 I S' 331
1. 4107 67-878 58. 181 1 - 12.2 20' 456 17 534
1 4065 66'948 57. 384 l' T 16S 19 - 526 16.737
1 - J 0.23 (86° 018 56' 587 I l l 00 18° 597 15- 940
1 - 3978 65' 090 55' 790 1 : 1 (),51 17 - (367 15° 143
1 - 394 5 64 - 158 54 - 993 1 : 1 () 10 l 7' 442 14:950
1 - 3882 63. 229 54 - 196 1 * ()003 16.737 14- 346
1 - 38.33 62.299 53.399 I 09:35 15'807 13'549
1 - 3783 (31 - 369 5.2. 602 1. OS78 14 877 12.752
1 - 37:32 60° 439 51 - S05 1 - 0821 13:947 I 1 - 955
1 - 3681 59.579 51 - 068 1 - 0.764 13:01.7 11 : 15S
I 3630 58-579 50: 21 l 1 - 0708 12' ()SS 10' 361
1.3579 57 - 650 49-4 14 1 ()(35.1 11 : 158 9° 564
1°35'29 56.720 48. 617 1 - 0595 10 - 228 8.767
1.3477 55. 790 47-820 1' ().540 9. 298 7. 970
1 - 3427 54 - S60 47.023 1 * 0.485 S. 368 7. 173
1. 3376 53-930 46-226 1 - 0430 7'439 6-376
1 : 3323 53 ()()0 45' 4 29 I 0.375 G - 508 5. 579
1. 3270 52. 069 44' 632 1 - 03:20 5'579 4-782
1. 3216 51 - 141 43-835 1.0267 4' 649 3.985
1 - 31 63 50: 211 43° 038 I 0212 3.719 3. I 88
1 - 31 10 49-281 42'241 1 () l 59 2.789 2-391
1 - 3056 || 48-355 41-447 1 () 106 1 - 860 1 : 594
1°3001 47-180 40°440 1'0053 0.930 0.797
APPENDIX. 727
TABLE II.
Showing the Percentage of real Sulphuric Acid (H2SO4) corresponding to
various Specific Gravities of Aqueous Sulphuric Acid.
Bineau; Otto. Temp 15°.
* Per tº Per g Per * Per
jºi. cent. of ; cent. of j. * | cent. of ; cent. of
W. H.S0, W. H.S0, 7 |H,SO, y. S0.
1-8426 100 1.675 75 1 - 398 30 1 - 182 25 º
1-842 99 1-663 74 1. 3886 49 1' 174 24
1-8406 98 1°651 73 I-379 48 I-167 23
1-840 97 1-639 72 1:370 47 1 - 159 22
1-8384 96 1-627 71 1-361 46 1 - 1516 21
1-8376 95 1 : 615 70 1° 351 45 l'144 20
1-83.56 94 1:604 69 1°342 44 1° 136 19
1°834 93 1° 592 68 I 333 43 1° 129 18
1°831 92 1-580 67 1°324 42 I 121 17
1.827 91 1-568 66 1-315 41 1° 1136 16
1-822 90 1:557 65 I-306 40 I - I 06 15
1:816 89 1:545 64 1:2976 39 1°098 14
1-809 88 1-534 63 I-289 38 1.091 13
1-802 87 1-523 62 1°281 37 1*083 12
1-794 86 1'512 61 I'272 36 1-0756 II.
1786 85 1 - 501 60 1 - 264 35 1 - 068 10
1,777 84 1.490 59 1.256 34 I'061 9
1.767 83 I-480 68 1:2476 33 1-0536 8
I-756 82 1'469 57 I 239 32 1 * 0.464 7
1:745 Sl 1-4586 56 1 - 231 31 1*039 6
1-734 80 I'448 55 1°223 30 1-032 5
1:722 79 1-438 54 1 - 215 29 1- 0.256 4
I-710 78 I'428 53 1-2066 28 I” () 19 3
1-698 77 1-4 18 52 1 - 198 27 1*013 2
1-686 76 I-40S 51 l" 190 26 1:0064 I



728 HANDBOOK OF MODERN CHIEMISTRY.
TABLE III.
Table showing the percentage quantities of Hydrochloric Acid, Sp. Gr. 12,
and of Hydrochloric Acid Gas contained in aqueous solutions of
different Specific Gravities.

Specific § º Hydrochloric Specific º d f Hydrochloric
Gravity. º * Acid Gas. Gravity. #. T. Acid Gas.
1 - 2000 100 40.777 1.0980 49 19-980
1 - 1982 99 40°369 1-0960 48 19:572
1 : 1964 98 39.961 1-0939 47 19 - 165
1 - 1946 97 39°554 1-0919 46 18-757
1 - 1928 96 39-146 1.0899 45 18° 349
1 - 1910 95 38.738 1.0879 44 17:941
I 1893 94 38. 330 1.0859 43 17:534
-1 - 1875 93 37.923 1.0838 42 17. 126
1-1857 92 37' 516 1 - 08.18 41 16.718
1- 1846 91 37: 108 l:0798 40 16:310
1- 1822 90 36-700 1-0.778 39 15'902
1.1802 89 36. 292 1.0758 38 15° 494
1-1782 88 35'884 1.0738 37 15:087
1. 1762 87 35-476 1.0718 36 14' 679
1 - 1741 86 35-068 1.0697 35 14 - 271
1' 1721 85 34 - 660 1.0677 34 13.863
1' 1701 84 34 252 1.0657 33 13:09.4
1' 1681 83 33-84.5 1.0637 32 12'597
1 - 1661 82 33'437 1.0617 31 12-300
1' 1641 81 33-029 1.0597 30 1 1-903
1 - 1620 80 32°621 1.0577 29 11-506
1-1599 79 32-213 1:05.57 28 11 - 109
I. 1578 B. P. 78 31.805 1.0537 27 10-712
1: 1557 77 31 - 398 1-0517 26 10 316
I 1536 76 30: 990 1 - 052 B. P. 10-290
1°1515 75 30.582 1-0497 25 0.919
1- 1494 74 30, 174 1. 0477 24 9-922
1- 1473 73 29-767 1 : 0457 23 9-126
1°1452 72 29.359 1-0437 22 8.729
1° 1431 71 28.951 1.041 7 21 8.332
1 - 1410 70 28'544 1.0397 20 7-935
1 : 1389 69 28. 136 1.0377 19 7.538
1° 1369 68 27.728 1.0357 18 7-141
1 - 1349 67 27:321 1-0337 17 6:745
I 1328 66 26.913 1 - 0.318 16 6:348
I 1308 65 26. 508 1 -0.388 15 5'951
1: 1287 64 26' 098 1.0279 14 5-554
1.1267 63 25-690 1-0259 13 5-158
... 1' 1247 62 25-282 2 : 0239 12 4.762
1 - 1226 61 24'874 1 * 0.220 11 4-365
I 1206 60 24'466 1-0200 10’ 3'998
1 - 1 185 59 24 () 58 1 - 0 180 9 3'571
1 - 1 164 58 23.650 1-0 || 60 8 3-174
T 1143 57 23'24.2 1 - 0140 7 2.778
1 - 1123 56 22.834 1 - 0120 6 2: 381
1-1 102 55 22°4′26 l" () 110 5 1-9S4
I 1082 54 22-019 1 : 0080 4 1 : 588
1° 1061 53 21 - 611 1-0060 3 1 - 191
1’ 1041 52 21:203 1 - 00:40 2 0.795
I 1020 51 20-796 1.0020 l 0.397
1’ 1000 50 20 388
APPENDIX.
729
TABLE TV.
Showing the Percentage Amount of Ammonia (NH3) in Aqueous Solutions
of the Gas of various Specific Gravities.
Carius. Temp. 14°.
Specific NH, Specific NH, Specific NH,
Gravity. per cent. Gravity. per cent. Gravity. per cent.
0-88.44 36 0.91.33 24 0-9520 12
0-8864 35 0-916.2 23 0-9556 11
0. S885 34 0.9 19.1 22 0-9593 10
0. S907 33 0-9221 21 0-9631 9
()- 8929 32 0.9251 20 0.9670 8
0-895.3 31 0-9283 19 0-9709 7
0-8976 30 0-93.14 18 0-97.49 6
0-9001 29 0.9347 17 0-9790 5
0-9026 28 0.9380 16 0-98.31 4
0-9052 27 0-9414 15 0.9873 3
0.9078 26 0-94:49 14 0-991.5 2
0-9106 25 0-9484 13 0-9959 1
|
TABLE W.


Showing the Percentage Amount of Potash (K20) in Aqueous Solutions of
various Specific Gravities.
Tünnermann, N. Tr. xviii., 2, 5. Temp. 15°.
Specific Gravity. º Specific Gravity. º
1 - 3300 28-290 1- 1437 14° 145
1' 3.131 27, 158 1 * 130S 13° 013
1 - 2966 26' 027 1 * 1182 11 - 882
1 - 2805 24'895 1° 1059 10- 750
1 - 2648 23-764 1 * 0.938 9 : 619
I “2493 22-632 1 - 08 l8 8-4.87
1 - 2342 21:500 1-0703 7-355
1 - 2268 20-935 1 - 0589 6-224
I 2122 19 - S03 l: 0478 5- 002
l: 1979 1S. 671 1 - 0.369 3-961
1 - 1839 17:540 1.0260 2.829
1. 1702 16-408 1.0153 1-697
1 - 1568 15-277 1-0050 0-5658
730
EIANDBOOK OF MODERN CHEMISTRY.
Table WI.
Showing Percentage Amount of Soda (Na2O) in Aqueous Solutions of
various Specific Gravities.
Tünnermann.
Specific | Per cent. || Specific | Per cent. || Specific | Per cent. || Specific | Per cent.
Gravity. of Na,0, Gravity. of Na,0. || Gravity. of Na,0. || Gravity. of Na,0.
1-4285 30 - 220 1' 31.98 22-363 1 - 2392 15' 110 1 : 1042 7.253
1'4193 29' 616 1' 3143 21-894 1 ° 2280 14 °500 1-0948 6-648
I '4 101 29' 011 1 - 3125 21-7.58 1:21.78 13-901 1-0855 6:044
1-4011 28.407 1°3053 21-154 1. 2058 13.297 1.0764 5'440
1:39:23 27.802 1-2982 20-550 I 1948 12' 692 I ()675 4 ‘835
1 - 3836 27-200 I 29 12 19.945 1’ 1841 12:088 1.0587 4'231
1' 37.51 26. 594 1.284.3 19° 341 1' 1734 11:484 1.0500 3' 626
I 3668 25' 989 1. 27.75 18-730 1 1630 10.879 l 0.414 3.02.2
1° 3586 25-385 1:2708 18- 132 1 - 1528 10:275 1.0330 2-4 18
1' 3505 24-780 1 - 2642 17:528 1 - 1428 9-670 I '02.46 1.813
1' 3.426 24. 176 I 2578 16'923 1 - 133 9.066 1 - 0 163 1-209
I 3349 23: 572 1:25.15 16:379 1 - 1233 8:462 1-0081 0' 604
1. 32.73 22.967 1'2453 15: 714 1: 1137 7.857 1 : 0040 0' 302
TABLE WII.


Proportion of Absolute Alcohol by Weight in 100 parts of Spirit, of
different Specific Gravities at 60°F.
(Fownes. Phil. Trans., 1847.)
Alcohol Specific || Alcohol | Specific || Alcohol | Specific || Alcohol | Specific
per cent. Gravity. || per cent. Gravity. || per cent. Gravity. || per cent. Gravity.
0. 5 1 - 0000 25 •9652 51 •9 160 76 '8581
() 0.999.1 26 • 96.38 52 • 9135 77 -8557
1 0 - 9981 27 • 9623 53 •9 113 78 • S533
2 0.9965 28 • 9(309 54 •9090 79 • 8508
3 0-9947 29 •9593 55 •9069 80 • 8483
4 0-9930 30 9578 56 •9047 81 • S459
5 0-9914 31 •9560 57 •9025 82 ‘8434
6 0.9898 32 ‘9544 58 • 9001 83 • S408
7 0.988.4 33 •9528 59 •8979 84 • S382
8 0 - 98.69 34 ‘95 || 1 60 • S956 85 -8357
9 0.985.5 35 •9490 61 •8932 86 • S331
10 0.984.1 36 •9470 (32 • S908 87 '8305
11 0-9828 37 •9452 63 ‘88S6 88 •8279
12 0-9815 38 •9434 64 ‘8863 89 •8254
13 () -98.02 39 •94 16 65 • 8840 90 •8228
14 0.9789 40 • 9396 66 ‘8816 91 • 81.99
15 0.9778 41 •9376 67 -8793 92 •817.2
16 0.9766 42 •9356 68 •8769 93 -81.45
17 0.9753 43 ‘93.35 69 ‘8745 94 •8 118
18 0.9741 44 ’93 14 70 -87.21 95 • S089
19 0.97.28 45 •9292 71 • 8696 96 • 8061
20 0-97.16 46 •9270 72 '8672 97 ‘8031
21 0.97.04 47 • 92.49 73 •8649 98 • 8001
22 0.969 1 48 •922S 74 •8625 99 •7969
23 0.9678 49 •9206 75 •8603 100 • 7938
24 0-9665 50 •918.4



In this Table every
alternate number is the result of a
direct
synthetical experiment; absolute alcohol and distilled water being
weighed out in the proper proportions, and mixed by agitation in
stoppered bottles; after a lapse of three or four days, each specimen
was brought exactly to 60°F, and the specific gravity determined with
great care.
APPENDIX.
731
TABLE VIII.
Specific Gravities corresponding to Degrees of Baumé's Hydrometer for
Liquids heavier than Water. (Water=1.000.)
Degrees | Specific || Degrees | Specific Degrees | Specific || Degrees | Specific
Baumé. Gravity. || Baumé. Gravity. || Baumé. Gravity. || Baumé. Gravity
0 1 : 000 20 1 - 152 40 1.357 60 1.652
l 1.007 21 1 - 160 41 1 - 369 61 1-670
2 l: 0 13 22 1 - 169 42 1 - 38.2 62 1 - 689
3 I 020 23 1 - 178 43 1 - 395 63 I-708
4 1-027 24 1 - 188 44 1.407 64 1.727
5 1 - 0.34 25 1- 197 45 1-420 65 1-747
6 1 - 041 26 1 - 206 46 I 434 66 1.767
7 1 * 0.48 27 1 ° 216 47 1'448 67 I-788
8 I - 0.56 28 1 - 225 48 1° 462 68 1 - 809
9 1 - 063 29 I 235 49 1-476 69 1-831
10 1-070 30 1 245 50 1 - 490 70 1 ‘854
11 1 - 078 31 1 - 256 51 1 495 71 1-877
12 1 - 085 32 I 267 52 1 - 520 72 1-900
13 1 - 09.4 33 1.277 53 1 - 535 73 1-924
14 1 - 101 34 1 - 288 54 1'55.1 74 1-949
15 1 - 109 35 1 - 299 55 1- 567 75 1-974
16 1 - 118 36 1 - 310 56 1 - 5S3 76 2°000
17 1 - 126 37 1 - 321 57 1 - 600
18 1 : 134 38 1 - 333 58 1 - 617
19 1° 143 39 1°345 59 1: 634


Specific Gravities on Baumé’s Scale for Liquids lighter than Water.


Degrees | Specific || Degrees | Specific || Degrees | Specific || Degrees | Specific
Baumé. Gravity. || Baumé. Gravity. || Baumé. Gravity. || Baumé. Gravity.
10 I 000 23 0.91 S 36 0-849 49 0-789
11 0-993 24 0.913 37 0-844 50 0-785
12 0-986 25 0.907 38 0 - S39 51 0-781
13 0.980 26 () ‘901 39 0-834 52 0.777
14 0-973 27 (). S96 40 (): S.S() 53 0 773
15 0.967 28 ()' SQ() 41 0.825 54 0.768
16 0-960 29 0 - SS5 42 (): S.20 55 0- 764
17 ()' 954 30 () - SS0 43 (): 816 56 (): 760
18 0-948 31 (). S74 44 0 - S11 57 0-757
19 0-942 32 0 - S69 45 (): S07 5S 0-753
20 0.936 33 0 - S64 46 0 - S02 59 0-749
21 0.930 34 ()- 859 47 0.798 60 0° 745
22 0-924 35 0.854 48 0-794
732
HANDBOOK OF MODERN CHEMISTRY.
TABLE IX.
Degrees on Twaddell’s Hydrometer, and the corresponding Specific
Gravities.
[NotE,--The degrees of Twaddell's hydrometer are converted into their cor-
responding specific gravities by multiplying by 0:005, and adding 1.000.]
Degrees Specific Degrees Specific Degrees Specific
Twaddell. Gravity. Twaddell. Gravity. Twaddell. Gravity.
1 1 - 005 8 1-040 15 1.075
2 1 : 010 9 1-045 16 1 - 080
3 1 - 0.15 10 1.050 17 1 - 085
4 1.020 11 1 : 05.5 18 1 - 090
5 1 - 0.25 12 1 - 060 19 1.095
6 1.030 13 1 * 0.65 20 1 - 100
7 1.035 14 1-070
TABLE X.
JEnglish Weights and Measures.—Avoirdupois.
Grs. Drms. Ozs. lbs. Qrs. Cwt. | Tons.
Grain . . 1
Drachm 27.34 I
Ounce.. 437' 5 16 1
Pound.. 7000 256 16 1
Quarter 196000 71.68 448 28 1
Cwt. . . . . 78.4000 28672 1792 112 4 1.
Ton 15680000 573440 35840 2240 80 20 1
Troy Weight.
Grains. Dwts. Ounces. lb.
Grain . . . . . . 1
Pennyweight .. 24 1
Ounce. . 480 20 l
Pound. . 5760 240 12 1



1 cubic inch of distilled water in air
1 gallon
1 pint
1 fluid ounce
1 litre
1 cubic centimètre
5
at 62°F. = 252.456 grains.
1 cubic inch of distilled water in vacuo at 62°F. = 252-722 grains.
Cubic inches,
1 cubic inch = 16-387 cubic centimètres.
277.276 (100 c.i. = 0.3606 gallon).
34-659
1.7329
61:024
0.061024
(For comparison of French and English weights, see page 50.)
APPENDIX. 733.
TABLE XI.
To Reduce Grammes to Grains.
Log. Grammes + 1-188432 = log. Grains.
To Reduce Cubic Centimétres to Cubic Inches.
Log. cubic centimetres + (−2.7855007) = log. Cubic inches.
To Reduce Millimetres to Inches.
Log. millimétres + (−2°5951663) = log. inches.
To Convert Grains into Grammes.
Log. grains + (−2.8115680) = log. grammes.
To Convert Cubic Inches into Cubic Centimetres.
Log. cubic inches + 12144993 = log. cubic centimètres.
To Convert Inches into Millimetres.
Log. inches + 1.4048387 = log. millimëtres.
TABLE XII.
Table of the corresponding Heights of the Barometer in Millimetres and
JEnglish Inches.

Milli- English Milli- English Milli- English
mêtres. T inches. mêtres. T inches. mêtres. T inches.
720 = 28-347 739 = 29.095 758 = 29-843
721 F. 28-386 740 == 29' 134 7.59 +. 29-882
722 +: 28-4.25 74.1 == 29-174 760 - 29-922
723 F 28.465 742 = 29-213 761 tº 29.961
724 - 28'504 7.43 = 29-252 762 - 30.000
725 - 28° 543 744 = 29-29.2 763 = 30'039
726 F 28° 5S3 745 - 29-331 764 == 30-079
727 F. 28.622 746 F 29:370 765 - 30- 118
728 == 28-662 747 – 29-410 766 - 30, 158
729 - 28-701 748 - 29-449 767 F 30-197
730 F 28-740 749 - 29°488 768 F. 30-236
731 - 28-780 750 - 29-52S 769 = 30-276
732 tº: 28:819 75] - 29'567 770 == 30-315
733 = 28 '85S 752 - 29'606 771 F. 30-355
734 F. 2S-S98 753 F. 29' 645 772 F. 30-394
º 35 = 28-937 754 == 29-685 773 F. 30°433
736 F 28.976 755 - 29.724 774 = 30°473
737 =: 29' 016 756 == 29-764 775 ~ 30°512
738 - 29' 055 757 ~ 29-S03
734 HANDBOOK OF MODERN CHEMISTRY.
|
TABLE XIII.
For Converting Degrees of the Centigrade Thermometer into Degrees of
Fahrenheit's Scale.


Centigrade. Fahrenheit. || Centigrade. Fahrenheit. || Centigrade. Fahrenheit.
— 90° —130° —60° —76° –30° –22°
85 121 55 67 25 13
80 112 50 58 20 4
75 103 45 49 15 + 5
70 94 40 40 10 14
65 85 35 31 5 23
0° +32° + 100° +212° +200° +392°
+ 5. 41 105 221 205 401
10 50 1 10 230 210 410
15 59 115 239 215 419
20 68 120 248 220 428
25 77 125 257 225 437
30 86 130 266 230 446
35 95 135 275 235 455
40 104 140 284 240 464
45 113 145 293 245 473
50 122 150 302 250 482
55 131 155 31 l 255 491
60 140 160 320 260 500
65 149 165 329 265 509
70 158 170 338 270 518
75 167 175 347 275 527
80 176 180 356 280 536
85 185 185 365 285 545
90 194 190 374 290 554
95 203 195 383 295 563
1° C. – 1.8° F.
2 2- 3-6
3 F 5'4
4 - 7.2
To Convert F. into C. degrees and C. into F. degrees.
***** = c.”; or (F.--82) + 1 s = c.”
*—º- + 32 = F.°; or (C.” X 1-8) + 32 = F.”
APPENDIX. 736
TABLE XIV.
Table of the Tension of Aqueous Vapor expressed in Inches of Mercury,
at 32°F., for each degree F. between 0° and 100°.

Temp. Inches of |Temp. Inches of |Temp. Inches of |Temp. Inches of
O Mercury. || * F. | Mercury. || * F. Mercury. || * F. | Mercury.
0 0.0439 26 0.1395 51 O'3742 76 0.8964
1 0.0459 27 0.1457 52 0.3882 77 0.9266
2 0-0481 28 0-1522 53 0-4026 78 0.9577
3 0-0503 29 0-1589 54 0-417.5 79 0.9898
4 0.0526 30 0-1660 55 0.4329 80 1-0227
5 0-05:51 31 0-1733 56 0°4488 81 1.0566
6 0-0576 32 0-1810 57 0.4653 82 1.0915
7 0° 0603 33 0- 1883 58 0°4822 83 1-1274 .
8 0-0630 34 0-1959 59 0-4997 84 1' 1643
9 0-0659 35 0-203S 60 0. 5178 85 I-2023
10 0-0689 36 0.2119 61 O-5364 86 1 - 2413
11 0-0721 37 0-2204 (32 0-5.556 87 1 2815
12 0.0753 38 (): 2291 63 0-5755 88 1-3228
13 0.0788 39 0-2381 64 0.5959 S9 1 - 3652
14 0.0823 40 0-2475 65 0.6170 90 1 4 088
15 0.0861 41 0.2571 66 0-6388 91 1'4537
16 0-0899 42 0-2672 67 0°6612 92 1-4.998
17 0.0940 43 0.2775 68 0-6843 93 1:54.71
18 0.0982 44 0-2882 69 0-70S1 94 1° 5958
19 0-1027 45 0-2993 70 0.7327 95 1:6457
20 0.1073 46 0-3108 71 0-7580 96 1.6971
21 0 1 121 47 0.3226 72 0- 7841 97 1:7498
22 0.1171 48 0°3349 73 0-8109 98 1-8039
23 0 1 223 49 0-3476 74 0-8386 99 I-8595
24 0- 1278 50 0-3607 75 0-8671 100 1.9170
25 0-1335
This Table is computed from Regnault's experiments, and is taken
from Dixon's “Treatise on Heat” (page 257).
“A” and “ia,” the terminations
Abietic acid *
Absorption coefficient
Acenaphthene . .
Acetal . tº º
Acetamide .
Acetate, aluminic
ammonic .
amylic
argentic . .
cupric
ethylic
ferric .
ferrous
hydric
methylic
plumbic .
potassic .
sodic .
zincic. • * *
Acetates—reactions .
Acetic acid . & ºn
—metallic salts of .
derivatives of
—reactions .
—action of chlorine on .
aldehyde
anhydride . .
chloride . .
ether .
peroxide . * *
Series, acids of the
— general reactions
—aldehydes of the
Acetification of alcohol .
Acetone tº dº tº
Acetonine
Acetonitrile e
Acetopropionic acid .
Acetous fermentation
Acetyl chloride
Acetylene
I N D E X.
. . . . 600
. . . . Goi
synonyms, preparation, properties 231
tests . . .
series. º
preparation .
properties
Acid amides º
Acid, an, what it is .
abietic
acetic
—reactions . º
—metallic salts of
—derivatives of sº
—action of chlorine on
. 228, 535-536
3
PAGE
22
. . 554
. . 202
. . 543
. 644
672
. 601
. 601
. 602
. 601
. 601
. 602
. 601
. 601
. 602
. 601
. 601
. 601
. 627
. 600
. 601
. 602
. 627
. 74
. .. 644
. . 602
. . . 602
. . . 602
. . 602
596-605
. . 598
643-644
64
. 646
. 647
. 673
• 60S
. 485
. 602
231-232
231-232
. 536
536-539
. 594
. 527
. 554
. 600
. 627
. 601
. . . . 602
. . . . 74
FAGE
Acid—continued.
acetopropionic * . 608
acrylic . . . . . . . 610
adipic . . - . 618
alloxanic . * º . 717
alphatoluic . . . . . . . 612
alphaxylic • * * . 612
amido-acetic º sº . . 694
amido-caproic . . . . . 604, 694
amylhydro-Oxalic . . . . 605
anchoic . . º . 618
angelic . . . . . g . 610
anhydrous sulphuric . . 150
anisic * * * * . 614
anthracene carboxylic . 617
anthraquinone-disulphonic . . 546
antimonic . . . . . . . 391
arachidic . . . . . . 597
arsenic . 398
arsenious . 396 .
atropic tº a tº . 616
behenic . . . . . . . . 597
benzamidacetic 613, 717
benzenic. . . 612
benzoic 538, 612
—reactions . . . . . . . . 629
bisulphuretted hyposulphuric . . 160
boric or boracic . . . . . 184
brassic . . . . . . ... 610
bromic . . . . . . 86
bromobenzoic . ... 613
butylactic . . 605
butyric . . . . 602-603
camphic . . . . . . 553
camphoric . 553
capric . * tº tº º . 597
caproic . . . . . . . 603-604
caprylic . 597
carbamic . 673
carbocresylic 614
carbohydroquinonic 615
carbolic . . . . . . . . 571
carbonic . . 100-102, 177, 606–607
carminic . . . . . . . 679
cerotic e - . 597
chenotaurocholic . 711
chlorhydric . . . . . 210
chloric • gº tº . 82
chlorobenzoic . 613
chlorocarbonic . . 181
chlorochromic . . 360
chlorosulphuric. . 149
chlorous . S0-81
cholic . & . 710
chromic . . . . . 359
738
INDEX.
PAGE PAGE
Acid, chromic—continued. Acid—continued.
—a powerful oxidizing agent . . 506 glyoxalic . . . . . . . . . 608
chrysammic . . . . . . . . 678 glyoxylic . . . . . . . . 609
cimicic . . . . . . . . . 610 Graham's sulphuric . . . . . 154
cinnamic . . 616 graphic, or graphitic . . 167
citraconic . 624 heptylic . . . . . . . 604
citramalic • * . 621 hexylic . . . . . 603-604
citramic . . . . . . . . . 673 hippuric . . 613, 717-718
citric . . . . . . . . . . 624 —reactions . . . 628
—reactions . . 628 homocumic . . g . 612
collinic e e g º a . 612 hyaenasic. . . . . . . . . 597
convolvulinoleic . . . . . 608 hydriodic. . 214-216, 577
cresotic º . 614 hydrobromic . . . 213-214
crotonic . . . . . 610 hydrochloric. . 210-213, 553
cumidic, . . 624 —table showing the percentage
cumic. º e . 612 quantities of, and of hydro-
cumylic . . . . . . . . . 612 chloric acid gas contained in
cyanic, preparation of . . . . 514 aqueous solutions of different
cyanuric . . . . . . . 515 specific gravities. . 728
damaluric . 610 hydrocyanic. 509-511
damolic - tº e - . 610 —estimation of . 523
dephlogisticated marine . . 70 —reactions . . . . . . . 522
desOxalic . . 625 hydrocoumaric . . 614
dialuric . . 717 hydrofluoboric . . . 185
diamyloxalic . 605 hydrofluoric. 216-217
dibasic . 253 hydrofluosilicic. . . . . 189
dibromacetic . 602 hydro-nitroprussic . 521
dichloracetic . . . . . . 602 hydroparacoumaric . 614
dichlor-anthracene-disulphonic. .. 545 hydroselenic. . 227
diethacetic . . . . . 602 hydrosulphuric . . 224
dioxyacetic . . 609 hydrosulphurous . 157
dioxyadipic . . 621 hyocholic. . 711
dioxybenzoic . . . 615 hypobromous 85
dioxypropionic . . 609 hypochloric . . 81
dioxysuberic . 621 hypochlorous 78-79
dioxysuccinic . 621 hypogeic . . . . . . . . 610
disulpho-dithionic . . 160 hyponitric (nitric peroxide). . 110
dithionic . . . . . . . 159 hyponitrous. . . . . ... 106
dithionous . . . . . . . . 158 —(nitrous anhydride). . . 108
doeglic . 610 hypophosphorous . . . . . 131
elaidic . 610 hyposulphuric (dithionic acid) . . 159
epihydric . 608 hyposulphurous 157-158
erucic . . 610 — (thiosulphuric acid). . . . . 158
ethacetic . . 602 iodacetic . . . . . . 602
ethylcrotonic . 610 iodic . . . . . . . . . . 90
ethylic . 600 isatropic . . 616
ferric . . 355 isophthalic . 624
ferricyanic . . 520 isoxylidic. . 624
—reactions . 524, 630 itaconic . 624
ferrocyanic . . . 518 jalapinoleic . . 608
—reactions . . . . . 523, 630 kakodylic . 668
fluoboric . . . . . . . . 185 lactic . º . 607
formic. . 599 —fermentation . . 484
formobenzoic . 614 lauric . . 597
fulminic . . . . . . . 515 leucic. . . 605
fulminuric . . . . . . . . 515 lithic . 715–717
fumaric . 624 malamic . . 673
gaidic . . . . . . . . . 610 maleic . 624
gallic . . . . . . . . . . 615 malic . . . 621
—reactions . . 630 -- reactions . 628–629
gallotannic . (336 malonic . . 618
glutanic . . 621 mandelic. . 614
glyceric tº º . 609 manganic - * . 328
glycocholic . . . 710 margaric . . . . . . . . . 604
glycollic . . 607 marine . 210
INDEX. 739
PAGE PAGE
Acid—continued. Acid—continued.
meconic . . . . . . . . . 625 parabanic. . . . . . . . . 717
—reactions . . . . . . . . 630 paraoxybenzoic . . . . . . . . 614
melissic . . . . . . . . . 597 paratartaric . . . . . . . . 49
mellitic . . . . . . . 625-626 pelargonic . . . . . . . . 597
mesaconic . . . . . . . . 624 pentathionic . . . . . . . . 160
mesidic . . . . . . . . . 624 pentyiic . . . . . . . . . 603
mesitic . . . . . . . . . 539 perbromic . . . . . . . . 86
Imesoxalic. . . . . . . 621, 717 perchloric . . . . . . . 82-83
metabismuthic . . . . . . . 375 periodic . . . . . . . . 90-91
metabismuthous . . . . . . 374 pernitrous . . . . . . . . 108
metantimonic . . . . . 391, 392 persulpho-molybdic . . . . . 409
metaphosphoric . . . . . . 134 phenic . . . . . . . 571
metastannic . . . . . . . . .386 phenoic . . . . . . . . . 612
metatoluic . . . . . . . . 537 phenylbenzoic . . . . . . , 547
metatungstic . . . . . . . 433 phenylic . . . . . . . . . 571
methacetic . . . . . . . . 602 phenyl-lactic . . . . . . . 614
methacrylic . . . . . . . . 610 phenyl-propiolic . . . . . . 616
methylcrotonic . . . . . . . 610 phlogisticated vitriolic . . . . 148
methylic . . . . . . . . . 599 phloretic . . . . . . . . . 614
metoxybenzoic . . . . . . . 614 phosphoric . . . . . . . . 47
monobasic . . . . . . . . 253 —conversion of phosphorus into . 130
monobromacetic . . . . . . 602 phosphorous . . . . . . . . 132
monochloracetic . . . . . . 602 phthalic . . . . . . . 624, 626
mono-oxy-acetic . . . . . . 607 physetoleic . . . . . . . . 610
moringic . . . . . . . . . 610 picric . . . . . . . . . . 678
moritannic . . . . . . . . 678 pimelic . . . . . . . . . 618
muriatic . . . . . . . . . 210 pinic . . . . . . . . . . 554
myristic . . . . . . . . . 597 polybasic . . . . . . . . . 253
myronic . . . . . . . . . 586 propionic . . . . . . . . . 602
nitric . . . . . 102, 115-119, 246 propylic . . . . . . . . . 602
—action of . . . . . . 12 protohydrate of sulphuric . . . 151
—test for . . . . . . . . . 460 prussic . . . . . . 509-511
—table showing the specific gra- pyrocatechuic . . . . . . . 615
vities and percentage strengths of 726 pyrogallic . . . . . . . . 577
nitrobenzoic. . . . . . . 613 pyromellitic . . . . . . . . 626
nitrous . . . . . . . . 109-110 pyrophosphoric . . . . . . . 134
—(nitrous anhydride) . . . . 108 pyroracemic . * & . . 608
—(nitric peroxide) . . . . . 110 pyrotartaric . . . . . 618
nonylic . . . . . . . . . 597 pyroterebic . . . . . . . 610
Nordhausen sulphuric. . . . . 356 pyruvic . . . . . . 608
octylic . . . . . . . . . 597 racemic . . . . . . . . 49, 623
Oenanthylic . . . . . . . . 604 ricinoleic . . . . . . . . 608
oleic . . . . . . . . . . 610 rocellic . . . . . . 618
orthophosphoric . . . . . . 135 ruberythric . . . . . . . . 586
orthoxybenzoic . . . . . . . 614 ruthenic . . . . . . . . . 382
osmic . . . . . . . . . . 381 rutic . . . . . . . . . . 597
oxalic . . . . . . . . 618-620 salicylic . . . . . . . 614
—reactions . . . . . . . . 628 Scheele's, preparation of . . . . 510
oxaluric . . . . . . . . . 717 sebacic . . . . . . . . . 618
oxamic . . . . . . . . . 673 Selenhydric . . . . . . . . 227
oxyadipic . . . . . . . . . 621 selenic . . . . . . . . . 163
oxybenzoic . . . . . . . . 614 separgylic . . . . . . . . 618
oxybutyric . . . . . . . . 605 silicie . . . . . . . . . . 187
oxygenated muriatic . . . . . 70 silico-fluoric . . . . . . . . 189
oxymalonic . . . . . . . . 621 silico-formic, or leukon . . . . 190
oxymethylbenzoic. . . . . . 614 sorbic . . . . . . . . . . 611
Oxymuriatic . . . . . . . 70, 82 stannic . . . . . . . . . 386
oxypicric . . . . . . . . . 678 Stearic . . . . . . 604-605, 635
oxysalicylic . . . . . . . . 615 stearolic . . . . . . . . . 611
Oxysuberic . . . . . . . . 621 suberic . . . . . . . . . 618
Oxysuccinic . . . . . . . . 621 succinamic . . . . . . . . 673
Oxytricarballylic . . . . . . 625 succinic . . . . . . . . . 620
oxyvaleric . . . . . . . . 605 —reactions . . . . . . 629-630
palmitic . . . . . . . . . 604 sulpharsenic . . . . . . . . 399
740
INDEX.
PAGE
Acid—continued.
sulpharsenious . . . . . . . 398
sulphidic . . . . . . . . . 224
sulphocarbonic . . . . . . . 182
sulphocyanic . . 516
—reactions 524, 630
Sulphodithionic. e e Q . 159
sulphomolybdic . . . . . . 409
sulpho-sulphuric . . . . . 158
sulphuretted hyposulphuric . . 159
Sulphuric . . .
47, 151-157
—action of, on oxysulpho salts . 274
—table showing the percentage of
real, corresponding to various
specific gravities of aqueous sul-
phuric acid . . . . . . . 727
sulphurous . . . . . . . 150
—a powerful reducing agent . . 506
—and sulphuric acids in the
air . . . . . . . . 103
tannic . . . . . . . . . . . 63
—reactions . . . . . . . . 630
tartaric 49, 621-623
—reactions . . . . . . . . 629
tartronic . . . . . . . . . 621
taurocholic . . . . . . . . 710
telluric - . . . . 165
terephthalic . 538, 547, 624
tetrathionic . . . . . 160
tetroleic . 611
tetrylic 602-603
thiacetic . * * * . 602
thionuric . . . . . . . . . 717
thiosulphuric - . 158
thymotic . . . . . . . . . 614
thymylcarbonic . . 614
titanic . 362
toluic . . . . . . . . . 612
tribasic - s - - . 253
tribromacetic . . . . . . . 602
tricarballylic . 625
trichloracetic - - . 602
trimellitic . . . . . . . . 626
trioxybenzoic . . . . . . . 615
trioxycarballylic . . . . . . 625
triosulphodithionic - * . 160
trisulphuretted hyposulphuric . . 160
trithionic . . . . . . . . 159
tungstic . . . . . 433
uric 715–717, 719
—reactions - - . . 628
valerianic . . . . . . . . 603
Valeric . . . . . . . . . 603
valero-lactic . . . . . . . . 605
vitriolic . 151
xylic . 612
xylidic . 624
xylilic . . . . . . . . . 612
Acid albumen . tº & . 689
anhydrides or oxides . . 593
carbonate - * * * . .309
chlorides, bromides, and iodides . 593
derivatives . 502– 595
peroxides e e - . 593
sodic sulphate . . . . . . . 301
Acid—continued.
sulphite . . . . . . . .
Acids. . . . . . .
effect of elasticity upon .
water unites with the anhydrides
to form . . . . . .
types of different
examination for
PAGE
. 302
. 252
. 205
. 253
453-463
reactions of some of the chief
626-630
haloid salts of the . . . 594
of the oxides of phosphorus. . 137
diatomic, amides of 672-673
dibasic . . . . 595, 617-624
fatty, supplement to the . 631-636
mineral and organic, as disinfect-
ants. e tº e º . 493
monatomic, amides of . . 672
monobasic . 595,596-617
organic . . . . . . . 591-630
—constitution of the . . . 592
—derivatives . 592
sulphonic . . . . 539
triatomic, amides o . 673
tribasic . . . . . . . 595, 625
Acids, action of, on—
alkaloids * . 649
bone . . 693
bromates . 278
carbon . 170
carbonates . 285
cellulin . . 683
chlorates . 278
chlorides . 258
glucose . . 584
glycerin . . 576
iodates . 278
iron . . 352
lead - * . 412
manganic oxides . . 327
metallic oxides. . 244
metals . 246
nitrates . . .276
nitric acid . . 117
nitric peroxide . 112
organic matter . 502
oxides of nitrogen . 114
phosphorus . 129
salts in solution . 5
silicates . * - - e. . 286
silver . . . . . . . . . 417
starch . 587
SUl{}I'OS6 . . 582
sulphates . 268
sulphides . 264
tin . . . . . . . 384
Acidulous waters . . . . . . 207
Acidum phosphoricum dilutum , 137
Aconitine . 653
tests for . . 675
Acrolein . . 644
Acrylic acid . 610
aldehyde . § º . . 644
series, acids of the . 609-610
—aldehydes of the . 644
INDEXe 74.1
PAGE IPAGE
Adhesion, affinity measured by the Alcohol, proportion of absolute, by
force of . . . . . . . 15 weight in 100 parts of spirit of
attraction between dissimilar mole- o
cules . . . . . . . . . ]
modifies chemical action . . . . 8
of gases to solids -
Adipic acid . • * * * *
AEsculin . . . . . . . . . . 586
Affinity (chemical)
definition, 1; conditions necessary
for the exertion of affinity, 2 ;
phenomena of affinity, 2-4;
changes in the sensible proper-
ties, 2; in the physiological pro-
perties, 3 ; in the physical pro-
ties, 3; circumstances influenc-
ing chemical affinity, 4-14;
gravitation, 4; cohesion, 4; elas-
ticity, 7; adhesion, 8 ; influence
of mass or quantity on affinity,
10; mechanical force may modi-
fy chemical action, 11 ; contact
decomposition, 11 ; influence of
heat and cold, 12 ; influence of
light, 14; influence of electri-
city, 14; influence of vitality,
14; degree, force, or energy of
affinity, 14; affinity measured by
reference to the specific gravity
of bodies, 15; by the force of
adhesion, 15; by the amount of
force required to effect the de-
composition of a compound, 16;
by the time of combination, 17;
by combining proportions, 18;
by the electrical condition,
19
Agate, amorphous variety of silica . 186
Air, action of, on—
different specific gravities at 60
. 730
reactions. . 589
an, what it is . 526
acetification of . . . . . . . 64
action of, on -
—chlorates, bromates and iodates. 278
—chlorides . . . . . . . . 258
–nitrates . . . . . . . . 276
—butylic. * - + . 529
Alcohol, dehydrogenatum . . 642
Alcoholic or vinous fermentation . 484
Alcohols, The 557-579
relation of, to the
—haloid ethers. . 557
—oxy-ethers . . . . . . . 557
—compound ethers . . . . . 557
dihydric . . . . 573-575
—aldehydes of * & . 645
—ethers of . . . . . . . . 640
hexhydric . . . . . 578
mercaptans or thio- 578-579.
monohydric . 558-572
—ethers of . . . . . . 638-640
tetrahydric . . . . . . . . 558
trihydric . . 575-578
—ethers of . . . . . . 640-641
supplementary chapter to the
580-590
Aldehyde, an . . 526
green . . . . 666
Aldehydes, The 642–645
reactions * e . 643
of the acetic series 643-644
of the acrylic series . 644
of the benzoic series . . 645
of the dihydric alcohols . . 645
of series (CaFIon—,COH). . 645
Algaroth, powder of . . . . . . 392
Alizarin . . 545, 546, 677, 679
Alkalamide. . 672
Alkali albumen * * . . 689
Alkali, volatile . . . . . . . .218
Alkalies, action of, on
—alkaloids . . 650
—metals . 248
—starch . 587
—Sugar . . . . . . . 582
as disinfectants . . . . . . 493
organic—the natural alkaloids . . 648
—definition, history, natural his-
tory, 648; preparation, 648-649;
properties, 649; action of heat, of
light, of electricity, of solvents,
649 ; of acids, 649–650; of alka-
lies, of haloids, of metallic salts,
of nascent oxygen, 650.
—fixed oils . . 632
—iron . . . . 352
—lead. • * * . 411
—sulphides . . . . . . . . .263
Air, weight of the . . . . . . 96
alkaline tº º . . .218
atmospheric . . . . . . 95-103
—history . . . . . . . . 95
—properties. . . . . . . . 96
—composition . . . . . . . 97
—constituents of . . 97-103
dephlogisticated . . . . . . 54
empyreal . . . . . . . . . 54
fixed or mephitic . . . . . . 177
hepatic . . . . . . . . . 224
inflammable . 191
—heavy . • * * . 228
pure . . . . . . . . . . 54
vital . . . . . . . . . . 54
Albumen in blood . 704
Albumens . * * , 688
derived . . . . . . . . . 689
Albuminate ſº q . . 689
Albuminoids or proteids 688-690
—reactions of . . 690
Albuminose . . . . . . . . 709
nitrites of the . . . . . . . .277
Alkalies and alkaline earths, action
of, on phosphorus . . . 129
and alkaline carbonates, action of,
on sulphides . . . . . . . 264
Alkaline air . . . . . . . . . 218
742
INDEX.
PAGE PAGE
Alkaline—continued. Aluminium—continued.
carbonates, action of, on organic reactions of the salts of . . . . 446
matter . * * * . . 504 || Amarine. . . . . . . . . . 663
earths, metals of the . 314-325 Amber 555
hydrates, action of the fixed, on
organic bodies . . 503
metals * * * * * 288-3 13
—characters, history, general pro-
perties . . . . 288
—reactions of the salts of the . . 440
nitrates . . . . . . . . . 56
silicates, preparation of . . . . 285
Waters. . . . . . . . . . 207
Alkargen . . . . . . . . . 668
Alkarsin . 667
Alkaloids, tests for certain of the 674-876
of vegetable origin. 651-653
—tests . . . . . 674-676
of animal origin . . . . . . 654
—tests * - . . 676
constitution of the . 654-658
Allantoin * @ & . 716
Allotropism . . . . . . . . . 50
Alloys . . . 249-251
changes in the sensible and physi-
cal properties of . º . 250
changes in the chemical properties 251
Alloxan . & e 4 . 716
Alloxanic acid . . 717
Alloxantin . . . . . . . 716
Allylamine . * * * * . 661
Allylbenzene . . . . . . . . 541
Allylene . . . . . . 228,536
Allylic alcohol . . . . . . . 568
ether . . . . . . . . 638
Almonds, artificial oil of 540, 541
Alphatoluic acid . . 612
aldehyde. © e . 645
Alphaxylic acid . . . . 612
Alum (potassic aluminic suiphate . 341
Amethyst, crystalline variety of silica 186
Amides, The . . . . 218, 671
Amides, acid . . . . . . 694
Amido-acetic acid. . . . . . . 694
Amido-benzene . . . . . . . 663
Amido-caproic acid 604, 694
Amidogen . . 218
Amido-toluene. . . 661
Amines, The . 658-663
properties of . . 659
Ammonia º . 218-221, 311
synonyms, history, natural his-
tory, 218; preparation, 218-219;
properties, 219–220.
table showing the percentage
amount of, in aqueous solutions
of the gas of various specific
gravities tº º e . . 729
portions of, in air . . . . . . 102
cake * * * . 341
chrome . . . . . . . . . 343
concentrated. . 341
gallium . - - , 434
iron . . . . . . . . . . 343
potash . 343
Roman . . 342
Alumina. * * . 340
Aluminate, trisodic . . 340
Aluminic acetate . . 601
bromide . . 340
chloride . , 341
ethide. . 670
fluoride • * . 341
iodide . . . . . . . . . . .340
oxide . . . . . . . . . . .340
phosphates e. . . , 343
silicates . . . . . . . . . 343
sulphate . . 34 l
—potassic . 341
sulphide . . . .340
Aluminium. 339-343
history, natural history, prepara-
tion, 339; properties, 339-340.
compounds of . . . . . 340-343
—in rain water. . 102
compound • * . 658
molecule of . . . . . . . . 46
solution of • * * 220-221
bases produced by the action of,
on the chlorides of platinum 406-408
action of, on phosphorus com-
pounds. . . . . . . . . 142
type g e º ºs s tº . 467
carbonate of. . . . . . . . 312
hydrosulphate of . . . . . . 31 l
muriate of e - e. e. . 311
purpurate of. . . . . 717
urate of . * * * * * . 719
Ammoniae phosphas . . . . . . 136
Aumonic acetate . e Լ . 601
bromide . . . . . . . . . 311
carbonate (normal) . 312
chloride . . 311
—zincic . e - © tº e . 332
chloride type . . . . . . . 467
cyanate . . . . . . . . . 49
—preparation . . . . . . . 514
cyanide . . . . . . . . . 611
dichromate . . . . 358
hydrate . . . . 311
hydric sulphide. . 311
iodide. * R & wº . 311
magnesic phosphate . . . 325
nitrate . . . . . . . . . 313
nitrite. e e . 277
pentasulphide . . 311
platino-chloride. . 405
rhodic-chloride. . . º . 380
sesquicarbonate . . . . . . 312
sulphocyanate . . . . . . . 516
sulphate . . . . . . 312
Ammonides, The . . 309
Ammonio-phosphate of magnesia . . 720
Ammonium . . . . . 221, 309-313
compounds of the hypothetical
metal ammonium . 310-313
INDEX,
743
PAGE PAGE
Ammonium—continued. Animal—continued.
bromide of . . . . . . . . 85 Solids . . . 691-695
sulphide of . . • , . . 311 | Anisic acid . 614
Amygdalin . . . . . . . 12, 586 aldehyde . 645
Amylainine. tº º º . . 660 | Annatto. 9. : 678
Amylbenzene . . . . . . . . 538 Anthracene . . . . . . . . . 544-546
Amylene. . 533 preparation, 544; properties. 544-546
glycol . . . 573 carboxylic acid. . . 617
Amylenic ether º . 640 series . . . . . . 543-546
Amylglycerin . . . . . . . . 575 | Anthracite, or steam coal . 174
Amylhydro-oxalic aci . 605 || Anthraquinone . . . . . . . 545
Amylic acetate. º . 602 || Antiseptic, an, what it is . . . . 493
alcohol . . . . . . . . . 567 | Antimonates, The . . . . . . 284
ether . . 638 Antimonic acid . . . . . . . 391
Amyloses. 586–588 — (antimonic oxide) . . . . . 390
Anaesthetic, nitrous oxide used as an 106
Analysis, organic . 467-482
notes for practical. 437-462
Anchoic acid . 618
Anethene . . . . . . . . . 552
Angelic acid . . . . . . . . 610
Anglesite . . . . . . . 410, 415
Anhydride, signification of the term 21
acetic. . . . . . . . 602
arsenic . 398
arsenious. . 396
auric . . 402
benzoic . • * . 613
boracie . . . . . . . . . 184
carbonic . . 177
chlorous . 79-80
chromic . . . . . . . . 359
hypochlorous 77-78
iridic . . 436
manganic. . . 327
molybdic. 408, 409
nitric . 114-115
—specific gravities and percentage
chloride . . . . . . . . . 392
chlorosulphide . . . . . . . 392
oxide . . . . . . . . . . 390
—hydrates (acids) of . . . . . 391
oxy-tri-chloride . . . . . . 392
Sulphide . . . . . . . . . 393
Antimonious antimoniate . . . . 391
bromide . . . . . . . . . 389
chloride . . . . . . . . . 392
hydride . . . . . . . . . 389
iodide . . . . . . . . . 389.
oxide . . . . . . . . . . 390
sulphide . . . . . . . . . 392
Antimoniuretted or antimonetted by-
drogen . . . . . . . . . 389
Antimonoso-antimonic oxide . . . .391
Antimony . . . . . 388-393
history, natural history, prepara-
tion, properties, uses, 388.
compounds of . . 389
—and oysgen . . . . . 390-391
—and sulphur . 392–393
chlorides of . . . . 391-392
reaction of the salts of . 452
ochre . * . 391
vermilion . . . 393
butter of . . 392
glass of . . . . 393
pentachloride o . 392
pentasulphide of . 393
terchloride of . . . . . . 392
tersulphide or sesquisulphide of . 392
Antozone . . . . . . . . 63-64
(hydric peroxide) . . 209
See Ozone.
Apocodeine . 652
Apomorphia e - . 652
Aqua fortis (nitric acid). . 115
strengths of various solutions of 726
nitrous . 108-109, 246
permanganic . . . . . . . 327
phosphoric . 133
phosphorous. . 132
ruthenic . . 38.2
selenious. * - e. . 163
silicic . . . . . . . . . . 186
sulphuric . 150
sulphurous . e tº . . 148
Anhydrides . . . . . . . . . 242
acid . . . . . . . . . . 593
Anhydrous hydrocyanic acid, pre-
paration of . . . . . . . 510
sulphuric acid . . . . . . . 150
Aniline . & . 661, 663-666
origin of name, synonyms, 663;
constititution, 663-664; proper-
ties, 664-665; uses, 665.
tests for . . . . . 676
blue . . . . 665
green . . 666
purple . 665
red . . . 665
yellow tº dº . . 666
Animal chemistry 68S-72S
Animal fluids, nutrient . 695–707
Aqueous vapor, determination of . 99
table of the tension of, expressed
in inches of mercury. . . . . . 736
power of carbon of absorbing . 171
Arabin tº a 588-589
Arachidic acid . tº e º - . 597
Archil and Cudbear, preparation of
77, 679
Argentic acetate . . . . . . . 601
bromide . . . . . . . . . 420
carbonate. . . . . . . . . 418
chloride . . . . . . . . . 419
744
INDEX.
g PAGE PAGE
Argentic—continued. Atmospheric air . . . . . . 95-103
chromate . . . . . . . . . 358 Atomic theory. . . . . . . . . 24
cyanide ... e. . . 511 | Atomic weights, relation between,
dichromate . . . tº º . 358 and specific gravity. 36
fluoride . . . . . . . . 4 18 and specific heats . 37
hyposulphate . . 418 || Atomicities, table of , 42
iodide . * * tº 418, 420 Atomicity or quantivalence . 39
metaphosphate . . . . . . . 418 Atoms . . . . . . . . . . . 25
nitrate. . . 75, 273, 277, 418, 421 | Atropic acid . 616
nitrite . . . . . . . . . 277 || Atropine. & e . 652
oxide : . 418 tests for . . . . . . . . . 675
peroxide . º . 419 || Attraction, table of 17
pyrophosphate . . 418 or action, chemical. . . . . . 1
sulphate . . 420 Aurates, the * - - - . 402
sulphide . . 420 Auric anhydride . . . . . . . 402
sulphite . . . . 273 chloride . . . . . . . . . 402
thiosulphate . . 418 cyanide . . . . . . . . . 511
Argentous chloride . 419 oxide . . . . . . . . . . 402
oxide . . . . . . . 418 sulphide . . 403
Aricin . . . 651 | Aurous chloride . 402
Arnicin . tº º . . 554 oxide . . . . . . . . . . 401
Aromatic series. . . . 537-54 1 sulphide . . . . . . . . . 403
Arsen-chloro-dimethide . . 668 || Austrapyrolene - . 550
Arsen-dimethyl . . 667-668 || Austraterebentheme . , 550
Arsen-mono-methyl . . . 667 || Azolitmine . . . . . . . . . 677
Arsenates . . . . . . . 283-284 || Azotates (nitrates) . 27.4
definition, properties, 283; tests, Azote (nitrogen) . . 93
- 283-284; uses, 284. Azotyl . . . . . . . . 106
Arsenic . . . . . . . . 396 chloride and bichloride of . 108
reactions of the salts of . . 452 bichloride (chloro-nitric gas) . 121
acid . . . 398 chloride (nitrous oxychloride) . . 120
anhydride . 398 || Azurite . . 367
sulphide . . .399
terchloride of . .399
tersulphide of . 398 IB
trihydride of . 395 º
white . . 396
compounds of . 395 | Balsams . . . . . . . . . . 555
—and hydrogen . 395 | Baric carbonate . . . . . . . 316
—and sulphur . . . 398 chloride . . . . . . . . . .316
Arsenicum . . . . . 394-400 chromate . . . . . . . . . 358
history, natural history, prepara- dioxide • * - - - . 315
tion, properties, uses, 394. dithionate . . . . . . . . 159
Arsenite, cupric . 372 hydrate . . . . . . . . . .316
Arsenites . 284 nitrate . . . . . . . 273, 316
Arsenious acid. . 396 oxide . * 9 & 4 . 315
—solubility of . . 397 peroxide . . . . . . . 56, 315
anhydride , - 396 selenate . . . . . . . . . 269
bromide . . . . . 400 sulphate . . . . . 269, 273, 316
chloride . . .399 sulphite . . . . . . . . . 273
dihydride. . 395 | Barium . . . . . . . . 314-316
hydride . 395 history, natural history, 314; pre-
iodide . . 400 paration, properties, 315.
pentafluoride . .395 compounds of . . . . . . . 315
sesquisulphide . . 398 —with oxygen and hydroxyl . . 315
trifluoride . . . . . . . 395 oxy-salts . . . . . . . . . 316
Arseniuretted or arsenetted hydrogen 395 reactions of the salts of . . . . 442
Arsine . . . . . . . . . 395 || Barometer, table of the corresponding
Arsines . 666-667 heights of the, in millimëtres
Artiads or evens . 43 and English inches . . . . . 733
Asparagin . . . . . . 653 | Baryta (baric oxide) . . . . . . 315
“Ate,” the termination . . 22 caustic (baric hydrate) . . . . 316
Atmolysis . . . . . . . . . 193 tungstate of . . . . . . . . 271
Atmosphere as a natural disinfec- Basalt . . . . . . . . . . 343
tant . 493 | Base, formation of a . . . . . . 59
INIDEX. 745
PAGE PAGE
Bases . . . 254 Bismuth, compounds of continated.
produced by the action of am-
monia on the chlorides of plati-
Illllll . . . . 406-408
examination for 440-458
effect of elasticity upon . . . . 8
Bassorin , * * * * . 5S9
Baumé's hydrometer, specific gravi-
ties corresponding to degrees of 731
Behemic acid * * . 597
Benzaldehyde . . . . . . . 645
Benzamidacetic acid . 613, 717
Benzamide . . . . . . 672
Benzene dº º ſº. . 539-541, 546
preparation, 539-540; properties,
540-541.
Benzenes, The 537-541
preparation, 537; properties, 537-539.
Benzenic acid . . . . . . . 612
Benzerythene . . . 540
Benzoic acid 538, 612
—reactions . . 629
aldehyde . , 645
anhydride . 613
chloride . 612
oxide * . 613
peroxide . . . . . . 613
series, acids of the 611-613
—aldehydes of the . 645
Benzol (see Benzene) . 539
Benzoline . 663
|Benzonitrile . 673
Benzoyl chloride . . 612
glycocoll . . 717
Benzyl benzene . 543
ethylbenzene . 543
metaxylene . . . . 543
paraXylene . 543
Benzylamine . . . 661
Benzylic alcohol . 570
chloride . . . . . 539
ether . , 638
series . . . 569-572
Benzyltoluene . tº § . 543
Berberine . . . . . . . 653
Beryllium & . 346
Biborate, sodic . . . . 304
Bicarbonate of potash
of Soda . . .
. 291, 295
tº * g * 304
Bicarburet of hydrogen . . 539
Bichloride of azotyl . . . . . 108
of carbon . . . . . . . . 180
Bile . . . . . . . . . 710–711
average composition per 1,000 parts 710
Bilin . . . . . . . . . . 710
Biliphaein . . . . . . . 711
Bilirubin . . . . . . . 711
Biliverdin . . . 711
“Bin,” “ter,” etc., the prefixes . . 22
Binary theory of salts . 25.2
Binoxide of nitrogen. . . . . . 106
Bismuth . . . . . . . . 372-375
natural history, preparation, 372;
properties, uses, 373.
compounds of . . . . . . . 373
—with oxygen and hydroxyl 374-375
—and chlorine . . . 375
—and sulphur . 375
oxysalts of * * * . 375
reactions of the salts of . 451
sesquioxide or trioxide of 374
submitrate of ge 277
trichloride of a s is & 375
Bismuthine . . . . . . . . . 667
Bismuthic oxide e i e º 37.4
Bismuthous bromide . . . . . . 373
chloride . . . . . . . 374, 375
fluoride * > 373
iodide . 37 3
nitrate 374, 375
oxide . . . . . . . . . 374
oxybromide . . . . . . . . 373
oxyiodide 373
Sulphate . e 374
sulphide . . . . . . . 374, 375
Bisulphate of soda. . . . . . . 301
potassic . . . . . . . . .
Bisulphite of soda . . . . . . 302
Bisulphuret or bisulphide of carbon .
Bisulphuretted hyposulphuric acid
Bitartrate, potassic . . . . . . 297
Bittern, the mother liquor of sea water 83
Bixine • * & ©
Black ash e es e. . 302
Black coloring matters . . 680
Bleaching powder. 280, 322
Bleaching power of chlorine 75, 76
Blood. . . & e <s 695–705
composition, 695; constitution,
696–697; properties, 697-700.
liquor sanguinis . . . . . . 703
Water in . . . . . . . . 703
albumen, fibrin, fatty matters, ex-
tractive matters in . & 704
mineral matters in . . . . . 705
average composition per 1,000 parts
of human . . . . 696
free gases present in 100 vols. of,
taken from the carotid of a
dog. º . 697
origin of the . . . 699
corpuscles . . 700-703
average composition of 1,000 parts
of, and of liquor sanguinis
crystals . . . . . . . 703
Bloodstone . g . 354
Blue coloring matters . 679
Bohemian glass $ sº e º 'º
Boiling point of water, variations
in . . . . . . . . . 199
Bones, properties of . . . . . . 693
action of heat, of water, of acids,
of burial on . . . . . . . 693
Bone-ash . . . . . . . . . 693
Bone black . . . . . . . . . 693
Bone earth . . . . . . . . 318
Bone oil . . . . . . . . . 693
Bones of a child and an adult, com-
position of the healthy human . 691
307
746
INDEX.
PAGE
Bones—continued.
of different mammals, birds, fishes,
and reptiles, composition of . . 691
composition of certain diseased . . 692
Boracic anhydride . . . . . . 184
Waters . . . . 207
Borate, magnesic . . 323
Borates, The * g. . 286
Borax (sodic biborate) . . 304
Boric or boracic acid 184-185
—preparation and natural history,
184-185
184; properties.
bromide . . . . . . 18.5
chloride . . . . . . . . . 185
ethide . . . . . . . . 669
fluoride . . . . . . . . . 185
methide . . . . 669
nitride . . . . 185
—preparation, properties . . . 185
sulphide . e . 185
Borides . . . . . . . . . . 266
Bornečne, a volatile oil . . . 553
Boron . . . 183-185
history, natural history, varieties,
183; preparation, 183-184; pro-
perties . . . . . . . . . 184
(amorphous) . . . 183-184
(crystalline) . . . . . . . . 184
Boyle's fuming liquor . 311
Brain and nerve tissue . . 695
Brassic acid . . . . . . . 610
Braunite . 327
Braziline . . . . . . . . 679
Dread-making, alcoholic fermenta-
tion in . 491
Brewing, alcoholic fermentation in . 490
Brimstone . . . . . . . . . 143
Brine . . . . . . 207
Brochantite . . * , 372
Bromates . . . . . . . . . 278
Bromic acid . . . . . . . . 86
Bromide of silver . . . . . . . 92
aluminic . * . 340
ammonic . . . . . . . . 31 l
antimonious. º . 389
argentic . . . . . . . . 420
arsenious º . 400
bismuthous . . . . 373
calcic . . º . 318
cupric . . . . . . 370
cuprous . . * . 370
hydric º . 213
magnesic. . . 324
plumbic . . 412
potassic . . . . . . . . .293
sodic . . . . . . . . . . 301
Bromides º e º 'º 260-261
definition, natural history, prepa-
ration, varieties, properties, 260;
tests, 260-261 ; estimation, uses 261
acid . . . . . . . . . . 593
cyanic . . . . . . . . . 614
Bromine * * * * 83-86
synonyms, 83; history, 83; natural
history, 83; preparation, 84;
-, ſº PAGE
Bromine—continued.
properties, 84; tests, 85; uses,
85.
compounds of, and oxygen . . 85-86
—and chlorine . . . . . . . 86
—nitrogen and . 120
—silicon with . . . . . . . 189
action of, on organic bodies. . 505
oxy-Salts of . . . . . . . . 279
estimation of chlorine, and iodine
in an organic body . . 473
Bromobenzoic acid . 613
Bromous chloride . . . . . . . 86
Bronze powder • . 387
Brown colouring matter . 680
Brucia, tests for . 676
Brucine . tº . 653
Burgos lustre . . 403
Burgundy pitch - - . 554
Burnett's disinfecting fluid. . 332
Butters, metallic . . . . . . . 257
Butylactic acid . 605
Butylbenzene . . 538
Butylamine . . 660
Butylene 228–533
glycol . . . . . . 573
Burylic alcohol . 529, 566-567
ether . . . . . 638
Butyric acid * * 602-603
aldehyde . . . . . . . . 643
fermentation . 485
Butyrone . . 646
C.
Cacodyl. . . . . . 667
Cadet’s fuming liquid . 667
Cadmium . 376
history, natural history, properties,
uses, 376; compounds of cad-
mium with oxygen, with the
haloids, and with sulphur, 376.
reactions of the salts of . . 451
Cadmic chloride . . . . . . . 376
hydrate . . 376
iodide. . º - - . 376
oxide . . . . . . . . 376
sulphide . º . 376
Caesic carbonate . . .309
chloride . * - © , 309
hydrate . . . . . . .309
nitrate . . . . . .309
oxide . tº e º 'º . .309
sulphate . . . . . . . . . 309
—hydric. . .309
Caesium . , 309
compounds of caesium and rubi-
dium . . . . . . . . . 309
Caffeine . . . . . . . . . . 653
tests for . . . . 676
Cairngorm, crystalline variety of si-
lica. . . . . . . . . .
Cajuputol . . . . . . . . . 552
Calamine, electric . . . . . . 333
INDEX. 747
PAGE PAGE
Calcareous waters . . . . . . 207 | Carbon–continued.
Calcic bromide . . . . . . . 318 preparation, 167-168; proper-
carbonate 318, 321 ties, 168-175.
chloride . 318, 320 compounds of carbon and oxygen . 175
disilicide. . . .318 — — and the haloids . . . . . 180
disulphide . . 318 — — with oxygen and the haloids 181
fluoride 318, 320 — — and Sulphur . . . 182
hydrate . . . .319 — — and hydrogen . . . 227
hypochlorite . 318 —experimental determination of
hyposulphite . 272 the carbon, hydrogen and oxygen
iodide . e . . 318 in an organic compound not con-
nitrate 318, 321 taining nitrogen . . . . . 469
oxalate . . . 318, 322 estimation of the hydrogen and
oxide . . . . . . . . . . 319 carbon in a body containing
pentasulphide . . . . . . 318 nitrogen . . . . . . . 471
peroxide . . . . . . . . . 319 chemistry of carbon and its
phosphate * 318, 322 compounds, (Laurent's definition
phosphide . . 3.18 of organic chemistry) . 464
sulphate . * - 318, 320
sulphide . . . . 318, 320
thiosulphate . . 158, 318
Calcis phosphas . . . . . . . 136
Calcium . . as º º 317-322
history, natural history, 317 : pre-
paration, 317, 318.
compounds of . . . . . . 318
—with oxygen and hydroxyl
318-319
reactions of the salts of . . 442
Calendulin . . . 588
Calico-printing - º 6S 1 - 682
Calomel (mercurious chloride). . 424
Camphic acid . . 553
Camphine (Boston turpentine) . . 549
Campbol a • * * . 553
Camphor, common 552, 553
Borneo . . . 553
Camphoric acid . . 553
oxide . . 553
Camphors . 552-553
Candles . . . 635-636
Cannabin . . . 554
Caoutchine . 556
Caoutchouc . 556
Capric acid . . 597
Caproic acid 603-604
alcohol º . 558
aldehyde . . . 643
Caprylic acid . 597
alcohol . . 55S
Capsicine . . . . . . . . .
Capsicum resin . . . . . . . 554
Carbamic acid
Carbamide . . . . . . . -
Carbides . . . . . . . . . 2
Carbimide . . . . . . .
Carbinol * - © - -
Carbolic acid . . . . . . . . 571
to distinguish, from kreasote . . 571
Carbocresylic acid 614
Carbo-hydrates . . . . 580-590
Carbo-hydroquinonic acid . . 615
Carbon . . . 166-183
synonym, history, natural his-
tory, 166; varieties, 166-167;
Carbon, a grouping agent in non-
nitrogenized bodies . . . . . 466
daily consumed as food, and daily
evolved as carbonic acid . . . 66
consumed per hour by males . . 66
action of, on the metals . . . . 245
of gas retorts . 167, 168
(amorphous) . . 167, 168
atom types . . . . . . . . 466
or carbonic dioxide . . . . 177
monoxide . . . . . . . . 175
Carbonate, acid . . . . . . . 309
argentic . . . . . . . . 418
baric . . . . . . . . . . 316
cºsic . . . .309
calcic 318, 321
diculpric . . 367
dipotassic . . . 295
ferrous * - . . 357
hydrated dibasic . . 367
hydric sodic . º . . 304
lithic . . . . . . . . .30S
magnesic . . . . . 325
manganous . . . . . . 330
Inickelous . . . . . 336
normal ammonic * . 312
plumbic . . . . . . . . 412
potassic . . . e . . . 309
sodic . . . . . . . . 302
thallous . . . . . 431
Zincic . . . . . . . .333
Carbonates tº e º - 284-2S5
definition, 284; natural history,
284-285 ; preparation, proper-
ties, tests, uses, 285.
alkaline, action of on organic mat-
ter . . . . . . 504
cobaltous . . . . . . . 334
cupric . . . . . . . 37.2
double . . . . 287
Carbonic acid . wº . 177, 606–607
—estimation of, in the air . . . 100
—proportions of, in the air . . . 101
—produced and air vitiated per
hour . . . . . . . . 102
anhydride . . . . . . . . 177
—synonyms, history, 177; natural
748
INDEX.
I’AGE
Carbonic anhydride—continued.
history, 177-178; preparation,
178; properties, 178-180; tests,
180.
chlorobromide . . . . . . . 181
dibromide . . . . . . . . 181
dichloride . . . . . . . . 181
—synonym, history, preparation,
properties tº tº ºn tº º
disulphide 182-183
–synonyms, history, preparation,
182 ; properties, 182-183. .
monochloride . . . . . . 181
—Synonyms, preparation, proper-
ties, 181.
oxide . . . 175
—synonyms, history, natural his-
tory, 175; preparation, 175-176;
properties, 176-177.
Oxychloride . . . . . . . 181
181; preparation,
—synonyms,
181-182; properties, 182.
Oxysulphide . . . . . . 183
—preparation, properties . . . 183
subchloride or hexachloride . . 181
tetrabromide . . . . . . . 181
tetrachloride 180, 532
—synonym, history, preparation,
properties . . . . . . .
tribromide . . . . . . . . 181
trichloride . * * * . 181
—synonym, history, preparation,
properties. . . . . 181
Carbonyl chloride. . . . . . . iși
Carburetted hydrogen . . 228-230
Carmine . . . . . . . . . . 679
Carminic acid. . 679
Carrageenin . . . . . . 588
Carré's ice-making apparatus . . 219
Carthamine . . . . . . . . 679
Carvene . . . . . . . . . . 552
Carvol . . . . . . . . . . 552
Casein º, º is a s 486, 689
Cassel green (basic manganate) . 329
Castile soap. . . . . . . 635
Castorin . . . . . . 554
Catalysis, a new force assumed by
FAGE
Cetene . & ſº º . 533
Cetin . . . . . . . . . 634
Cetylic alcohol . . . . . . 558
Chalcedony, amorphous variety of
silica . . . . . . . . 186
Chalk . . . . 318
Chalk-stones . . 716
Chalybeate waters . . 207
Charcoal g & 172, 174
as a disinfectant . . . . . . 494
as a fuel . . . . . . . . . 174
in medicine . . . . . . . . 175
animal 167, 168, 172
vegetable. . . . . 172
wood . & . 167, 168, 172
Chemistry, organic . 463
—definitions of . . . 463
animal g e 688-721
vegetable. . . . 683-687
Chenotaurocholic acid . 711
Chessylite º . 37.2
Chili saltpetre . . 304
China stone . 346
Chinoline tº gº tº . 662
Chitin . . . . . . . . . . 586
Chloral * * * g. . 644
Chloralum, an impure aluminic
chloride . e gº º . 341
Chlorate, hydric . . . . . . . 82
potassic e 11, 56, 297
Chlorates . . . . . . . . 278
Chloric acid . . . . . . . . 82
—synonyms, history, preparation,
properties . . . . . . . 82
dioxide . . . . . . . . . 81
peroxide . . . . . . . . . 81
—synonyms, history, preparation,
properties. . . . . . . 81
of azotyl ... 108
Chlorhydric acid . * > * . 210
Chloride of hydrogen . . . . . 210
of lime . . . . . . 280, 322
of nitrogen . & 119-120
—history, preparation . . . . 119
—properties. g ºr º 119-120
of nitryl (nitrylic chloride) . . . 121
Berzelius . g . 489
doctrine of . . . . . . . . 12
Celestine (strontium) . . 316
Cellulin 683-684
preparation, properties, 683; ac-
tion of acids, 684; uses, 684.
Cellulo-nitrin . . . . . . . 684
Cellulose . . . . . . . . . 683
Cements, or hydraulic mortars . 319
Centimetres, to reduce cubic, to cubic
inches . . . . . . . . . 733
Cerasin . . . . . . . . . . 589
Cerium . . . 346
Cerotene * 533, 558
Cerotic acid . . . . . 597
Ceruse, or white lead . . 416
Cervantite . . . . . . . . 391
Cerylic alcohol . . . . . . . 558
of silver . . . . 92
acetic . . . . . . . . . 602
acetyl . . . . . . . . . 602
aluminic . . . . . . . . 341
ammonic . . . . . . . . 311
—type . . . . . . . . . 467
—platino- . . . . . . . . 405
—rhodic . . . . . . . . . 380
antimonic . . . . . . . . 392
antimonious . . . . . . . 392
argentic . . . . . . . . . 419
argentous . . . . . . . . 419
arsenious . . . . . . . . 399
auric . . . . . . . . . . 402
aurous . . . . . . . . . 401
baric . . . . . . . . . 316
benzoic . tº ſº : . . . 612
benzoyl . . . . . . . . . 612
benzylic . . . . . . . . 539
INDEX.
749
PAGE PAGE
Chloride—continued. Chlorides—continued.
bismuthous . . . . . 374, 375 acid º & . 593
bromous . . . . . . . . 86 cyanogen . 513
cadmic . . . . . . . . . 376 | Chlorine . . . . . . . 70-77
Caesic . . . .309 synonyms, 70; history, 70; na-
calcic. 318, 324 tural history, 71; preparation,
chromic . & . . 360 71-72; properties, 72-76; esti-
chromous . . . . . . . . 360 mation, 76; uses, 76.
cobaltic . . 334 compounds of copper and 369-370
cobaltous . 334 —of iodine and . . . . . . 91
cupric . 370 —of iron and . . . . . 355
cuprous . . 369 —of lead and . . . 414
ferric . . . . . 355 —of mercury and . 424-427
ferrous . 355 —of molybdenum and . 409
gallium . 434 —of nitrogen and . . . . 119
indic . . 338 —of nitrogen, oxygen and . 120-121
iridic . . 436 —of oxygen and . e 76-77
iridious . 436 —of platinum and . 406
magnesic . 324 —of selenium and . . . 164
Imanganic . 329 —of silver and 419–420
manganous . . 329 —of sulphur and . . 161
mercurious . . 424 —of titanium and . 363
mercurio . . 425 See Chlorides.
methenyl . 532 estimation of chlorine, bromine,
methylic. . 532 and iodine in an organic body . 473
methylene . 532 oxysalts of . . . . . . . . 279
molybdic * - . . . 409 peroxide of . . . . . . . . 81
molybdous . . . . . . . . 409 action of, on
nickelous . 336 —alcohol . . . . . 565
nitrylic . . 121 —organic bodies . 504
Osmic . . 381 —oxides . . . . . . . . . 244
palladic . 378 action of sulphurous anhydride on 149
palladious . . . 378 Chlorisatin . . . . . . . . . 679
phosphoric 140, 506 Chlorite, distinction between a, and a
phosphorous . . 139 hypochlorite . . . . 281
platinic . . . . 406 Chlorites . . . . . . 280
platinous. '. 406 —definition, preparation, properties 280
plumbic . 414 Chlor-benzenes * * * • *
potassic . . 292 | Chlorobenzoic acid . 613
—platino . . 405 Chlorocarbonic acid . . 181
—rhodic . . 380 | Chlorochromic acid . 360
rhodic . 380 | Chloroform . . . . . . . 532–533
ruthenic . . 382 | Chloro-nitric gas . . . . . . 121
ruthenious . 38.2 —synonyms, preparation, properties 121
silicic . 181 | Chloro-nitrous gas (nitrous oxychlo-
sodic . . 299 ride). . . . . . . . . . 120
—platinic . 405 | Chloropernitric gas (nitrylic chloride) 121
—rhodic . 380 | Chlorophyll . . . . . 680
Stannic . 387 | Chloropicrin . . . . . . . . 533
Stannous . 386 Chloro-platinates . . . . . . 406
sulphur . . . . . 161 | Chlorosulphuric acid . . . . . 149
sulphuryl hydroxyl . 162 | Chlorosulphuric oxide . . . . 162
thallic * * * . 431 Chlorotoluene . . 539
thallous . . 431 Chlorous acid * * * * * 80-81
thionyl . 161 —preparation, 80; properties, 80-81.
ll I’ll] OllS . . 337 anhydride. . . . . . 79-80
zincic. * * * * . 332 —history, preparation, properties . 60
—a dehydrating agent . 506 | Chlorozone as a disinfectant . 494
—ammonic . . . . . 332 | Choke damp . . 177
zirconic . . . 347 Cholesterin . & e - a 572, 721
Chlorides • * * 256-259 | Cholic acid . . . . . . . . 710
definition, natural history, 256; Cholophaein e . 711
preparation, 256-257; varieties, Chrome-iron-slate . ë . 358
257; properties, 257-258; tests, Chondrin, ultimate composition of
258; estimation, 259; uses, 259. 694,695
750 INDEX.
PAGE | Coal—continued. PAGE
Chromate, argentic . . . . . . 358 composition of various kinds of . , 172
baric . . . . . . . . . . 358 ash of . . . . . . . . . 173
hydric sodic . . . . . . . . 358 amount of sulphur in different
plumbic . . . . . . . 360, 415 varieties of . . . . . . . 173
—as an oxidizing agent . . . . 469 burning of, in close vessels and
potassic . . . . . . . . . 359 in the open fire . . . . . . ] 73
sodic. . . . . . . . . . . 358 anthracite or steam coal . . . 174
Chromates . . . . . . . . . 269
definition, 269 ; tests, 270.
Chrome, orange . . . . . 360
yellow . . . . . . . . . 360
Chromic acid - . . 359
Chromium * * * * * . 357-361
history, 357; natural history, pre-
paration, properties, 358.
compounds of . . . 358-361
reactions of the salts o . . 446
fluorides of . . . . . . . . 360
sesquichloride of . 360
sesquioxide of . . . . . 358
Chromic acid, a powerful oxidizing
agent . . . . . . . . . 506
anhydride * * . 359
chloride . . . . . . . . . 360
dioxide . tº º . 358
nitrate . . . . . . 358
oxide . . . . . . . . . . 358
oxydichloride . 360
sesquisulphide . . 361
sulphate . . . . . . . . . 361
sulphide . . . . 358
Chromous chloride & . 360
dichromic tetroxide . . . . . . 358
oxide . . . . . . . . . . 358
Chrysammic acid . . 678
Chrysaniline . . . . . . 666
Chrysene . . . . . . 540, 546, 547
Chryseon or silicone . . . 190
Chrysoquinone. . . . . . . 547
Chyle and lymph . . . . . . 705-706
percentage, composition of . 705
Cinchonicine . . . . . . . . 651
Cinchonidine * G . 65.1
Cinchonine . . . . . . . . . 651
tests for . . . 675
Cinchovatine . 651
Cinnabar . 421
Cinnamene . . 541
Cinnamic acid . . 616
alcohol . 572
aldehyde . . . . . 645
series, acids of the . . 616
Citraconic acid . . 624
Citramalic acid. . , 621
Citramic acid . . . . . 67 3
Citramide . . . 673
Citric acid . 625
natural history, preparation, pro-
perties. . 625
reactions . . . 628
Clay . . 343-346
formation, 343-344; composition,
344; properties, 344.
Coagulation of the blood
Coal . . . . . .
698-699
172- 174
products of the action of heat on 497
—of the distillation of . . . . 498
Coal-gas . . . . . . . . . 232
composition of . . 232
Coal-tar dyes 665-666
Cobalt g & ſº 333-335
history, natural history, prepara-
tion, properties . . . . . . .333
compounds of 333-335
reactions of the salts of . . . . 449
protoxide of (cobaltous oxide) . . .333
sesquioxide of (cobaltic oxide) . . 334
Cobaltic chloride . . . . . . . 334
nitrate . . . . . . . . . 334
oxide . . . . . . . . . . 334
Cobalticyanogen . . . . . . . 518
Cobaltous carbonates . . . . . 334
chloride . . . . . . . . . 334
cyanide . . . . . . . . . 511
nitrate . . . . . . . . . 334
Oxide . . . . . . . . 333, 334
—hydrated . . . . . . . . 334
sulphate . . . . . . . . . 334
Cobaltoso-cobaltic oxide . . . . 334
Cocaine . . . . . . . . . . 653
Cochineal . . . . . . . . . 679
Codamine . . . . . . . . . 662
Codeine . . . . . . . . . . 652
Cohesion, attraction between similar
molecules . & º 1
modifies chemical action . 4
Cohesion of the constituents . 5
of the resultant . . 5
Coke se 167, 168
Colchicine . . . . . . . 653
Colcothar . . . . . . . . . 354
Cold, influence of heat and, on attinity 12
Collidine . . . . . . . . . 661
Collinic acid . . . . . . . . 612
Collodion . . . . . . . . . 684
Colophene . . . . . . . . . 550
Colophony . . . . . . . . . 554
Coloring matters . e 677-680
—power of carbon of absorbing . 171
Combination, atomic and molecular 28
molecular . . . . . . . . 33
by volume . . . . . . . . 33
by weight . . . . . . . . 27
Combining proportions, affinity mea-
sured by . . . . . . . . 18
Combustion, use of oxygen as an
agent of . . . . . . . . 67
temperatures requisite for . . . 233
Compound radicals, Liebig's chem-
istry of . . . . . . . . 47
Compounds, elements and . . . . 20
Concrete . 320
Condy's green disinfecting fluid 270, 329
INDEX. - 751
PAGE
Conine sº 651, 661
tests for . * * * * * . 674
Contact decomposition . . . . . 11
Convolvulinoleic acid . 608
Copal . . 555
Copper 364-372
natural history, 364; preparation,
364-366; impurities, 366 ; pro-
perties, 366; uses, 367.
compounds of . . . . . 367
—and hydrogen . 368
—and oxygen . . 368-369
—and chlorine . * 369-370
—and sulphur . . . . 370-371
cupric oxysalts . ſº 371-372
reactions of the salts of . . 451
pyrites . . . . . . . . 370
ammonio-sulphate of . . . . . 372
basic phosphates of . 37.2
black oxide of . . 369
chloride of . . . . . . . . 370
monoxide . . 369
phosphide of . 371
subbromide of . . 370
subchloride of . . 369
Subiodide of . tº tº $ , 370
suboxide or red oxide of . . 368
subsulphide of . • 370
sulphate of . . . . . . . 371
sulphide of . 371
Copperas . . . . . . . . . 356
Corky matter . . . 685
Coridine . & a $ sº º & . 662
Cornelian, amorphous variety of silica 186
Corrosive sublimate . 425
Corpuscles, blood. 700-703
—white . . . . . . . . . 700
—red . . . . . . . . . . 701
— —chemistry of the constituents
701-703
Corundum . . . . . . . 340
Cream of tartar . . . . . . . .297
Cresol . . . . . . . . . . 572
Cresotic acid . & & © . 614
Cresylic alcohol . . . . . . . 572
Crith, the . . . . . . . . . 35
Crocus of Mars . . . . . . . .354
Crotonic acid . . 610
aldehyde . . . . . . . . 644
Crotonylene 228, 536
Crystallin . . . . . . . . 701
Crystallization, water of . . . . 205
Cubic nitre tº tº . . 304
Cudbear, preparation of 677, 679
Cumene (mesity}ene of coal tar oil) . 537
Cumic acid * * * . 612
aldehyde . . . . 645
Cumi ic acid * . 610
Cumidic acid . . . . . . 624
Cumidine º , º is tº º . 662
Cumilic alcohol . . . . . . . 569
Cumylic acid . . 612
Cupellation tº gº º & . 411
Cupric acetate . . . . . . . 601
arsenite . 284, 372
Cupric—continued. FAGE
bromide . . . . . . . . . 370
carbonates . . 372
chloride . . 370
ferrocyanide . 517
hydrate . . 367
iodide . 370
nitrate . 370
oxide. . . .369
Oxysalts . . . 371-372
pentasulphide . . 371
phosphide . 371
selenide . . . . 367
sulphate . . . . . 371
sulphide . . 371
Cuprous bromide . . 370
chloride . . 369
hydrate . . 367
hydride . 368
iodide . . 370
oxide . . . . . 368
quadrantoxide . . . . 368
sulphide . . . . . . . . . 370
Cuprylic aldehyde . . . . . . 643
Curcumine . . . . . . . 679
Currying, mode of . . . . 637
Cyamelide . . . . . . . . . 515
Cyanate, ammonic . . . . . . 49
Cyanates, preparation of . 514
Cyanic acid . . . . . . . . 514
bromides . . . . . . . 514
chloride (gaseous, liquid, and solid) 513
iodide . . . . . . . . 514
sulphide . . . . . . . 514
Cyanide, ethyl . . . . . . . 532
methyl . . . . . . . . . 532
palladious tº tº . 379
potassic . . . . . . . . . 293
Cyanides, 512-513
preparation of metallic cyanides,
512; properties, 513; uses, 513.
double . . 517-522
Cyanine *: . 679
Cyano-ethane. . . . 532
Cyanogen . 49, 508-509
derivation, history, natural his-
tory, preparation, 508; proper-
ties, 508-509,
and its compounds . . . 508-524
chlorides of . . . . . . . . 49
cyanides, chlorides, and hydroxides
of . . . . . 511-516
double salts of . * 517-524
and hydroxyl, compounds of . . 514
Cyanomethane . . . . . . . 532
Cyanuric acid, preparation and pro-
perties . . . . . . . . 515
Cydonin . . . . . . . . . 588
Cymene . . . . . . . 537, 553
Cymidine . . . . . . . . . 662
Cymylamine . . . . . . . . 661
Cystine . . . . . . . . . . 719
D.
Damaluric acid . . . . . . . 610
752
INDEX.
PAGE PAGE
Dammar resin . 554 | Dichloride—continued.
Damolic acid . e is . 610 sulphuryl . 161
Daniel's hygrometer . . . . . . 99 || Dichlorides . 257
Daturine . . . . . . 652 | Dichlorobenzene . . 540
Decane . . . . . 528 | Dichloromethane. . 532
Decatylic alcohol. . 558 | Dichromate, ammonic . 358
Decay, conditions necessary for . . 495 argentic . , 358
Decene . * @ tº & . 533 potassic . . . . 359
Decine * * * * * * . 536 Dicupric carbonat . 367
Decomposition of a compound, affi- Dicymylamine . 661
nity measured by the amount of Didymium . - . 347
force required to effect the . . 16 | Diethacetic acid . . 602
Decomposition, artificial 496-507 | Diethyl . . 528
contact . . . . . . . . . 11 | Diethylamine . . 660
Decone . * * * . 536 | Diethylbenzene tº a 3. . 537
Delphinine . . . . . . . . . 653 | Diethyl carbinol . . . . . . 559
Density of bodies increased by affinity 3 | Diethylenic glycol . 575
maximum, of water . 200 | Diethyl ketone . . . . . 646
Deodorizer . • * * * - 493 | Diethyl methylbenzene . . . . . 537
I)ephlogisticated nitrous air . 104 Diethyl phosphine . 666
Desoxalic acid. e . 625 | Diffusiometer of Graham . . 193
Deutoxide of nitrogen . 106 | Digestion, and the fluids concerned
Devitrification . . . . . . . .307 in it . . . . . . . 707-712
Dextrin . . 588 Dihydric alcohols, aldehydes of the . 645
Dextro-glucose . 584 disulphide . . . . . . . . 226
Dextrose . . . . . . . 584
“Di,” “tri,” “tetra,” etc., the prefixes 22
Diacetamide . . . . . . . 672
Diacetenylbenzene . . . , 547
Diadelphic or methyl type. . 466
condensed, type . 467
Diallyl . . 536
Dially)amine . 661
Dialuric acid . 717
Diamines • * * * . (362
Diammonic disulphide . . 311
sulphide or protosulphide . . . 311
I)iamond, the . 166, 167, 169, 172
Diamylamine . * * * . 660
Diamylene . - . 533
Diamyloxalic acid . 605
Diantimonic tetroxide . 391
Diarsenic pentasulphide . 399
Diarsenious disulphide . . 398
Diaspore -> . 340
I)iastase . . . . . . . . 486
Diatomic acids, amides of . 672-673
Dibasic acids , - * * . 253
Dibenzyl . . . . . . . 543
Dibenzylamine e . 66 I
Dibismuthic tetroxide . . 373
Dibismuthous dioxide . 374
disulphide . . 375
tetrachloride . 373
Dibromacetic acid . 602
I)ibrom-anthra-quinone . 545
Dibromide, Sulphuryl . 16.2
Dibromobenzene . . 540
Dibutyl . 528
Dibutylamine . . 660
Dichloracetic acid , 602
Dichlor-anthracene . . 545
Dichloride, carbonic. . 181
osmious . ºr gº . 381
sulphur . . . . . . . 161
Selenide . º . . . . . 227
sulphate . . . . . . . . . 151
sulphide . . 224
tetrathionate . 160
trithionate . . 159
Dihydride, arsenious . 395
Diiodate, potassic gº tº . 278
Dimanganic hexachloride . 327
Dimethylamine . . . 660
Dimethylanthracene. . 543
Dimethylbenzenes , 537
Dimethyl carbinol . 559
ethyl carbinol . . 559
isopropyl carbinol . . 559
ketone . . . . 646
phenylic alcohol . 569
phosphine . . 666
propyl carbinol . 559
Dinitride, dititanic . . . 362
Dimitrobenzene 540, 541
Dinoxide, nitrogen . 106
Diorite . - , 343
Dioxide, baric. . 315
chloric . 81
chromic . tº t e º 'º . 358
dibismuthous . . . . . . 374
hydric (hydric peroxide). . 209
iridic . . . . . . . . 436
manganic . 328
potassic . . 291
sodic . . .299
Dioxides -> . 242
Dioxyacetic acid . ... 609
Dioxyadipic acid . . 621
Dioxybenzoic acid . 615
series, acids of the . 615
Dioxypropionic acid. - . 609
Dioxysuberic acid . . . . . 621
Dioxysuccinic acid . . . . 621
Diphenyl . 540, 543
INDEX. 753
PAGE PAGE
Diphenylbenzene. . . . . . . 547 | Ebonite . . . . . . . . . . 556
Dyphenylketone . . . . . . . 547 | Elaidic acid . . . . . 610
Diphenyl methane . . . . . . 543 | Elasticity modifies chemical action .. 7
Diplatosamine . . . . . . . 407 | Elayl (ethylene) . . . . . . 229
hydrochlorate of . . . . . . 407 | Elective gravitation . . . . . . 1
sulphate of . . . . . . . . 407 | Electric calamine . . . . . . 333
Dipotassic carbonate . . . . . . 295 | Electrical condition, affinity measured
disulphide . . . . . . . . 294 by the . . . . . . . . 19
pentasulphide . . . . . . . 294 | Electrical properties of metals . . 240
sulphate . . . . . . . . . 295 | Electricity, action of, on
sulphide . . . . . . . . . 294 —alkaloids . . . . . . . . 649
trisulphide . . . . . . . . 294 —chlorides . . . . . . . . 258
Dippel's oil . . . . . . . . 693 —metallic oxides . . . . . . 243
Dipropargyl . . . . . . . . 537 —organic bodies . . . . . . 506
Dipropyl ketone . . . . . . . 646 —phosphorus . . . . . . . 126
Disilicide, calcic . . . . . . . 318 influence of, on chemical action . 14
Disinfectant, bromine a . . . . 85 | Electrolysis of water . . . . . 196
Disinfectants, natural . . . . . 493 Elements and compounds . . . . 20
artificial . . 493 Eloeoptene . . . . . . . . . 551
Disinfection, power of, of chlorine is, 76 Embolite . . . . . . . . . 417
Disodic hydrogen phosphate . . . 281 Emery . . . . . . . . . . 340
Dissociation, partial decomposition of Emetin . . . . . . . . . 651
some bodies at a high tempera- Emulsin . . . . . . . . . 486
ture . . . . . . . . . 13 | Enamelling glass . . . . . . . 307
Distannic trisulphide . . . .385 | Epihydric acid . . . . . . . 608
Distillation, process of destructive . 468 Epson salts . . . . . . 260, 325
Disulphide, calcic . . . . . . 318 Equation, chemical . . . . . . 23
carbonic . . . . . . . . . 182 | Erbium . . . . . . . . . . 346
diammonic . . . . . . . . 311 || Eremacausis, or slow oxidation 60,495-496
dibismuthous . . . . . . . 375 conditions necessary for decay . . 495
dihydric . . . . . . . . . 226 circumstances influencing . . . 495
dipotassic . . . . . . . . 294 | Ergotin . . . . . . . . . . 554
ferric . . . . . . . . . . 355 | Erucic acid . . . . . . . . . 610
molybdic . . . . . . . . 409 | Etaldehyde . . . . . . . . . 644
Disulpho-dithionic acid . . . . 160 Ethacetic acid . . . . . . . . 602
Diterebene . . . . . . . . . 550 Ethal . . . . . . . . . . . 55S
Dithionates . . . . . . . . . 273 Ethane . . . . . . . 228, 526, 528
Dithionic acid . . . . . . . 159 Ethelmethylbenzene . . . . . . 537
synonyms, preparation, properties 159 | Etheme (ethelene). . . . . 526, 533
Dithionous acid . . . . . . 15S hydroxyl . . . . . . . . . 564
Dititanic dinitride . . . . . . 362 Ether, solubility of chlorides in . . 258
hexachloride . . . . . . . 362 acetic . . . . . . . . . Ö02
hexafluoride . . . . . . . 362 Ethers, The . . . . . . . 638-641
Ditolyl . . . . . . . . . . 543 compound ethers . . . . . . 593
Dixylylamine . . . . . . . . 661 haloid ethers . . . . . . , 641
Dodecane . . . . . . . . . 528 sulpho- or thio-ethers . . . . . 641
Doeglic acid . . . . . . . . 610 oxy-ethers . . . . . . 638-641
Dolomite . . . . . . . . . 287 Ethers of monohydric alcohols. 63S-640
Dolerite . . . . . . . . . . 343 of dihydric alcohols . . . . 640
Draconine . . . . . . . . . 679 of trihydric alcohols . . . 640-641
Dragon's blood . . . . . . . 554 Etherene (ethylene) . . . . . . 229
Dry methods, examination of sub- lºtherin (ethylene) . . . . . . 229
stances by . . . . 437-439 Ethine (acetylene) . . . 231, 526, 536
Dualistic theory of salts . . . . 251 Ethyl, nitrite of . . . . . . . .277
Dulcite . . . . . . . . . . 578 acetamide . . . . . . . . 672
Dyeing and calico-printing . 681-682 amylamine . . . . . . . . 661
Dyes, coal-tar . . . . . . 665-666 Ethylbenzene . . . . . . . . 537
benzyl tº tº º º 543
Bthylcrotonic acid . . . . . . 610
E. Ethyl cyanide . . . . . . . . 532
diacetamide . . . . . . . . 672
Earth, constituents of the solid crust Ethyldimethylbenzene . . . . . 537
of the . . . . . . . . . 55 | Ethyl methyl carbinol . . . . . 559
Earths, metals of the . . . 339-363 Inaphthalene . . . . . . . . 542
lºarthenware, manufacture of common 345 phosphine . . . . . . . . 666
3 C
754
INDEX.
PAGE PAGE
Ethyl-continued. Ferric—-continued.
propyl ketone . 646 cyanide . . . . . . . . . 511
Ethyl-urea . . 662 disulphide . . . . . . . . 356
Ethylamine . . . . . . . . . 660 ferrocyanide . . . . . . . 521
Ethylene, or heavy carburetted hy- nitrate . . . . . . . . . .357
drogen * 229-230, 533 oxide . . . . . . . . . . 354
synonyms, history, natural history, phosphate . . . . . . . . .353
229; preparation, 229-230; pro- sulphate . . . . . . . . . .357
perties, 230. Ferricyanic acid . . . . . . . 520
diamine . e . 662 reactions . . . . . 524, 630
glycol . . . 573 | Ferricyanide, potassic . . . . . .293
Ethylenic ether . 640 | Ferricyanides, tests for the . . . 524
Bthylic acetate . 602 | Ferrocyanic acid . . . . . . . 518
acid . . . . . . . . 600 reactions . . . . . 523, 630
alcohol . . . 526, 527, 564-566 | Ferrocyanide, potassic . . . . . .293
aldehyde . . . . . . . . . 644 | Ferrocyanides, tests for the . . . 523
amylic ether . 638 | Ferrocyanogen or ferricyanogen . . 517
butylic ether . . 638 | Ferrous acetate . . . . . . . 601
ether . . . . . . 526, 638 carbonate . . . . . . . . .357
hydride . . . . . . . . . 528 chloride . . . . . . . . . 355
series . tº gº tº 558-567 cyanide . . . . . . . . . 511
sulphydrate . . . . . . . 526 ferricyanide . . . . . . 517, 520
Eucalyn, an unfermentable sugar 583, 585 hydric phosphate . . . . . . 353
Euchlorine . . . . . . . . . 83 iodide . . . . . . . . . . 356
Evens or artiads . . . . . . . 43 nitrate. . . . . . . . . . 357
Everitt’s white salt . . . . 517 oxalate . . . . . . . . . .353
Examination of substances by dry oxide . . . . . . . . . . .353
methods s & 437-439 sulphate . 269, 356
Excrementitious products 712-721 sulphide . . . . . 356, 519
Excretin wº . 720 | Fibrin . . . . . . . . . . 689
Excretolic acid . . . . . 720 in blood . . . . . . . . . 704
Explosions, theory of gunpowder. . 297 || Fibrinogen . . . . . . . . 689
Extractive matter in blood. . 704 || Fire damp . . . . . . . . . 228
—in urine º . 718 Fish scales, composition of . . . 693
Fixed air . . . . . . . . . 177
Flame . . . . . . . . 232-234
F. varieties, 233; light, 234; color . 234
Flesh, composition of . . . 693
Facces. . . . . 720 | Flint ; amorphous variety of silica . 186
Fats and oils * * * * 631-636 | Fluids, nutrient animal. G95–707
definition, natural history, prepara- digestive tº gº 707-712
tion, classification . . . . . 631 | Fluoboric acid * † tº . . 185
solid, table of . . . . . 633 Fluor spar (calcic fluoride) 318, 320
Patty acids, supplement to the. 631-636 | Fluoric radical . . . . . . . 69
matters in blood . . . . 704 | Fluoricum . . . . . . . . . 69
Fecula (amidine). . 586 | Fluoride of silver . . . . . . 92
Felspar . & . 343 aluminic . 341
IFerment diseases . . 487 argentic . . 418
Fermentation . 483-492 bismuthous . . . 373
varieties of . . . 483-486 calcic . . . . . .318, 320
cases of . . . . . . . . . 12 hydric . . . . . . . . . 216
conditions necessary to produce 486-488 plumbic . & & 8 . 412
circumstances influencing 48S-489 potassic . . . . . . . . . 298
theories to account for 489-490 silicic . . . . . . . . . 189
practical applications of the pro- titanic . 362
cesses of . . . . 490-492 zirconic . . . . .347
acetous . . . . . . . . . 485 | Fluorides * * * . 261-262
alcoholic or vinous . . . . . . 484 definition, natural history, prepa-
butyric . . . . . . . 485 ration, 261 ; properties, 261-
lactic acid . . . . . . . . 484 262; tests, estimation, uses . . 262
mucous or viscous . . . . . . 485 of chromium . . . . . . . 360
Ferri phosphas . . . . . . . 136 | Fluorine * tº tº # 69-70
Ferric acetate . . . . . . . . 601 synonyms, 69; history, 69; na-
acid . . . . . . . . . . 355 tural history, 69; preparation,
chloride . . . . . . . . . 355 69-70; properties . . . . . 70
INIDEX.
PAGE
Fluorine—continued.
compounds of silicon with . . . 189
Fluosilicate, potassic . . . . . .293
Force, mechanical, may modify che-
mical action . . . . . . . 11
vital, influence of so called, on
chemical action . . . . . . 11
Formate, hydric . . . . . . . 599
Formic acid . . . . . . . . 599
aldehyde . . . . . . . . 643
Formobenzoic acid . . . . . . 614
Formonitrile . . . . . . . . 673
Formulae, chemical . . . . . . 23
experimental or empirical . . . 44
rational or theoretical . . . . 44
Formyle, terchloride of . . . . . 532
Fuller's earth . . . . . . . . 343
Fulminate of mercury . . . . . 516
of silver . . . . . . . . . 516
Fulminates, double . . . . . . 516
Fulminic acid . . . . . . . . 515
Fulminuric acid, preparation . . . 515
Fumaric acid . . . . . . . . 624
series, acids of the . . . 623-624
Furfurine . . . . . . . . . 663
Furnace, principle of the blast . . 349
Fusel oil . . . . . . . . . 558
G.
Gadolinite . . . . . . 346
Gahnite, a zincic aluminate . . . 341
Gaidic acid . . . . . . . . 610
Galactose 583, 585
Galena . . . . 410, 415
Gall-stones . . . ... . 711
Gallic acid . . . . . . . . . 615
—natural history, preparation, pro-
perties. º º 615
—reactions . . . . . . . . 630
series, acids of the . . . . . . 615
Gallium . . . . . . . . . . 434
history, occurrence, preparation,
properties, chloride, Sulphate,
alum . . . . . . . . 434
Gallotannic acid . . . . . . . 636
Galvanic current, action of the, on
organic bodies . . . . . . 507
Gamboge . . . . . . . . . 678
Gas, the word adopted by Van Hel-
mont . . . . . . . 95
chloro-nitric . . . . . . . 121
coal . . . . . . . . 232, 498
—composition of . . . . . . 232
inflammable . . . . . . . 191
marsh, series . . . . . . . 228
olefiant, series . . . . . . . 22
phosgene . . . . . . . . 181
pit . . . . . . . . . . 228
liquor . . . . . . . . . 500
sylvestre 177
Gases, relative weights of compound
and elementary . . . . . .
power of carbon of absorbing . . 171
Gases—continued.
adhesion of, to Solids . . . . 9
solubility of . . . . . . . 202
free, in urine 718–719 -
Gastric juice . . . . . . 708-709
composition of human, per 1000
parts . . . . . . . . . 708
Gelatin . º 694-695
uses of - ºr e gº . 695
and chondrin, ultimate composi-
tion of . . . . . . . . 694
“Gen,” the termination . . . . 20
Gerhardt’s base . 407
German dried yeast . . 486
Gibbsite - . . .340
Glass * 306–308
varieties of . . . . . 306
enamelling, coloring, painting,
etc. . . . . . 307-308
Glauber's salts 269, 301
Glazing, salt . . 346
Globulin . 701
Globulins . 689
Glucinum . * * * * , 346
Glucose . . . . . . . . . 584
left-handed . . . . . . . . 585
Glucoses, The . . . . . . 584-586
Glucosides . . . . . . . . . 586
Glue . 695
marine e . 556
Glutanic acid . . 621
Glyceric acid . . . . . . . 609
Glycerin . . . . . . . . . 576
reactions . . . . . . . . 589
series * * 575-577
Glycerin soap . . . . . . 635
Glycocholic acid . . . . . . . 710
Glycocin . . . . . . 602, 694, 710
Glycocol - * * 602, 694
benzoyl . . . . . . . 717
Glycogen or animal starch. . 5SS
Glycollic acid. , 607
Glycols, The . . . 573-575
aromatic . . . . . . . . 575
Glycylic ether . . . 640-641
Glycyrrhizin . . . . . . . . 586
Glyoxal . . . . . . . 645
Glyoxalic acid. 60S, 609
series, acids of the . 609
Gneiss . . . . . . . . . . 343
Gold 400-403
history, natural history, extraction,
400; properties, uses, 401.
compounds of, and oxygen . 401-402
—and chlorine. * 402-403
—and sulphur . . . . . 403
reactions of the compounds of gold 403
fulminating. . . . . . 402
protochloride of . 402
peroxide or sesquioxide of . 402
suboxide of . * . 401
terchloride of . es . 402
Graham's sulphuric acid . 154
diffusionmeter * * . 193
Grains, to convert, into grammes . 733
756 INDEX.
PAGE
Grammes, to reduce to grains . . . 733
Granite . . . . . . 343
Graphic or graphitic acid . . . . 167
Graphite . . . 167, 168, 172
Gravitation modifies chemical action 4
elective or molecular . . . . . 1
Green coloring matter . . . . . 680
Greenockite . . . . . . . . 376
Greenstone . . . . . . . . 343
Guanine . . . . . . . . . 654
Guiacum resin . . . . . . . 555
Gum, reactions of . . . . . . 590
resins . . . . . . . . . 555
Gums . . . . . 588-589
Gun-cotton . . . . . . . . 684
preparation, constitution, proper-
ties. . . . . . . . . . 684
Gunpowder. 296-297
composition, properties, decomposi-
tion. . . . . . . . . . 296
theory of gunpowder explosions . 297
Gutta percha . tº g tº a 556
natural history, composition, pro-
perties . 556
Gypsum . . . . . . . . . 318
II.
IHaematein . . . . . . . . . 678
IIaematin . . . . . . . . . 703
hydrochloride . . . . . . . 703
Haematite . . . . . . . . . .354
IIaemato-crystallin . . . . . . 702
Haemato-globulin . . . . . . 702
Haematoidin . . . . . . . . 702
Haematosin . . . . . . . . 703
Haematoxylin . . . . . . . . 678
Haemin crystals . . . . . . . 703
Haemoglobin tº e sº 65, 02
preparation, 702; properties, 702-703.
Hair . . . . 695
IIalogens, or haloid elements . . 69-92
generalisation on the . . . . 91-92
IIaloid acids, action of, on organic
matters . . . . . . . 50.3
elements . . . . . . . . 69-92
—estimation of the, in an organic
body . . . . . . . . . 473
—water dissolves the . . . . 204
—compounds of hydrogen and
the . . . . . . . . . 210
—action of the, on the metals . . 245
— — on Organic bodies . . . . 504
ethers . . . . . . . . . 641
salts, double . . . . . . . 287
—of the acids . . . . . . . 594
Iſaloids, general review of the com-
pounds of hydrogen and the . . 217
compounds of carbon and the . . 180
—phosphorus and the 139-142
—sulphur and the . . . . . 161
—silicon and the . . . . . . 188
—sodium and the . . . . . . 299
as disinfectants . . . . . . 493
l’AGE
IIaloids—continued.
action of the, on
—alkaloids . . . . . . . . 650
-ammonia . . . . . . . . 220
—carbon . . . . . . 169
—ethylene . . . . . . . . 229
—methane . . . . . . . . 229
—phosphorus . . . . . . . 128
--starch . . . . . . . . . 587
Iſard and soft water . . . . . 208
Harmaline . . . . . . . . . 653
Hartshorn, spirit of . . . . . . 218
Hausmannite . . . . . . . . 328
IIeat may promote affinity . . . 12
may destroy affinity . . . . . 13
modifies chemical action . . . . 13
action of, on -
—acids 627-630
—aikaloids . . . . . . ." §
—bone . . . . . . . . . 693
—carbon . . . . . . . . . 169
—carbonates . . . . . . . 285
—chlorates, bromates, and iodates 278
—chlorides . . . . . . . . 257
—fluorides . . . . . . . . 261
—glycerin . . . . . . . . 576
—iodides . . . . . . . . 259
—metallic oxides . . . . . . 243
—nitrates . . . . . . . . 275
—nitric acid . . . . . . . 117
–nitric peroxide . . . . . . 111
—oils . . . . . . . . . . 632
—Organic bodies . . . . . . 496
—phosphates . . . . . . . .305
—phosphorus . . . . . . . 126
—silicates . . . . . . . . 286
—starch . . . . . . . . . 587
—sugar . 582, 583, 584
—sulphates . . . . . . . 267
—sulphides . . . . . . . . .263
—sulphur . . . . . . . . 146
—sulphuric acid . . . . . . 155
water . . . . . . . . . 197
IIeat and cold as natural disin-
fectants . . . . . . . . 493
—influence of, on affinity . . . 12
Heated (super-) water . . . . . 202
Hepatic air * * * * 224
Heptane . . . . . . . . 528
IIeptylene . . . . . . . . . 533
IIeptylic acid . . . . . . . 604
alcohol . . . . . . . . . 558
IIesperidene . . . . . . . . 552
Heterogeneous affinity . . . . . 1
Hexabromide, benzene . . . . . 540
Hexachloride, benzene . . . . . 540
dimanganic . . . . . . . . 327
dititanic . . . . . . . . 362
Osmic . . . . . . . . . 381
Hexachlorides . . . . . . . 257
Hexachlorobenzene . . . . . . 540
Hexafluoride, dititanic . . . . . 362
JHexane. . . . . . . . . . 528
Hexdecane. . . . . . . 528
Hexothylenic glycol. . . . . . 575
INDEX. 757
P.A.G.E. IPAGE
Hexylene . . . . . . . . . 533
glycol . . . . . . . . . 573
Hexylic acid . we 603-604
alcohol . . . . . . . . . 558
Hippuric acid. . . 613, 717-718
preparation, 718 ; properties, 718.
reactions . . . . . . . . 628
Homberg's pyrophorus . . . . . 342
Homocumic acid . . . . . . . 612
Horn-lead . . . . . . . . . 414
Horn-silver . . . . . . . . 417
Houzeau's ozonometer . . . . . 62
Humboldtite or iron resin . . . . .357
“Hydr” or “Hydro,” the prefix . 22
Hydrate, ammonic . . . . . 311
baric . . . . . . . . . . 316
cadmic . . . . . . . . . 376
cassic . . . . . . . . . . 309
calcic . . . . . . . . . 319
cupric . . 367
cuprous . . . . . . . . . 367
iridic . . . . . . . . . . 436
lithic . . . . . . . . . . .308
magnesic . . . . . . . . 324
potassic . . . . . . . . . 291
sodic . . . . . . 299, 526
IIydrated cupric oxychloride of cop-
per . . . . . . . . . . 367
diammonic sulphide . . . . . 311
dibasic carbonate . . . 367, 372
oxide . . . . . . . . 332
oxy-carbonate . . . . . . . 372
—of copper . . . . . . . . 367
zincic oxycarbonate . . . . . 333
Hydrates, water unites with bases to
form . . . . . . . . . . 203
action of the fixed alkaline, on Gr-
ganic bodies . . . . . . . 503
Hydric acetate . . . . . . . 600
ammonic sulphate . . . . . . 312
bromide . * * * * . . 213
cassic sulphate . . . . . . . 809
chlorate . . . . . . S.2
dioxide (hydric peroxide) . . . 209
disodic phosphate . 2S1, 309
fluoride . . . . . . . . . 216
formate . . . . . . . . . 599
hypochlorite . . . . . . . 7 S
iodide. . . . . . . . . . 214
magnesie phosphate . . . . . 323
metaphosphate . . . . . . . 134
nitrate . . . . . . . . . 1 lá
perchlorate . . . . . . . . $2
peroxide . . . . . 209-210
—synonyms, history, preparation,
209; properties, 209-210; tests,
uses, 210.
—a powerful oxidising agent . . ll
persulphide . . . . . . . . 226
phosphate . . . . . . . . 135
pliosphite. . . . . . . . . 134
potassic carbonate . . . . , 295
—metantimoniate . . . . . . .391
—Sulphate . . . . . . . . 295
— —a dehydrating agent . . . 506
Hydric, potassic—continued.
—tartrate . . . . . . . .297
sodic ammonic phosphate . . . 281
—carbonate . . . . . . . . 304
— chromate . . . . . . . 358
—phosphate. . . . . . . 305
—sulphide . . . . . . . . 302
—sulphate . . . . . . . . 301
Hydride of ethyl . . . . . . . 526
of methyl . . . . . . . . 526
antimonious . . . . . . . . 389
arsenious . . . . . . . . . 395
Cuprous . . . . . . . . 36S
methylic . . . . . . . . . 228
phenylic . . . . . . . . . 539
silicic . . . . . . . . . . 235
Hydriodic acid . . . . . . . 577
(anhydrous) . . . . . . 214-216
—synonym, 214; history, prepara-
tion, 215; properties, 215-216.
(solution) . . . . . . . . 216
Hydrobromic acid (anhydrous). 213-214
—synonym, history, 213 ; pre-
paration, 213-214 ; properties,
214.
(solution) . . . . . . . . 214
Hydrocarbons, the . . . . 525-556
series of . . . . . . . . . 527
Hydrochloric acid (anhydrous)
210-211, 5
—synonyms, history, 210; natural,
history, 210-211; preparation,
properties, 210.
(solution) . . . . . . 211-212
—preparation, 211; properties 211-212
impurities . . . . . . 212
preparation of pure . . . . . 213
decomposes nitric acid . . . . 117
table showing the percentage
quantities of, and of hydro-
chloric acid gas contained in
aqueous solutions of different
specific gravities . . . . . 72S
Hydrochloride, haematin . . . . 703
Hydrocoumaric acid . . . . . . 614
Hydrocyanic acid. . . . . 509-5 ll
history, natural history, 509 ; pre-
5
3
*
paration, 509-510; properties,
510-5ll.
estimation of . . . . . . . 522
reactions . . . . . . . . . 522
Hydrofluoboric acid . . . . . . 185
º
Hydrofluoric acid (anhydrous) . . 216
— synonym, history, properties . 216
(solution). . . . . . . 216-217
—preparation, 216 properties,
216-217 ; tests, 217.
Hydrofluosilicic acid. . . . . I SQ
Hydrogen . 191-235
synonyms, history, matural history,
191; preparation, 191-192; pro-
perties, 193-195.
combinations of chlorine with . 73
compounds of, and carbon . . .
—and copper . . . . . . 368-
7.58
lNDEX.
PAGE
Hydrogen, compounds of continued.
—and the haloid elements . . . 210
— — review of . . . . . . 217
—and nitrogen . . . . . . 217
—and oxygen . . . . . . . 195
—with phosphorus . . . . . 221
—and silicon . . . . . . . 235
—and sulphur . 224
estimation of the hydrogen and
carbon in a body containing ni-
trogen . . . . . . . . .
experimental determination of the
carbon, hydrogen and oxygen, of
an organic compound not con-
taining nitrogen . 469
action of carbon on . . . . . 170
—on the metals . 245
—nascent, on organic bodies . 506
— —on the oxides . . . 244
liquefaction and solidification of,
by Pictet . . . . . . . . 723
471
molecule . . . . . . . . . 46
monosulphide . . 224
nitrate . . . . . . . . 115
pyrophosphate . . . . . . . 134
bicarburet of . . . . . . . 539
methane, or light carburetted . . 228
ethylene, or heavy carburetted. . 229
chloride of * * * * . 210
peroxide of (hydric peroxide) . 209
persulphide of . . . . . . . 226
gaseous phosphoretted 221-223
—synonyms, 221; matural history,
preparation, 222; properties,
222-223.
liquid phosphorctted . . . . . 223
—preparation, properties, 223.
solid phosphoretted . . . 223
—preparation, properties, 223.
Selenetted . . . . . . . . 227
Seleniuretted 227
—synonyms, history, preparation,
proporties, 227.
sulphuretted . . . . . 224-226
—synonyms, history, natural his-
tory, 224; preparation, 224-225;
properties, 225-226; uses, tests,
226.
—action of, on sulphides. . 264
persulphuretted ‘226-227
—synonyms, history, preparation,
226; properties, 226-227.
IIydrogenium . . . . 194, 240
IIydrogenous compounds, action of
chlorine on . . . . . . . 73
IIydrometer, specific gravities cor-
responding to degrees of Baumé's 731
degrees on Twaddell's, and the cor-
responding specific gravities. . 732
Hydro-nitro-prussic acid . . . . 521
liydroparacoumaric acid . . . . G14
Hydroquinone. . . . . . . . 575
IIydroselenic acid . . . . . . 227
Hydrosulphates 262-265
Hydrosulphites , , 271
PAGE
Hydrosulphuric acid . . . . . . 224
Hydrosulphurous acid . . . . . 157
Hydrosulphyl . . . . . . . . 226
Hydrotrichloride, silicic . . . . 188
Hydroxide, a . . . . . . . . 240
Hydroxyl . . . . . . . 209
compounds of barium with oxygen
and . . . . . . . . . 315
—of calcium with oxygen and . 318
—of cyanogen and . . . . . 514
—of potassium and oxygen and
291, 295
—of sodium with oxygen and . . 299
—of sulphur with oxygen and . . 147
IIydroxyl ethene . . . . . . . 564
Hydroxymethane . . . . . . . 562
Flyaenasic acid . . . . . . . 597
IIygrometers . . . . . . . . 99
Hyocholic acid . . . . . . . 711
Hyoscyamine . . . . . . . . 652
“Hyper,” the prefix. . . . . . 22
“Hypo,” the prefix . . . . . . 22
Hypobromous acid . . . . . . 85
Hypochloric acid . . . . . . . 81
Hypochlorite, calcic . . . . . . 318
IIypochlorites . . . . . . . . 280
definition, preparation 28.1-2S2
IIypochlorous acid . . . . 78-79
—synonym, 78; preparation, 78;
properties, 78-79.
anhydride * * * * *
—preparation, 77; properties 77.
ITypomitric acid (nitric peroxide) . . 110
77-78
IIyponitrites g . .278
Ilyponitrous acid . . . . . . . 106
(nitrous anhydride) . . . . . I08
ITypogasic acid . . . . . . . 610
IIypophosphites . . . . 282
definition, preparation, properties 282
used in medicine . . . . . . 132
IIypophosphorous acid . 131-132
preparation, 131 ; properties, 131-132
IIyposulphate, argentic . . .] 18
IIyposulphates . . . . . . . 273
definition, preparation, 273; pro-
perties, 273-274.
IIyposulphite . . . . . . . . 158
sodic . . . . . . . . . . 302
ITyposulphites or hydrosulphites . . .271
IIyposulphuric acid (dithionic acid) . 159
Ilyposulphurous acid 157-15S
—synonym, history, 157; prepara-
tion, 157-158; properties, 158.
(thiosulphuric acid) . 158
Hypoxanthin . +º 654
I.
“Ic,” the termination . . . . . 21
Ice, absorption of heat by, in becomi-
ing water . . . . . . . 198
Ice-making apparatus . . . . . 219
“Ide,” the termination . . . . . 21
Imides, The 217, 672
INDEX. 7.59
PAGE PAGE
Imidogen . . . . . . . . . 217 | Iodides—continued.
Inches, to convert cubic, into cubic of phosphorus . 141
centimètres . . . . . . 73 Iodine . . . . . . . . . 86-91
to convert, into millimètres . . 733 history, 86; natural history, 86-87;
India-rubber . . . . . . . 556 preparation, 87; properties, 88;
natural history, constitution, pre-
paration, properties of Solid caout-
chouc, uses, 556.
Indian ink . . . . . . . . 554
Indic chloride . . . . . . . .338
nitrate . . . . . . . . . .338
oxide . a u ę & B . 338
sulphate . . . . . . . . . 338
sulphide . . . . . . . . . .338
sulphite . . . . . . . . . 338
Indican . - e. 586, 677
Indigo . . . . . . . . . . 679
preparation of . . . 677
Indium . - - g - 337-338
history, natural history, 337; ex-
traction, 337-338; properties,
338.
reactions of indium compounds . 338
atomic weight of
. 725
“Ine’’ and “in,” the terminations 20, 22
Inflammable air of gas . . 191
Ink, composition of . - . 637
blue sympathetic . . . . . . 334
Inosite, or sugar of muscle .
586, 694
Intestinal juice 7 11-712
Inulin starch - . 588
Iodacetic acid . . . . . . . . 602
Iodate, potassic . 27S
Iodates . . 278
Iodic acid . * * * * * * 90
preparation, 90; properties, 91.
Iodide of nitrogen . . . . . . . 120
—preparation, properties. . 120
of silver . . . . . . . 92
aluminic . . S40
ammonic . . 311
antimonious . . 389
argentic . 418, 420
arsenious . 400
lismuthous . . .373
cadmic . 376
calcic . . 31 S
cupric . 370
cuprous . . 370
cyanic * * * * . 514
ferrous . . . . . . . . . 356
hydric * - ºr . 214
mercuric . . . . . . . . . 427
II].01°CUll'OllS - - . 427
palladious . . . . . . . . 378
plumbic . . . . . . . . . 4.15
potassic . .293
sodic . . . . . . . . 301
thallic . . . . . . . . . 431
thallous . . . 431
Iodides . * * * *
definition, natural history, prepara-
tion, 259; properties, 259-260;
tests, estimation, uses, 260.
acid . . . . . . . .
2.59-260
. 593
tests, 89; uses, 90.
compounds of iodine and chlorine .
—of iodine and oxygen .
—of mercury and iodine .
91
90
427-438
—of nitrogen and iodine . . . . 120
—of silicon with iodine - 189
estimation of chlorine, bromine,
and iodine in an organic body . 473
action of, on organic bodies. . 505
oxysalts of & is º is . 279
green . . . . . . . . . . 666
Iodobenzenes tº º . 540
Iodoform . . . . . . . 532
silicic * * * * * . 189
Iodopropane . . . . . . . . . 630
Iridic anhydride . . . . . . . 436
chloride . . . . . . . . . 436
dioxide . . . . . . . . . 436
hydrate . . . . . . . . . 436
oxide . . . . . . . . . . 436
sulphide . . 436
tetrachloride s - - . 436
Iridious chloride . . . . . . . 436
oxide . . . . . . . 436
sulphide . . . . . . . . . 436
Iridium . * - s a 435-436
history, derivation, natural history,
preparation, 435; properties, 435-
436.
compounds of iridium . . . . 436
Iron . . . . . . . 347-357
natural history, 347; preparation,
348-351; impurities, 351 ; pro-
perties, 351–352.
compounds of iron . 353
—with oxygen . . 353
—and chlorine . . 355
Iron ores . . 348
oxy-salts . * * * 356-357
reactions of tho salts of . . . 4.46
perchloride, sesquichloride or tri-
chloride of . . . . . . . 355
persulphate or sesquisulphate of . 357
protocarbonate of . . . . .357
protochloride of . . . . . . 355
protosulphide or sulphide of. 356
protosulphate of • * 356
protoxide of . - - 3.53
sesquioxide or peroxide of 354
Iron resin or Humboldtite . 357
Iron, cast, composition of 350
galvanised * - 331
specular 354
wrought 350
Isatin . 62, 679
Isatropic acid . . . . . . . .
lsoamylbenzene . . .
Isoamyldimethylbenzene
Isoamylmethylbenzene
Isobutylbenzene . . . .
760
INDEX.
IPAGE P_AGE
Isobutyric aldehyde . . 643 Lævulose • * e º ºs . 585
Isologous series . 526 natural history, preparation, pro-
Isomerism . 48 perties. © tº * * . . 85
Isomorphism * * * * * 50 Laevoglucose tº e ... jS5
Isophthalic acid . . . . . . . 624 || Lake and marsh water . 206-207
Isoprene . . . . 556 Lakes (pigments). . . . . 341
Isopropylbenzene & 4 . 537 || Lampblack. 167, 168, 172
Isopropyldimethylbenzene. . 537 Ilanarkite . • . 415
Isopropyliodide * - . 530 | Lanthanum . 347
Isopropylmethylbenzene . . 537 Lanthopine . (52
Isovaleric aldehyde . 643 | Lapis lazuli . . . . . . . . 343
Isoxylidic acid . 624 Laudanine . . . . . . . . . 652
Itaconic acid ... . . . . . . . . 624 || Laughing gas (nitrous oxide). . 104
“Ite” and “Ate,” terminations 22 Lauric acid & # - . 597
alcohol . 358
Lead . . . . . . . 4.10-4 10
J. history, natural history, prepara-
tion, impurities, purification,
Jalap resin . . . 554 410.
Jalapinoleic acid . . . . . . 608 extraction of silver from 4 10-411
Jasper, amorphous variety of silica . 180 properties 4 l 1-4 12
salts of . 4 12
uses . . . . . . . . . . 413
K. compounds of lead and oxygen . 413
— of lead and Sulphur . 415
Rakodyl tº e º 'º - 667-668 oxy-salts - 4 15-416
preparation, 667-668; properties . 668 action of water upon . . . . . 208
chloride . . . . . . . . 668 reaction of the Salts of . . . . 455
cyanide . . . . . . . . . 668 acetate of . . . . . . . . 416
dioxide . . . . . . . . . 668 carbonate of. . . . . . . . 416
disulphide . . . . . . . . 668 chlorosulphide of . . 414
iodide . . . . . . . . . 668 chromate of . . . . . .357-360
Oxide . . . . . . . . . 668 oxychlorides of . . . . . . . 414
sulphide . . . . . . . . . 668 protosulphide of . . . . . . 4.15
trichloride - * * . 668 protoxide or monoxide . . 413
Rakodylic acid . . . . . . . 668 subsulphide of . . . . . . . 4 15
Kaolin, a white clay . . . . . 346 suboxide of º . 4 13
Relp, or varec, ash of sea-weed 37 Sugar of . . . . 60 l
soda from gº º . 302 Lead, brown, oxid . 4 l 4
ICetone, a . . . . . . . . . 527 red • * * * * à:5
Retones, The . . . 646–647 white, preparation of. . 4 16
constitution, 646 ; preparation, Leads, red . . . . . . . . . 414
properties, and reactions, 647. Leucic acid . . (;05
|Klumene * a s - e. . 231 Leucine s a tº * * G04, 694
Roumiss, fermented mare's milk . . 491 Leukon or silico-formic acid . I ()()
Roussin . . . . . . . . . . 654 Libavius, fuming liquor of . 387
R reasote, coal tar . . . . . . 571 Lichen starch . . . . . . . . 588
to distinguish carbolic acid from . 571 || Light, air a refractor of . 96
Kreatine e 654, 694 influence of, on affinity . 14
Krcatinine . 654, 694 action of, on alkaloids . . . . 649
—chlorides . . 257
—iodides . .259
L. —nitric acid * - . 117
—organic bodies . . . . . . 506
Lac . . . . . . . . . . . 554 —phosphorus . . 126
seed . 554 || Lignin . • - . (S3
stick . . 554 || Lime, uses of . . . . . 3 19
shellac tº gº º . 554 slaked (calcic oxide) . . 31)
Tacquer . . . . . . . . . 554 chloride of . 280, 322
Lactic acid. . . . . . . . . 607 oxalate of . - * - . . 720
—fermentation . . 484 phosphate of . . . . . . . 720
series, acids of the 605-608 || Limestone. • * g e . 349
—general preparation of the nor- Liquation of silver . • s . 417
nial acids of the . 606 || Liquids, solubility of, in water . . 202
Lactin or lactose . . 583 Liquor sanguinis. . . . . . . 703
INDEX.
761
is: PAGE PAGE
Litharge (plumbic oxide) . . . . 413 ; Manganese—continued.
Lithia. . . . . . . . . . 308 red, oxide . . . . . . . . . . . 328
Lithic acid. . . . . . . . 715–717 binoxide, peroxide or black oxide of 328
carbonate . . . . . . . . .308
hydrate . . . . . . . . . 30S
sulphate . . 308
Lithium is is º º 30 S-309
history, natural history, prepara-
tion, properties, uses, 308.
compounds . . tº . 30S
Litmus gº tº * 677, 679
Loam . . . . . . . . . . .344
Lunar caustic . . 421
Luteoline . 678
Lutidine it tº . 661
Lymph and chyle 705-706
percentage composition of . . . 705
M.
Madder, preparation of . . . . . 677
red . . . . . . . . . . 679
Magnesia (magnesic oxide) . . 323
ammonio-phosphate of . . . . 720
Magnesic borate . . . . . . . 323
bromide . . . . . . . . . 324
carbonate . . . . . . . . 325
chloride . . . . . . . . . 324
hydrate . . . . . . . . . 324
nitrate . 323
nitride * e º º . 324
oxide . . . . . . . . . . 323
phosphate . . . . . . . . 323
—(ammonic) . . . . . . . 325
pyrophosphate . . 323
silicates . . . . . . . . . . 325
sulphate . . . . . . . . . 324
sulphide . . . . . . . . . 324
Magnesium. . . . . . 322-325
history, natural history, prepara-
tion, 322; properties, uses, 323.
compounds of . . . . . 323-325
reactions of the salts of . . . . 442
Magnetic oxide of iron . . . . . .354
properties of metals . . . . . 240
Malachite . . . . .367, 372
Malamic acid . . . . . . . . 673
Mulamide . . . . . . . . . 673
Maleic acid. . . . . . . . . G24
Malic acid . . . . . . . . . 621
—reactions . . . . . 628-629
series, acids of the . . . 620-621
Malimide (?) . . . 673
Malonic acid . . . . . . 618
Mandelic acid . . . . . . . 614
Manganates . . . . 270, 320
definition, preparation, properties,
uses, 270.
Manganese . . . . . . .
history, natural history, prepara-
tion, properties, uses, 326.
compounds of . * * *
—of manganese and oxygen . . 326
reactions of the salts of . . . . 4.49
dithionate of 159, 273
protochloride of 328, 329
protoxide of. . . . . . 327
sesquioxide of . . . . . . . 327
Manganese spar . . . . . . . 330
Manganic acid . . . . . . . 328
anhydride . . . . . . . . 327
chloride . . . . . . . . . 329
dioxide . . . . . . . . . 328
oxide . . . . . . . . . . 327
oxychloride . . . . . . . . .329
perchloride . . . . . . . . 329
peroxide . . . . . . . . . 65
tetrachloride . . . . . . . .329
Manganous carbonate . . . . . 330
chloride . . . . . . . . . 329
oxide . . . . . . . . . . 327
sulphate . . . . . . . . . 330
Mannite . . . . . . . . . 578
preparation, properties, 578.
Mareasite . . . . . . . . 356
Margaric acid . . . . . . . . 604
Margarin . . . . . . . . . 634
Marine acid . . .210
Marl. * g e º a 344, 345
Marsh gas, action of chlorine on . . 74
—series . . . . . .228-229
—series or paraffins 528-533, 548-549
—type . . . . . . . . . 466
Mason's wet and dry bulb thermo-
meters . . . . . . . . 99
Mass or quantity, influence of, on
affinity . . . . . . . .
Massicot (plumbic oxide) . . . . 413
Mastich . . . . . . . . 554
Mauve (aniline purple) . . . . . 665
Measures—see Metric System.
Mechanical force may modify chemi-
cal action . . . . . . . 11
Meconic acid . . . . . . . . 625
—Teactions . . . . . . . . 630
Meconidine . . . . . . . . 652
Melene . . . . . . . . . . 533
Melissic acid . . . . . . . . 597
—alcohol . . . . . . . . 558
Melissine . . . . . . . 558
Melitose . . . . . . . . . . 583
Melizitose , 583
Mellitic acid 6.25-626
7:23-725
Mendeleeff's law of periodicity
Mendipite . * * * *
Mentheme . . . . . . . . . 552
Mephitic air . . . . . . . .
Mercaptans or thio-alcohols . 926, 578
Mercur-ammonic chloride . . . . 426
Mercuric chloride . . . . . . . 425
cyanide . . . . . . . . , 511
ethide . . . . . . . . . . 670
iodide . . . . . . . . . 427
methide . . . . . . . . . 670
nitrate . . . . . . . . . .429
oxide . . . . . . . , 55, 423
762 INDEX.
PAGE º PAGE
Mercuric-continued. Metals, alkaline e 288-313
oxy-chlorides . 426 of the alkaline earths. 314-335
sulphate . . 429 of the earths 339-363
sulphide . . 428 of Group I. . 4.10-433
Sulphocyanate . . 516 of Group II. 364-409
Mercurous chloride . . 424 of Group III. 339-363
iodide . . . 427 of Group IV. . . . . . 326-338
nitrate . . 76, 429 || Metals, action of, on the oxides of
oxide . . 422 nitrogen e e º is . 113
sulphate. . 429 action of carbon on the . . . . 170
Sulphide . . . 429 —of chlorine on metals and metallic
Mercury • & © tº 421-429 oxides . * * * * 75
history, natural history, extrac- —of hypochlorous acid on . . 78
tion, 421; properties, 421-422 ; —of nitric acid on metals and
uses, 422. metallic oxides. . . . . 117
compounds of, and oxygen . . 422 —of nitric peroxide on metals and
— table of - . . 423 their compounds 112
—and chlorine . 424-427 —of oxygen on the 58
—and iodine 427-428 —of ozone on . . . . . . 62
—and Sulphur . 428-429 —of sulphurous anhydride on . 149
oxy-salts . . . . . . . 429 || Metals, non-, symbols, atomic weight
reactions of the salts of . . 455 and relative weight of . 53
biniodide of . - . 427 —action of chlorine on the . 3
black or grey oxide of . . . 422 || Metantimonate of potassium . 284
chloride, bichloride, or perchloride Metantimonic acid 301, 392
of . . . . . . . . . . . 425 | Metapectin . . . . . . 589
fulminate of . 516 || Metaphosphate, argentic 4 18
nitride of , 424 Sodic . . . . . . . . . 305
nitric oxide of . . 423 Metaphosphates or monophosphates. 138
protonitrate of . 429 || Metaphosphates . . . . . 282
red oxide of . . . . . . . 423 definition, preparation, tests 282
subchloride or protochloride of . 424 Metaphosphoric acid 9 * 134
subsulphide of . . . . . 428 synonyms, preparation, properties,
Mesaconic acid . 624 tests . . . . . . . . . 134
Mesidic acid . 624 | Metastannic acid. 386
Mesitic acid . 539 Metaterebenthene 550
Mesitylene. . . 537 || Metatoluic acid 537
Mesoxalic acid 621, 717 | Metatoluidine. 665
“Meta,” the prefix . . . 22 || Metaxylene 537
Metabismuthic acid . . 375 benzyl 543
Mctabismuthous acid . 374 || Methacetic acid 602
Metacresol. . 572 | Methacrylic acid . (310
Metaldehyde . . . . . . 644 || Metha-moglobin . 702
Metallic compounds, action of hypo- Methiomatin . . . . . . 702
chlorous acid on . . . . . 78 Methane or light carburetted hydro-
Metallic salts, action of, on alkaloids (#54) gen 228-229, 526, 528
action of ammonia on . . . . .220 synonyms, history, natural history,
Metallic solutions, action of phos- preparation, 228; properties,
phorus on . . . . . . . 129 229.
Metallic, non-, elements, action of diphenyl . . . 543
OZO]] (2 OIl . º w 62 Methenyl chloride 532
Metalloids, The . 54-235 | Methylamine . 660
action of oxygen on the 58 || Methylbenzene - - 537
Metals, The . . . 236-436 Methyl butyl carbinol . 559
general remarks on 230–248 butyl ketone 646
derivation, definition, order of dis- carbinol 564
covery, natural history . 236 crotonic acid º (310
sensible and physical properties 236-2 #0 cyanide tº s 532
cheutical properties 240-248 diethyl carbinol 559
classiſication . . 248 ethyl ketone . 646
supplement to the . 434-436 ethylamine - . 661
Metals whose Sulphides are insoluble ethyl-phenylamine . 561
in the alkaline sulphides . 364-383 glycocin . . . . 602
—are soluble in the alkaline sul- hexyl carbinol 559
383-409 isoanyl ketone . . 646
phides .
INDEX. 763
PAGE IPAGE
Methyl—continued. Monatomic acids, amides of . 672
isopropyl ketone . . . . 646 || Monobasic acid . . . . 253
isopropyl carbinol . . . . . . 559 || Monobromacetic acid . 602
nonyl carbinol . . . . . . . 559 || Monobromcamphor . . . . . . 553
pentyl carbinol . . . . 559 || Monobromobenzene . . 540
naphthalene . . . . . . . . 542 || Monochloracetic acid . 602
phosphine . . . . . . . . 666 Monochloride, carbonic . . . . . 181
propyl carbinol . . 559 || Monochlorides . . . . . . . 257
propyl ketone . 646 || Monochlorobenzene . . . . . . 540
type . . . . . . . . 466 | Monochloromethane . . . . . . 532
Methylene chloride . . . . . . 532 || Monohydrogen phosphate . 134
Methylic acetat . 602 || Mono-oxy-acetic acid . 607
acid . . . . 599 || Monophosphate, sodic . 305
alcohol . 526, 562-564 || Monosulphide, hydrogen . 224
aldehyde . * * * * . 643 || Monoxide, carbon . . 175
amylic ether . . . . . . . 638 nitrogen . . . . . . . . . 104
chloride . . . . . . . . . 532 Monoxides . . . . . . . . . 242
—dichlorinated. . . . 532 || Morindin . 678
ether . . . . . . . . . . 638 || Moringic acid . . 610
ethylic ether & . . . 638 || Moritannic acid . 678
hydride . . . . . . . . . 228 Morphia 49, 652
sulphydrate . . . . . . . 526 tests for . © tº . 675
Metoxybenzoic acid . . . . . 614 Morphine . . . . . . . . . 652
Metric system as a measure of length 50 pseudo- . 652
—as a measure of surface . . . 51 Mortar . 319
—as a measure of capacity . . . 51 Mosaic gold . 386
—as a measure of weight . . . . 51 || Mucin . . . . . . . . . . 721
Mezereon resin . . . . . . . 554 || Mucoid sugar . . . . . . . . 585
Mica . . . . . . . . . . .343 || Mucous or viscous fermentation . . 485
Microcosmic salt . . . . . . . 281 || Mucus ę & E. . 721
Milk 706-707 || Murexide . . . . . . . . . 717
composition per 100 parts of human
compared with that of the cow . 706
Millimëtres, to reduce, to inches . . 733
Mineral and other substances, power
of carbon of absorbing
action of ozone on . . . . . 62
Mineral matters in blood . . . . 705
Mineral waters . . . . . . . 207
Minium . tº ſº e º 'º º . 414
Moisture, general facts respecting . 99
Molecule, 25; compound molecules,
25; elementary molecules, 26.
Molecular gravitation . . . . . 1
Molybdates . . . . . . . . 271
Molybdenum 408-409
matural history, preparation, 408;
properties, 408-409.
compounds of molybdenum . , 409
—tests for . . . . . 409
Molybdic anhydride . 408, 409
chloride * . 409
disulphide . 409
oxide . . . . 409
tetrasulphide . 409
trisulphide . . . . . 409
Molybdous chloride . . . 409
oxide . . . . . . . . . . 409
“Mon” or “mono,” “deut,” etc., the
prefixes . . . . . 22
Monadelphic double type . 4 (37
Monadelphic or marsh gas type . 466
Monamides, primary, secondary, and
tertiary . . . . . . . . 672
Monamines . . . . . 658-662
Muriate of ammonia . . 311
of soda . . . . . . . . . .299
Muriatic acid . . . . . . . . 210
Muriaticum or muriatic radical . . 70
Muride . . . . . . . . . . 83
Muscle . , 693
Sugar . . . . . 694
Mycoderma aceti. . 485
Mycose . . . . . . . . . . 584
Myosin . * = & . GSS)
Myricin . . . . . . . . . . 634
Myristic acid tº º . 597
Myronic acid . . . . . . . . 586
Myrosin . . . . . . . . . 4 S6
Mysorin . . . . . . . . . . 367
Names of bodies . . . . . . . 20
Naphtha, wood . . . . . . . 558
Naphthalene 542, 546
occurrence and preparation, 542;
properties, 542-543.
series . 542-543
Naphthaladine . * e º ºr . 66 I
Naplithoie series, acids of the . 616-617
Narceine * * * * * . (352
Narcotine . . . . . . . . . 652
tests for . . . . . . . 675
Nascent matter, action of . 9
Nerve tissue . . . . . . 695
764
INDEX.
P
Nickel tº s & g g 335-
history, natural history, prepara-
definition, synonyms, natural his-
tory, 274; theories of nitrifica-
tion, 274–275 ; purification of
nitre, preparation, 275, proper-
ties, 275-276; tests, 276 ; uses,
277.
AGE
336 Nitric acid—continued.
tion, properties, uses . . . . 335
compounds of & 335-336
reactions of the salts of . . 449
protoxide of . . 335
Nickelous carbonate . . 336
chloride . . 336
nitrate . . . . . .336
oxide . . . 335, 336
—hydrated . . . 336
sulphate . . 336
Nicotine & © tº . 651
tests for . . . . . . 674
Nil album (zincic oxide) . 331
Nitrate, ammonic . . . . . . . 313
argentic . . 75, 273, 277, 418, 421
baric tº e s tº e 273, 316
bismuthous . 374, 375
cassic . . . .309
calcic . 318, 321
chromic . . 358
cobaltic . 334
cobaltous. . 334
cupric. . 370
ferric . . 357
ferrous . 357
hydric . 115
hydrogen. . 115
indic . . .338
magnesic, . 323
mercuric . . . 429
IOleI'Cllr OllS 75, 429
nickelous . . 336
platinic . . 405
plumbic . 412, 415
potassic . . .295
sodic . 304
thallous . . 431
uranic . . 337
Nitrates . 274–277
salts allied to the . 278-279
– natural history, preparation,
278; properties, 278-279; tests 279
alkaline a e º is is “ 56
basic plumbic . . . 4.15
Nitre or saltpetre . . 291, 295
purification of . * . 275
spirit of . . . . ! . 115
cubic (sodic nitrate) . 304
cubical . 27.4
prismatic . . . . . 274
Nitric acid . . 102, 115-119
synonyms, 115; history, 115 ;
natural history, 115; prepara-
tion, 116; impurities, 116; pre-
paration of pure acid, 116 :
properties, 116-118 ; tests, 118;
uses, 119.
table showing the specific gravi-
ties and percentage strengths
PAGE
of various solutions of . . 723
tests for gº tº $ tº . 460
dissolves most metals. . 246
action of . tº ſº & . 12
—on organic matters. . . 503
Nitric anhydride . ll 4-llä
history, preparation, 114; pro-
perties, 115.
table showing the specific gravities
and percentage strengths of
various solutions of . . . . 726
Nitric dioxychloride (nitrylic chlo-
ride) . . . . . . . . . 121
dioxy-tetrachloride (chloro-nitric
gas) . . . . . . . . . 121
oxide. tº gº tº gº e 106-108
—synonyms, 106 ; preparation,
106; properties, 107-108.
—action of, on metals . 246
oxy-dichloride (chloro-nitric gas) . 121
peroxide . . . . . . 110-113
—synonyms, 110; history, 110 ;
preparation, 110 ; properties,
110.
—action of, on metals . .247
trioxide . & . 108
boric . * . 18.5
magnesic . . . . . . . . . 324
silicic . , 190
Nitrification 64
theories of . 274
Nitrile st . 673
Nitrite, argentic . . . . . . . .277
potassic . . . . . . . . . .297
Nitrites . tº s is 277–278
definition, preparation, properties,
tests, uses is tº 6 & • 2 (
plumbic . . 415
Nitrobenzenes . 540
Nitrobenzoic acid. . 613
Nitro derivatives . . 539
Nitro-ethane . 532
Nitrogen . . . . . . 93-121
synonyms, 93; history, 93; natural
history, 93 ; preparation, 94;
properties, 94; tests, 95; uses,
95.
general remarks on the oxides of
nitrogen . . . . . . . 113
compounds of nitrogen and oxy-
gen . . . . . 103-113
compounds of nitrogen and the ha-
loids . . . . . . . 119
—nitrogen, oxygen, and chlorine
120-121
—hydrogen and nitrogen . . . 217
a grouping element for nitrogenized
bodies . . . . . . . 466
experimental determination of the
carbon, hydrogen, and oxygen
of an organic compound not con-
taining . . . . . . . . 469
INDEX.
765
IPA GE I’AGE
Nitrogen—continued. Octane . . . . . . . . . . 528
estimation of the hydrogen and Octene . . . . . . . . . 533
carbon in a body containing . 471 || Octylene . . . . . . . . . 833
recognition of, in organic bodies 471 Octylene glycol . . . . . . . 573
estimation of . . . . . . . 471 Octylic acid . . . . . . . . 697
in the air . . . . . . . . 98 alcohol . . . . . . . . . 668
present in various animal substances 93 Odds or perissads . . . . . . . . . .43
action of carbon on . . . . . 170 Odors, power of carbon of absorbing 171
on the metals . . . . . . 245 OEnanthic alcohol . . . . . . . 558
binoxide and deutoxide of . . . 106 CEnanthylic acid . . 604
Nitrogen, chloride of 119-120 aldehyde . . . . . . 643
dinoxide . . . . . . . . . 106 || Oil of camphor . . . . . . . 552
iodide of . . . . . . . . 120 of turpentine and its allies . . . 549
Imonoxide . . . . . . . . 104 bitter almond g . 645
oxides of, general remarks on the . 113 bone . * * * * * . 693
peroxide of . . . . . . . . 110 fusel . . . . . . . . . . 558
protoxide of . . . . . . . 104 paraffin . . . . . . . . . 548
tetroxide . . . . . . . . . 1 iO rock, or petroleu . . . . . 548
trioxide . . . . . . 108 || Oils, essential or volatile . 551-552, 634
Nitrogenous, non-, bodies, types of . 466
Nitro-methane . 532
Nitro-Prussides . . . . . . . 521
tests for . & º ºr . 524
Nitrosyl . . . . . . . . . 106
chloride (nitrous oxychloride) . . 120
Nitrotrichloromethane . 533
Nitrous acid tº º º 109-1 10
—preparation, 109 ; properties,
109.
anhydride . . . . . . . . 108
Nitrous air, dephlogisticated . . . 104
anhydride & 4 & 108-109
—synonyms,108; preparation, 108;
properties, 109.
—action of, on metals . . . . 246
chloride . . . . . . . . . 119
gas (nitric oxide) . . . . . . 106
—(nitric peroxide) . . . . . 110
oxide . . . . . . . 104-106
—synonyms, 104; history, 104;
preparation, 104; properties,
104-106; uses, 106.
—action of, on metals . 246
—(nitrous anhydride). . . . . 108
oxychloride . tº gº tº 120-121
—synonyms, 120; preparation, pro-
perties, 121.
Nitryl . . . . . . . . . . 110
Nitrylic chloride . . . . . . . 121
—synonyms, preparation, proper-
ties, 121.
Nonane . . . . . . . 528
Nonene . . . . . . . . . . 533
Nonylene . . . . . . . 533
Nonylic acid . . . . . . . . 597
alcohol . . . . . . . . . 558
Nordhausen sulphuric acid . . . . 356
Notes for practical analysis 437-462
O.
Obsidian or volcanic glass . . . . 343
Occlusion of hydrogen . . 193, 240
Ochre . . . . . . . . . .344
preparation, properties, 551 ; table
of essential oils . . . . . 552
volatile, as disinfectants . . . . 494
fixed . . . . . 631-634
—saponifiable . . 632-634
—-action of heat, solubility . . 632
— —-air . . . . . . . 632, 683
—tabulated list of fats and oils . 633
—list of fatty bodies . . . 634
—non-Saponifiable. . 634
drying, table of . . . . . . 633
non-drying, table of . . . . . 633
fish, table of . . . . . . . 633
Olefiant gas series . . . . . . 228
Olefine type . . . . . . . . 467
Olefines, The . . . 533-535
4
preparation, 534; properties, 534-535.
Oleic acid . (310
Olein . . . . . . . . . . . 634
Oleo-resins. . . . . . . . . 555
“On,” the termination, . . . . 20
Onyx, amorphous variety of silica . 186
Opal, amorphous variety of silica . 186
Opianine . . . . . . . . . 652
Orange chrome . . . . . . . 360
Orceine, red coloring matter 677, 679
Orcin . . . . . . . . . . 575
Orcins . 475
Orcine . tº wº . . 677
Organic analysis . . . . 467-482
Organic bodies, ultimate analysis
of . . . . . . 468-481
proximate analysis of 4S1-482
natural and artificial changes of 483-507
action of nitric acid on . . . . 118
—of nitric peroxide on . . . . 112
Organic chemistry . 463
definitions of tº s tº º . 463
Organic compound and organised
body, distinction between . 463
Organic matter, action of ozone on,
and on organic compounds . . 62
Organic matters in the air . . 103
Organo-boron compounds . 669
Organo-metallic compounds . 669
Organo-silicon compounds. . 669
766 INDEX.
PAGE -- PAGE
Orpiment . . . . 398 || Oxide—continued.
Orthophosphates . º . 281 ethylenic. . . . . . . . . 640
definition, preparation, varieties, ferrous . . . . . . . . . .353
properties, tests . . . . . . 281 ferric . . . . . . . . . . 354
Orthophosphates or triphosphates . 138 hydrated cobaltous. . . . . . 334
Orthophosphoric acid , 135-136 indic . . . . . . . . . . .338
Synonyms, natural history, pre- iridic . . . . . . . . . . 436
paration, properties, 135; tests, iridious . . . . . . . . . 436
136; uses, 136. magnetic, of iron . . . . . . 354
Orthotoluidine . 665 magnesic . . . . . . . . . 323
Orthocresol. º . 572 Imangan Olls . . . . . . . . 327
Orthoxybenzoic acid . 614 manganic . . . . . . . . 327
Orthoxylene . . . . . . . . 53 mercuric . . . . . . 55, 423
Osmic acid . . . . . . . . 381 Imercurous . . . . . . . . 422
chloride . . 381 molybdous . . . . . . . . 409
hexachloride . 381 molybdic . . . . . . 409
oxide. . 381 nickelous . . . . . . 335, 336
tetroxide * * . 381 nitric . . 106-108, 246
Osmious dichloride . . 381 nitrous tº $ & . 104-106, 246
oxide. tº . . 381 —(nitrous anhydride) . . . . 108
Osmium . . . . . . 380-381 Osmic . . . . . . . . . 381
history, natural history, extrac- Osmious . . . . . . . . . 381
tion, 380; properties, 381. palladic . . . . . . . . . 378
compounds of osmium . 381 palladious . . . . . . . . 378
—reactions of . 381 perchloric . . . . . . . . 81
Osmosis. . . . . . . . . . 193 pernitric . . . . . . . . . 110
Ossein tº a g º º 693, 694 phosphoric, a dehydrating agent . 506
“Ous,” the termination . . . . 21 platinic . . . . . . . . . 405
Ov-albumen . 688 platinous . . . . . . . . 405
Oxalate of lime . . 720 plumbic . . . . . . . . . 413
calcic. 318, 322 plumbous . . . . . . . . 413
ferrous . 353 potassic . . . . . . . . . 291
Oxalates, iron. gº º . . .357 pyrographitic . . . . . . . 167
Oxalic acid . . . . . 618-620 red . . . . . . . . . . 354
—natural history, preparation, rhodic . . . . . . . . . 380
618; commercial preparation, ruthenic . . . . . . . . , 382
618-619; properties, uses, 619. Tuthenious . . . . . . . . 382
—reactions of . . . . . . . 628 sodic . 299, 526
aldehyde . . 645 stannic . . . . . . . 386
Oxaluric acid . . 717 Stannous . . . . . . . . . 385
Oxamide. . 673 strontic . . . . . . . . . 317
Oxamic acid . 673 sulphuric, a dehydrating agent. .. 506
Oxide, aluminic . 340 telluric . . . . . . . 165
antimonious . . 390 tellurous . . . . . . . . . 164
antimonic . . . . . 390 thallous . . . . . . . . . 431
antimonoso-antimonic . 391 thallic . . . . . . . . . 431
argentic . . . . . . . . . 418 uranic. . . . . . . . . . 337
argentous. . 418 uranous . . . . . . . . . 337
auric . 402 uranyl . . . . . . . . . 337
{ll II'OllS . & ſº is , 401 Zincic. . . . . . . . . . 332
baric . . . . . . . . . . 316 Oxides, The, of metals . 240-245
benzoic . 613 —preparation of . . . . . . 241
bismuthic . 374 —varieties of . . . . . . . 242
bismuthous . . 374 —table of gº tº ſº. . 242
cadmic. . 376 —properties of . . . . . . . 243
cassic . . .309 acid . . . . . . . 593
calcic . tº º . 319 of nitrogen tº e º º 103, 113
carbonic . . . . . . . . . 175 —general remarks on the . . . 113
chloro-sulphuric . 162 of tungsten . . . . . . 432-433
chromic . 358 auric, argentic, platinic . . . . 56
cobaltic & ſº tº º . 334 Oxidising bodies, action of, on sugar 582
cobaltoso-cobaltic . . . . . . 334 || Oximide P . . . . . . . 673
cobaltous 333, 334 || Oxyadipic acid. . . . . . . 621
cupric . 369 || Oxy-arsenicum salts . . . . . 284
cuprous . , 368 || Oxy-benzene . . . 571
INDEX.
767
PAGE PAGE
Oxybenzoic acid . . . 614 || Oxygen, action of—continued.
series, acids of the . 613-614 —on carbon . . . . . . . 169
Oxybromide, bismuthous . 373 —on iron. . . . . . . . . . . . 332
Oxybutyric acid . . . . . . . 605 —on the metalloids . . . . . 58
Oxycarbonate, hydrated zincic. . . 333 —on the metals . . . . . . . _58
Oxychloride of phosphorus . . . . 140 —nascent, on organic bodies . . 505
carbonic . . . . . . . . . 181 — —on alkaloids . . . . . . 650
manganic . . . . . . . . . 329 Oxygenated water . . . . . . 209
nitrous 120-121 Oxyhaemoglobin . . . . . . . 65
uranium . . . . . . 337 Oxyiodide, bismuthous . . . . . 373
Oxy-chlorides, mercuric . 426 Oxymethylbenzoic acid. . 614
silicic . . . . . . . . . . 188 || Oxymalonic acid . . 621
chromic . . . . . . . . . 360 | Oxymuriatic acid . . . . . . . 82
Oxygen . . . . . . . . 54-68 || Oxyphenol . • e e s tº . 575
synonyms, 54; history, 54; natural Qxy-phosphorus salts . . . . . 282
history, 55; preparation, 55; pro- Oxypicnic acid . . . . . . . . 678
perties, 57; allotropic oxygen, Oxy-Salicylic acid . 615
59-63; uses of oxygen, 64. Oxysalts. . . . . . . . .266
liquefaction of . . . . . . . . 723 —double . . . . . . . . . . . 287
daily consumed by the food taken of chlorine, bromine, and iodine . . 279
by an average man. . . 66 of lead • * * 415-416
use of, in medicine . . . . . 68 of mercury . e . 429
in the air . . . . . . . . 97 of potassium. . . . . . . . 295
compressed, a fearful poison . . 58 of silver 420-421
experimental determination of the barium . . . . . . . . . .316
carbon, hydrogen and oxygen of cupric 371-372
an organic compound not con- iron . 356
taining nitrogen . . . 469 Sodium - . 301
determination of e . 470 Oxysuberic acid . . 621
compounds of bromine and 85-86 Oxysuccinic acid . e . 621
—of barium with oxygen and Oxysulphide, carbonic . . 183
hydroxyl . . . . . . . . .315 Oxysulpho salts . . . . . . . 271
—of calcium with oxygen and Oxytricarballylic acid º . 625
hydroxyl . . - - 318 . Oxytrichloride, phosphoric . . . 140
—of carbon and . . . . . 175 | Oxyvaleric acid . . . . . . . 605
—of carbon with oxygen and the Ozone * * * * * 59–63
haloids . 181 history, 59; nature, 59-60; pre-
—of hydrogen and . . . . . 195
—of iodine and . . . . . . 90
—of iron with. . . . . . . .353
—of lead and . . . . . . . 413
—of manganese and . . . . . 326
—of mercury and . . . . . . 422
—of molybdenum and . . 4US
-—of nitrogen and . . 103-113
—of nitrogen, oxygen, and chlorine
120-121
—of phosphorus and . . . 130-139
—of platinuin and 405-406
—of potassium, oxygen and
hydroxyl. . . . . . . 291
—of Selenium and . . . . . 163
—of silicon and . . . . . . 1S6
—of silver and. iº 41S-419
—of sodium with oxygen and hy-
droxyl . . . . . . . . . . .299
—of sulphur with oxygen and hy-
droxyl . . . . . . . . .
—of sulphur, oxygen, and the
haloids tº º tº º . 161
—of tellurium and . . . . . 164
147
—of thallium and . 431
—of titanium and . 362
—of tungsten and. - . 432
action of, on ammonia . . . . 219
paration, 60; properties, 61-62;
special tests, 62; quantitative
determination, 63.
faculty of phosphorus of evolving,
in damp air . . . . . . . 130
presence of, in the air 99
See Antozone.
P.
Painting on glass. . . . .30S
Palladium . . . 377-379
history, natural history, extraction
from platinum ores, from gold
ores, 377; properties, 377-378.
compounds of palladium 37S-379
—Teactions of . . . . . . . 379
chloride of . . . . . . 378
suboxide of . . . . . . . . 378
Palladic chloride . - . 378
oxide . . . . . . . . . . 378
Sulphide . . . . . . . . . 378
Palladious chloride . . . . . . 378
cyanide . 379, 511
iodide . 378
oxide . 378
Sulphide . . 379
768
INDEX.
IPA GE PAGE
Palm oil . . . . . . . . . 634 || Perchloric—continued.
I’almitic acid . . . . . . . . 604 oxide - - - º ... 81
aldehyde 4 s • . 643 | Perchloride, manganic . . 329
Palmitin . . . . . . . . . 634 | Pericline - * . 343
Pancreatic fluid . . . . 709–710 | Periodates . . 279
composition of, per 1000 parts . . 709 | Periodic acid . * * * 90-91
Pancreatin . . . . . . . 710 | preparation, 90; properties, 91.
Papaverine . . . . . 652 | Periodicity, Mendeleeff’s law of
“I’ara,” the prefix . 22 723-725
I’arabanic acid . 717 | Perissads or odds . . . . . . . 43
Paraglobulin . . 689 | Permanganates, the . - . 329
Paracresol . . 572 with superheated steam . . . . 56
Paracyanogen . . . . . . 49 | Permanganic acid . 329
Paraffins 528-533, 548-549 anhydride . 327
preparation of . a º is . 530 | Pernitric oxide . I 10
general properties. . 530 | Pernitrous acid tº e. ... 108
Paraldehyde . 644 Peroxide of chlorine . . . . . . 81
Paramorphine. . 65.2 of hydrogen (hydric peroxide) . . 209
Paramylon . . . . 588 of nitrogen . . tº º - . 110
Paranaphthalene . . 544 acetic . . 602
Paraniline . • . 661 argentic . . 419
Paraoxybenzoic acid . 614 baric . 56, 315
Parapectin . e . 589 benzoic . . 613
Paratartaric acid . . . 49 calcic . - * * * * . 319
Paratoluic aldehyde . . 645 chloric . . . . . . . . . 81
Paratoluidine . . 665 hydric * * g e is . 209
Paraxylene . . . . 537 —a powerful oxidizing agent . . 11
Parchment, vegetable . 684 manganic . . . . . . . . 55
Parvoline . . . . . . . . 662 nitric * * * * * 110, 247
Pattinson's white oxychloride . 414 plumbic peroxide or dioxide. . 414
IPearl hardener (calcic sulphate) . 321 potassic . • * * * . .291
Pectin tº $ ºr tº . 589 strontic & tº . 317
Pectose . . 589 || I’eroxides, acid . . . . 593
Pelargonic acid . . 597 | Persulphide of hydrogen . 226
Penicillium glaucum 485, 486 hydric • * > . 226
Tentachloride of iodine . . . . 91 potassic . . . . . . 29.4
Pentachloride or perchloride of phos- Persulphomolybdic acid . 409
phorus . . . . . . . 140 | Persulphuretted hydrogen . 226-227
Pentachlorides . 257 | Petroleum © tº tº dº . 548
Pentachlorobenzene . . 540 spirit . . 548
Pentadecane - s . 528 Phenanthrene . . 546
Pentafluoride, arsenious . 395 Phenic acid . 571
Pentasulphide, ammonic . 311 Phenoic acid . . 612
calcic . . . . . . . 318 || Phenol . * - . . 571
cupric . 371 || Phenols, The . 569-572
dipotassic . 294 || Phenose, same composition as grape-
phosphorus . . 162 sugar . . . . . . . . . 541
Pentane . 528 Phenylamino - - 661, 663
Pentathionates , 274 Phenylbenzylic ether . 638
Pentathionic acid . 160 | Phenylbutylene . . 541
synonyms, history, preparation, Phenylia º . 663
properties, 160. Phenylic acid . . 57 l
Dentethylenic glycol. . 575 alcohol 570-572
Pentylic acid . . . . 603 ether . . 638
alcohol . 558 hydride . . . . 539
Pepsin . º . 709 || Phenyl-lactic acid . 614
I’eptones . . . . . . 690 Phenyl-propiolic acid. .. - . 616
“Per,” the prefix . . . 22 Philosopher's wool (zincic oxide) . 331
l’erbromic acid º 86 Phlogisticated vitriolic acid . 148
Perchlorate, hydric . . . 82 | Phlogiston . e tº 93
potassic . e 279, 297 hydrogen . 191
Perchlorates . . .279 || Phloretic acid . . 614
I?erchloric acid - e. 82-83 || Phlorizin . 586
—synonyms, 82; history, 82; pre- Phlorol. . 569
paration, 82; properties, 83. Phosgene gas . . 181
INDEX. 769
&Y
O
D
PAGE IPAGE
Phospham . . . . . . 142 Phosphorus—continued.
preparation, propertie . 142 preparation, 123; varieties, 125;
Phosphamine . * * . 221 properties, 125; solubility, 126;
Phosphate of lime . 720 tests, 129; uses, 130.
of soda . . . . . 305 compounds of phosphorus and oxy-
ammonic magnesic . 325 gen . . . . . . . . . . 130
calcic . . . 318 —of phosphorus and the haloids . 139
ferric - . 353 —of hydrogen with . . 221
ferrous hydric . . 353 —of sulphur and . . . . . . 162
hydric disodic . . 309 action of ammonia on phosphorus
—magnesic . . 323 compounds . . . . . . . 142
—sodic . . 305 general remarks on the acids of the
magnesic . . . . . 323 oxides of phosphorus . . . . 137
sodic ammonic hydric . 313 estimation of, in an organic body . 473
triargentic . . 418 action of, on the metals . . . . 245
tricalcic . . 318 proportions of, per cent. present in
trilithic . . . . . 308 various animal tissues. . . 123
Phosphates 134, 281, 305 —in which certain gases stop the
allies of the . . . . 283 slow combustion of. . . . 128
aluminic . 343 quantities of vapor required to
calcic . 322 check the luminosity of, in air
thallous . • . 431 at elevated temperatures . 12S
Phosphide, calcic . . 318 tables of solubility of, in various
cupric * * * . . 371 liquids. . . . . . . . 126
Phosphides . . . . . . 265-266 Phosphorus, iodides of . . . . 141
definition, natural history, pre- oxide (phosphorous anhydride). 132
paration, 265; properties . . 266 oxychloride of . . . . . . 140
Phosphines. . . . . . . . 666 pentachloride or perchloride of . 140
l’hosphite, hydric . 132 pentasulphide . 16.2
l’hosphites . . . . . . . 282-283 protosulphide 162
definition, 282; properties, tests . 283 sesquisulphide . 162
Phosphoretted hydrogen, gaseous 221-223 suboxide of . . . 131
—liquid . . . . . . . . . 223 sulphochloride of . * - 141
—solid . . . . . 223-224 trichloride or terchloride of . . . 139
l’hosphoric acid . . . . . . . 47 trioxide (phosphorous anhydride). 132
—conversion of phosphorus into . 130 I3aldwin's (calcic nitrate) . 122
—action of, on organic matters . 503 Bolognian (baric sulphate) . . l 22
—(orthophosphoric acid) . 135 Homberg's (fused calcic chloride). 122
anhydride . . . . . 133-134 Phosphoryl chloride or trichloride . 140
—preparation, 133 ; properties, l’hthalic acid . - e. 624, 626
133-134. . series, acids of the. º 624
—quantity of, per cent, present in Phyllocyanine. 679
different substances . . 123 Phylloxanthin. 678
chloride . wº, ºr 140, 506 || Physetoleic acid . 6I ()
—synonyms, preparation, proper- Physostigmia . 653
ties, 140. l’icocarpine ($53
oxide, a dehydrating agent. . 506 || Picoline. . . ($61
oxytrichloride . º 140-141 Picric acid . . . . . . . 678
—synonyms, preparation, 140 ; Pictet's liquefaction of oxygen and
properties, 140-141. hydrogen . * * * 723
sulphotrichloride . . . . 141 Pigments in urine 718
—synonym, preparation, proper- Pigmentum nigrum . 6S0
ties, 141. Pimelic acid * - - 618
Phosphorous acid . . 132-133 || Pinic acid . . . . . . 554
—synonym, preparation, 132; pro- Piperidine . . 661
perties, 133. Piperine. 49, 653
anhydride . . . . . . . . 132 || Pit gas . . . 22S
—synonyms, preparation, proper- I’lant, life of a . . . . . . 685
ties, 132. Plaster of Paris . . . . . 269, 320
chloride . . . . . . . . . 139 Platinate of soda . . . . . 406
—synonyms, preparation, proper- Platinamine e 407
ties, 139. hydrochlorate of 407
trihydride . . . . . . . 221 nitrate of 407
Phosphorus . . . . 122-142 | Platinic chloride . . . . . . . 406
history, 122; natural history, 123; nitrate . . . . . . . . . 405
770 INDEX.
n PAGE I? AGE
Platinic—continued. Potash—continued.
oxide. . 405 table showing the percentage
Salts J 408 amount of, in aqueous solutions
Sulphate . . . 405 of various specific gravities . . 729
sulphide . 405, 408 anhydrous (potassic oxide) . . . 291
I’latino-chlorides . . . . 406 bicarbonate of . . . . . . . 295
l’latino-cyanogen. . . . . . . 518 bichromate of . . . . . . . .359
I’latinous chloride . . . . . . 406 caustic (potassic hydrate) . . . 291
oxide . . . . . . . . . . 405 red prussiate of . . . . . . 520
sulphide . . . . . 405, 408 yellow prussiate of . . . . . 518
sulphite . . . . . . . . . 405 | Potassa (potassic oxide) . . . . 291
Platinum . . . . . . 403-408 || Potassic acetate . . . . . . . 601
history, natural history, 403; ex- aluminic sulphate . . . . . . 341
traction, 404 ; properties, 404- antimonious tar(rate . . . . . 297
405; uses, 405. bisulphate . . . . . . . . 295
compounds of . . . . . . . 405 bitartrate . . . . . . . . 297
—reactions of . . 408 bromide . . . . . . . . . .293
—and oxygen 405-406 carbonate . . . . . . . . .309
—and chlorine . . . . . . . 406
—and sulphur . . . . . . . 408
bases produced by the action of
ammonia on the chlorides of
platinum . . . . 406-408
binoxide of . . . . . . . . 405
protochloride of . . . . 406
letrachloride, perchloride or bi-
chloride of . 406
Platosamine . 407
hydrochlorate of . 407
Plumbago or black lead. . . . . 167
Plumbic acetate . . . . . . . 601
bromide . wº . 412
carbonate . . . . . . . . 412
chloride . . . 414
chromate. 360, 415
—basic . . . . . . . 360
—as an oxidising agent . . . 469
ethide. . . . . . . . . . 670
ferricyanide . . . . . . . 517
ferrocyanide . . . . . . . 517
fluoride . - - - - - . 412
iodide . . . . . . . . . 415
nitrate 412, 415
basic nitrates . 415
nitrites . 415
oxide. g - * . 413
peroxide or dioxide . 414
phosphates . . 415
Selenide . . . . . . . . . 412
sulphate. 412, 415
sulphide . . 415
sulphite . . 4 16
sulphocyanate . . . . . . . 516
Plumbous oxide . . 413
sulphide . t . 415
Podophyllum resin . 554
Polybasic acid . . . . . . . 253
Polymerism . . . . . . . . 49
chlorate . . . . . 1 1, 56, 297
chloride . . . . . . . . . 292
chromate . . . . . . . . 359
cyanide, 293, 511, 512; its uses, 513.
dichromate . e - - - 359
diiodate . . 278
dioxide . . 291
ferricyanide. . 293, 520
—reactions . . . . . . . . 520
ferrocyanide . . 293, 518
fluoride . . . . . . . . . 293
fluosilicate . . . . . . . . .293
hydrate . - . 291
hydric sulphide . . . . . . 394
hydroxide - * . 291
iodate . . . . . . . . 278
iodide . . . . . . . . . 292
manganate . . . . 328
nickelous cyanide . . . . . . 517
nitrate 274, 295
nifrite . 297
oxide. - - tº - . . 291
perchlorate . . . . 279, 297
permanganate as a disinfectant. . 494
peroxide . . . . . . . . . 291
persulphide . . . . . . . . 294
platino-chloride . 405
rhodic chloride. . 380
—sulphate e , 380
sulph-hydrate . . 294
sulphocyanate . . 516
tart ratc . . . . . . . . 297
triiodate . . . . . . . , 278
Potassium . . . . . . . 289-297
history, natural history, prepa-
ration, properties, 289.
table of compounds of potassium , 290
compounds of potassium and oxy-
gen and hydroxyl . . . 201-293
—of potassium and sulphur. . , 294
I’opulin. • * * . 586
Porcelain and pottery . 344-346
mode of manufacture. 345-346
Porphyroxine. tº a . 652
Porphyry . . . . . . . 343
IPortland cement . . . . . . . 320
Potash (potassic hydrate) . . . . 291
oxysalts of potassium . 295-297
Pottery, Porcelain and . 344-346
l’refixes . . . . . . . . . 22
Pressure, average, of the air in Eng-
land . . . . . . . . . 96
standard . . . . . . . . , 32
Preston Smelling salts . . . . . 312
INT) EX, 771
PA GTE PAGE
Propane. . . . . 228, 528 Pyrophosphates . . . . . . . 282
Propargylic alcohol . . 569 definition, preparation, tests . . 282
Propene . . . . . . . 533 or tetraphosphates . . . . . . 138
Propenyl alcohol . . . 576 || Pyrophosphoric acid . . . . 134-135
Propine. & . 536 synonyms, preparation, 134; pro-
Propione . 646 perties, tests, 135.
Propionic acid. . 602 || Pyroracemic acid . . . . . . . 608
aldehyde. . 643 Pyrotartaric acid . . . . . . . 618
Propionitrile . 673 || Pyroterebic acid . . . . . . . 610
Propylbenzene . 537 | Pyroxylic spirit . . . . . . . 562
Propylene . * 228, 533 || Pyroxylin . . . . . . . . . 684
glycol . . . . 573 || Pyrrol . . . . . . . . . . 661
Propylenic ether . 640 || Pyruvic acid . . . . . . . . . 608
Propylic acid . 602 series, acids of the . . . . . . 608
alcohol 566
Propyliodide sº 630
l’ropylmethylbenzene . . 537
Proteid, coagulated . . 690 Q.
Proteids * > 6SS-690
reactions of . . . 690 | Quadrantoxide, cuprous . . . . 368
“Proto,” the prefix . 22 | Quantivalence . . . . . . . . 39
Protochloride of carbon . . 181 or atomicity of the body, method of
of iodine . . . . . . 91 determining the . . . . . 40
Protosulphide of nickel . . 336 | Quartene . . . . . . . . . 533
diammonic iº . 311 Quartine . . . . . . . . . 536
phosphorus . . 162 | Quartz, crystalline variety of silica . 186
Protoxide of cobalt . 333 Quercitrin . . . . . . 586, 679
of nitrogen . . 104 || Quicklime (calcic oxide) . . . . 319
Prussian blue . . . . . 520, 521 Quicksilver . . . . . 421-429
Prussiate of iron (prussian blue) . . 521 | Quinicine . . . . . . . . . 651
of potash, red g . 293, 520 | Quinidine . . . . . . . . . 651
—yellow . 293, 518 | Quinine . . . . . . . . . . 651
Prussic acid . . 509-511 tests for . . . . . . . . . . 675
Tseudocumene . . . . . . . 537 | Quinoidine . . . . . . . . . 651
Psilomelane . . . . . . . . 328 Quinones . . . . . 528, 546
Ptyalin . . . . . . . . . 708 | Quintene . . . . . . . . . 533
Puce or brown lead oxide . . . . . 414 | Quintine . . . . . . . . . 536 .
Puddling of iron . . . . . . . 350 | Quintone (valylene) . . . . . . 536
Pumice stone . . . . . . . . 343 -
Purple of Cassius . . . . . . . 403
Purpurate of ammonia . . . . . 717 T
Purree or Indian yellow . . . . 678 V -
Pus . . . . . . . . . . . 721
Putrefaction, definition of . . . . 492 || Racemic acid . & 49, 623
conditions necessary for . . . . 492 || Radicals, compound . . . . . . 28
means of preventing . . . . . 493 chemistry of, (Liebig's definition of
Pyin . . . . . . . . . . 721 organic chemistry) . . . . . 464
Pyrene . . . . . . . . . . 547 | Rain water . . . . . . . . . . 206
Pyrethrin . . . . . . . . 554 | Reagents, action of, on organic bodies 506
Pyridine . . . . . . . . . 661 | Red-bole . . . . . . . . . .344
Pyrites . . . . . . . . . . 143 | Red coloring matters . . . . . 679
mundic . . . . . . . . . 356 | Red lead . . . . . . . . . 55
Pyrocatechin . . . . . 575, 636 | Red precipitate . . . . . . . 423
Pyrocatechuic acid . . . . . . 615 | Redruthite . . . . . . . . . 370
Pyrogallic acid . . . . . . . 577 | Regelation, phenomenon of . . . 198
series . . 577-578 Reiset's first base . . . . . . . 407
Pyrogallol . . . . 577, 636 second base . . . . . . . . 407
Pyrographitic oxide . . . . . . 167 | Resinification . . . . . . . . 64
Pyroligneous ether . . . . . . 562 | Resins . . . . . . . . 553-555
Pyrolusite . . . . . 55, 328 preparation, 553, properties, 553–
Pyromellitic acid . . . . . . . 626 554; varieties, 554, uses, 555.
Pyrophorus (Homberg's) . . . . .342 gum . . . . . . . . . . 555
Pyrophosphate, argentic . . . . . 418 oleo- . . . . . . . . . . 555
magnesic . . . . . . . . . 323 | Resorcin . . . . . . . . . 575
sodic . . . . . . . . . 305 | Respiration . . . . . . . 64-67
772 INDEX.
TAGIE
Rhodic chloride . 380
oxide . * * - e. . 380
sulphate . . . . . . . . . 380
Rhodium 379-380
history, natural history, extraction,
379; properties, 379-380.
compounds of rhodium . 380
—reactions of . 380
Rhubarb resin . . . . . . . . 554
l{icinoleic acid . 60S
l{inman's green . 333
River water . 207
Rocellic acid . . 618
Rochelle salt 287, 297
Roman cement • * . 319
Rosaniline (aniline red) . 665
Rosin, common . 554
Rottlerin e . 554
Rouge, jewellers'. . . . . .354
Ruberythric acid . . . . . . . 586
Rubian . te 677, 679
Tubidine . . 662
Rubidium . . . . . . . 309
compounds of caesium and rubidium 309
Ruthenic acid. . 38.2
anhydride . 38.2
chloride . . .382
oxide . . . . 382
sulphide . tº e . 382
tetroxide . . . . . . . . 382
Ruthenious chloride . . . . . . 382
oxide . He . . .382
Ruthenium . * * * 381-383
history, 381; natural history, ex-
traction, properties, 382.
compounds of ruthenium . 38.2
—reactions of 382-383
oxides of . . 38.2
Tutic acid . . 597
alcohol . 558
Rutile or iron sand . 362
lèutylene . . . . . . . . . 536
S.
Safflower * * * * * . 679
Saffron . . . . . . . . . . 679
Sal ammoniac . . . . . . . . 311
Sal prunelle balls . 295
Salicin . . . . . . . . . . 586
Salicylic acid . . 614
alcohol s e - . 575
aldehyde . . . . . . 645
series, acids of the 613-614
Saligenin . . . . . . . . . 575
series. º 4 & a . 575
Saline matters in the air . 103
Saline waters, aperient . . . 207
Saliva. . . . . . . . . 707-708
composition per 1000 parts of . . 707
Salt, common (sodic chloride). . 299
Everitt's white. . . e . 517
microcosmic . . . . . . . 313
radicals, generalisation on the . 91-92
IPAGE
Saltpetre © tº 291, 295
Chili . . . . . . 304
Saltpetres (nitrates). . . . . . 374
Salts * - - - 251-266
in Solution, action of acids on . . 5
—action of bases on . . . . . 6
—action of salts on . . . . . 6
in urine . . . . . . . . . 718
effect of elasticity upon . . . . 8
varieties of . . . . . . . . 255
spirit of . . . . . . . . . 210
Salts allied to the nitrates . . . . 278
haloid * * * 256-266
—of the acids . . 594
double 286-287
—of cyanogen . 517-524
—haloid . . . . . . . . 287
—sulphur . . . . . . 287
metallic, of acetic acid . . . . 601
—action of ammonia on . . . . 220
nitro-oxygen . . . . . . . 277
Salts of the alkaline metals, reactions
of the . . . . . . . 440
of aluminium . . . . . . . 340
of aluminium, chromium, and ilon,
reactions of the . . . . . . 446
of antimony . . . . . . . 389
of arsenic . . 395
of barium, strontium, calcium, and
magnesium, reactions of the . . 442
of bismuth . . . . . . . . 373
of cobalt . . . . . . . . 334
of copper, bismuth, and cadmium,
reactions of the . . . . . . 451
of gold . . . . . . . . . 401
of indium . . . . . . . . 338
of lead . . . . 412
of lead, silver, and mercury, reac-
tions of the . . . . . . . 455
of magnesium . . . . . . . 323
of manganese . . . . . 327
of manganese, zinc, nickel, and
cobalt, reactions of the . 449
of mercury . . 423
of molybdenum - 409
of nickel . 337
of osmium - * * . 381
of palladium . . . . . . . 378
of platinum . 405
of potassium . 290
of rhodium . . 380
of ruthenium . 382
of silver . . 418
of thallium . . . . 431
of tin . . . . . . 385
of tim, antimony, and arsenic, re-
actions of g 452-453
of uranium . . 337
of zinc . 332
oxy-arsenicum . º . 284
oxy-phosphorus . . . . . . 282
oxy-Sulpho salts . 271
oxy-salts . . . . . . 266
—of barium . . . . 316
—of chlorine, bromine, and iodine 279
1Nî).E.X. * 773
PAGE IPAGE
Salts, oxysalts—continued. Sextine . . . . . . . 536
—cupric. * 371-372 Shamoying, mode of . . . 637
—of iron . 356 Shellac . & & ſº . 554
—of lead 415-416 | Shells, composition of . 692
—of mercury . 429 | Sienna. . . . * . . .344
—of potassium. . . 295 Silica * * * * 186-187
—of silver . . . 420-421 synonyms, natural history, 186;
—of sodium . 301 properties 186-187
double oxy-salts . 287 | Silicates . * * * * 285-286
Sand, nearly pure silica . 186 definition, natural history, varie-
Sandarach . . . 554 ties, preparation, 285; proper-
Santaline tº º sº ºr . 679 ties . . . . . . . . . 286
Saponification by lime . . 635 of Sodium . . . . . 305
by steam . . . . . 636 aluminic . 343
by sulphuric acid . . 635 double . 2S7
Saponin tº a $. , 588 magnesic . 325
Sarcine . . . . . 654 Siliceous waters . . . 207
Sarcosine tº º 602, 654, 694 Silicic acid. tº e e 187-18S
Saturated solutions . . . . . 202 —preparation, 187; properties, 18S
Scagliola, or artificial marbles . 321 anhydride . . . . . . . 1S6
Scheele's acid, preparation of . . . 510 chloride . tº . 188
green . . . . . . . 284, 372 ethide . 669
Scheelite . 432 ethylate . . 669
Schlippe's salt . . .393 fluoride . tº ſº º & . 189
Schweinfurt green 284, 372 –synonym, preparation, properties 189
Sclerogen . 685 hydride . . . . . . . . 235
Scott's cement tº e . . .320 –synonym, preparation, properties 235
Sea-water, analyses of . 207-208 hydrotrichloride . . . . . 18
Sea-weed, soda from . 302 iodoform . 189
Sebacic acid . 618 methide . . 669
Sedative salt . . 184 methylate . 669
Selenate, basic . 269 nitride . 190
Selenates . 3º . 269 oxychlorides . 18S
definition, tests . 269 sulphide . . 190
Selenetted hydrogen. . 227 tetrabromide . I S9
Selenhydric acid . . 227 tetrafluoride . 189
Selenic acid . 163 tetrachloride . . . . . 1SS
Selenide, cupric . 367 —synonym, preparation, properties 18S
dihydric. 22 tetriodide . . . . . . . . 189
plumbic . . 412 tribromide . . 1 S9
Selenides tº e º & . 265 trichloride . 1 SS
Seleniuretted hydrogen. . 227 triodide . , 189
Selenious anhydride. . 163 | Silicides & . .266
Selenium * * * g e 162-164 Silico-fluoric acid . . . . 189
history, natural history, prepara- Silico-formic acid or Leukon . 190
tion, 162; varieties, 162-163; Silicon or Silicium tº ſº; 1S,5–190
properties, 163. history, natural history, varieties,
compounds of selenium and oxygen. 163 185; preparation, 185-186; pro-
—selenium and chlorine . . . . 164 perties, 186.
Separgylic acid . 618 compounds of silicon and oxygen . 186
Sepia . . 680 —of silicon and the haloids. . ISS
Septene . 533 —of silicon with bromine, iodine,
Ser-albumen & . 688 etc. . . . . . . . .
“Sesqui,” the prefix . 22 —of silicon with fluorine . . 189
Sesquicarbonate, ammonic • 312 —of hydrogen and . . 235
Sesquichloride of carbon . 181 hydride of . . . . 235
Sesquichlorides . 257 dioxide . 1S6
Sesquioxide of cobalt . 333 adamantine . . 185
of nickel . 336 amorphous . 185
Sesquioxides . . . . . . 242 graphoidal . 1 S5
Sesquisulphide, arsenious . . 398 || Silk . & . . 695
chromic . g is a . 361 | Silver * * * * * * 416.421
phosphorus . . . . . . . . 162 history, 416; natural history, ex-
Sexdecene . . 533 traction, properties, 417; uses,
Sextene . . . . 533 417-418.
774 INDEX.
PAGE PAGE
Silver—continued. Sodic—continued.
compounds of silver . . . . . 418 potassic tartrate . . . . . . .297
—of silver and oxygen . . 418-419 pyrophosphate . . . . . . . 305
—of silver and chlorine . . 419–420 rhodic chloride . . . . . . . 380
—of silver and sulphur . . . . 420 Stannate . . . . . . . . . 386
oxy-salts of silver . . . . 420-421 Sulphate . . . . . . . . . 301
extraction of, from lead . . . . 411 sulphite . . . . . . . . . 301
reactions of the salts of . . . . 455 thiosulphate or hyposulphite . . 158
frosted . . . . . . . . . 417 tungstate . . . . . . 271
fulminate of . . . . . . . 516 Sodium . . . . . . . . 297-306
fulminating . . . . . . . . 419 history, 297; matural history, 297-298
oxidized . . . . . . . . . 417 oxy-Salts . . . . . . . . . 301
fluoride, chloride, bromide and table of compounds of . . . . 298
iodide of . . . . . . . . 92 compounds of sodium with oxygen
nitrate of . . . . . . . . 421 and hydroxyl . . . . . . 200
protoxide of . . . . . . . 418 —of sodium and the haloids . . 299
subchloride of . . . . . . . 419 phosphates . . . . . . . . 305
suboxide of . . . . . . . . 418 silicates of . . . . . . . . 305
Silver glance . . . . . . . . 417 | Soil, as a natural disinfectant . . . 493
Size . . . . . . . . . . . 693 Solanin . . . . . . . . 586, 652
Slate . . . . . . . . . . . . . 343 | Solids, solubility of, in water . . . 201
hornblendo . . . . . . . . .343 animal . . . . . . . 691-695
mica . . . . . . . . . . 343 Solubility of solids in water . . . 201
Smalt . . . . . . . . . . . 333 Solutive water (nitric acid). . . . 115
Smcke nuisances . . . . . . . 174 | Solvents, action of, on the alkaloids. 649
Soaps . . . . . . . . . 634-635 | Soot . . . . . . . . . 167, 168
Soda, table showing percentage Sorbic acid . . . . . . . . 611
amount of, in aqueous solutions series, acids of the . . . . . . 611
of various specific gravities . . 730 | Sorbite . . . . . . . . . . 585
ball . . . . . . . . . 302 || Spar, heavy (barium) . . . . . .314
caustic . . . . . . . . . 299 || Spartein gº tº gº is ſº . 651
common washing . . . . . . 302 || Specific gravities, tables of . . 726-7.32
muriate of . . . . . . . . 299 —of bodies, affinity measured by
platinate of . . . . . . . . 406 reference to the, 15.
phosphate of . . . . . . . .305 || Specific heats of elementary bodies . 38
Scotch . . . . . . . . . 302 || Speiss . . . . . . . . . . 335
tungstate of . . . . . . . . 433 || Spelter (zinc). * . 330
urate of . . . . . . . . . 716 || Spinelle ruby . . . . . . . . 341
Sodac hypophosphis . . . . . . 282 || Spirit making, alcoholic fermentation
phosphas . . . . . . . . . 136 in . . . . . . . . . . 491
Sodic acetate . . . . . . . . . . 601 || Spirit of salts . . . . . . . . 210
ammonic hydric phosphate . . . 313 || Spirits of wine . . . . . . . 564
ammonic sulphate . . . . . . 312 || Spiritus nitro-aerius . . . . . . 54
biborate . . . . . . . . . 304 || Spring and well water . . . . . 206
bromide . . . . . . . . . 301 | Stannic acid . . . . . . . . 386
carbonate . . . . . . . . 302 chloride . . . . . . . . . 387
—in well waters . . . . . . 206 ethide . . . . . . . . . 670
chromate . . . . . . . . . 358 oxide . . . . . . . . . . .386
chloride . . . . . . . . . 299 sulphate . . . . . . . . . 385
cyanide . . . . . . . . . fill Sulphide . . . . . . . . . 387
dihydrogen phosphate . . . . 281 | Stanmous chloride . . . . . . 386
dioxide . . . . . . . . . 299 ethide . . . . . . . . . 670
ethide . . . . . . . . . . . . . 670 oxide . . . . . . . . . . 385
hydrate . . . . . . 299, 526 Sulphide . . . . . . . . . 387
hyponitrite . . . . . . . . 278 || Starch . . . . . . . . . . 12
hyposulphite . . . . . . 272, 302 common . . . . . . . . . 587
iodide . . . . . . . . . . . 301 —preparation, properties, action of
manganate . . . . . . . . 328 heat, action of acids, action of
metabismuthite . . . . . . . 374 alkalies, action of haloids, 587.
metaphosphate . . . . . 282, 305 reactions. . . . . . . . . 590
nitrate . . . . . . . . . 274, 304 Starches . . . . . . . 586–588
nitro-prusside . . . . . . . 521 natural history, 586; preparation,
oxide . . . . . . . . 209, 526 varieties, 587.
periodate . . . . . . . . . 279 || Steam, latent heat of . . . . . 200
platino-chloride . . . . . . . 405 | Stearic acid . . . . . 604-605, 635
INDEX. 775
IPAGE PAGE
Stearin . . . tº e º 'º' . 634 Sulphantimonite . . . . . . . 417
Stearolic acid . . 611 Sulphantimonites. . . . . . 393
Stearoptene . . . . . 551 Sulphantimonious anhydride . . . 392
Steel, preparation of 350-35 L Sulpharsenic acid . . . . . . 399
Stibethyl . 667 Sulpharsenious anhydride . . . . 398
Stibine . . 389 Sulphate of copper . . . . . . 371
Stibines. . . 667 of diplatosamine . . . . . . 407
Stibnite 388, 393 acid sodic . . 301
Stilbene. * e º º . . 546 aluminic . . . . . . . . 341
Strontianite . . . . . . . 316 ammonic . . . . . . . . 312
Strontic oxide. . 317 argentic . . . . . . . . . 420
peroxide . . . 317 baric . * : * . 269, 273, 316
Strontium . . . . . . 3.16-317 bismuthous . . . . . . 374
history, natural history, prepara- cassic . . . . . . . . . .309
tion, properties, 316. calcic . . . . 318, 320
compounds of . . 317 chromic . . . . . . . . . .361
—tests for . . . . . . . . .317 cobaltous . . . . . . . . 334
reactions of the salts of . . 442 cupric . . . . . . . . . 371
Strychnine. . 653 dipotassic . . . . . . . 295
tests for . . 676 ferric. . . .357
Stucco . * . 321 ferrous . . . . . 269, 356
Styrolene . . . . . . . 541 gallium . . . . . . . . . 434
“Sub,” the prefix . . . . 22 hydric ammonic . . . . . . 312
Sub-carburetted hydrogen . . 228 hydrig cassic . . . . . . . 309
Subchlorides . tº º . 257 hydric - potassic, a dehydrating
Suberic acid & º & . 618 agent . . . . . . . 506
Suboxide of phosphorus . 31 hydric sodic. . . . . . . . 301
Suboxides . . . . . . 242 indic . * ſº e º ºs . 33
Substitution, inorganic. 46 lithic . . . . . . . . . . 308
organic . . . . . . . 47 magnesic . . . . . . . . 324
Subsulphide of palladium . . 378 manganolls . . . . . . . 330
Succinamic acid . tº & . 673 mercuric. . . . . . . . . 429
Succinamide . 673 ImerCllrollS . . . . . . . . 429
Succinic acid . . . . . . . 620 nickelous e . 336
—natural history, preparation, platinic . . . . . . . . . 405
properties, distinctive reactions 620 plumbic . . . 412, 415
—reactions . * 629-630 potassic aluminic . . . 341
series, acids of the 617-620 potassic rhodic . . . . . . . .380
Succinimide 672, 673 rhodic. . 380
Sucrose . * . . 580 sodic . * 9. . 30 l
Sucroses, The . 580-584 sodic ammonic . . 312
Sugar . . . . . . . 12 stannic . . . . . . . . . 385
cane or sparkling 580-583 thallic. . . 431
—natural history, 580; preparation, thallous . . 432
580-581 ; sugar refining, 581 ; trimercuric . . 423
properties, 581; action of heat, tribasic . . . . 37.2
solubility, action of acids, action zincic. * 56, 269, 332
of alkalies, 582; action of oxi- Sulphates . * * * * 266-269
duzing bodies, 582-583. definition, natural history, varie-
grape . . . . . . . 584-585 ties and constitution, 266; pre-
—history, preparation, properties, paration, 266-267; properties,
action of heat, 584; action of 267-268; tests, 268; uses, 269.
acids, 584-585. allies of the . . . . . . . . 269
milk . . . . . . . . . . 585 mineral, as disinfectants. . . . 494
—natural history, preparation, pro- Sulphide, aluminic . . . . . . . .340
perties, solubility, action of ammonic hydric . . . . . . 311
hent, 585. antimonious . . . . . . 392
granular (grape sugar) . . . . 584 antimonic . 393
mucoid . . . . . . . . 585 argentic . . 420
muscle § . 694 arsenic & & 9 º' . $99
Sugar of lead . . 601 auric . . . . . . . . - 403
Sugars, reactions . . . . . . . 590 tlūrollS . . . . . . . . . 403
“Sulph " or “Sulpho,” the prefix . 22 bismuthous . . . . 374, 375
Sulphantimonates . . . . . . 393 cadmic . . . . . . . . . 376
Sulphantimonic anhydride . . . .393 calcic . . . . . . 318, 320
776
INDEX.
PAGE FAGE
Sulphide—continued. Sulpho-urea - - . 715
chromic . . . . . . . . . 358 Sulphonic acids . . . . . . . 539
cupric . . . . . . . . . 371 Sulphur . . . . . . . . 143-162
Cuprous . . . . . . . . . 370 synonyms, 143; history, 143; pre-
cyanic. . 514 paration, 144; varieties, 144 :
diammonic . - - . 311 properties, 145; uses, 147.
dihydric . . . . . . . . . 224 compounds of sulphur with oxygen
dipotassic . . . . . . . . 294 and hydroxyl . . . . . .
ferrous is e 356, 519 —sulphur and the haloids . 161
hydrated diammonic . . . .311 —sulphur, oxygen, and the haloids 161
hydric sodic . 302 —sulphur and phosphorus . . . 162
indic . . .338 —of carbon and . . . . . . 182
iridic . . 436 —copper and 370-371
iridious . 436 —hydrogen and . . . . 224
magnesic . 324 —lead and . . . . . . . . 145
mercuric . 428 — mercury and . 428-429
Iller CllrollS . 429 —platinum and . . 4.08
palladic . tº s . 378 —potassium and 290–294
palladious . . . . . . . . 379 —silver and . . . . . . 420
platinic 405, 408 estimation of, in an organic body . 473
platinous. 405, 408 action of carbon on . . . . . 170
plumbic . . 415 —on the oxides - . 244
plumbous . 415 oil of . . . . . . . . . . 151
potassic hydric . . 294 volatile spirits of . . . . . . 148
ruthenic . . . . . . . 382 Sulphur auratum . - . 398
silicic . . . . . . . . . 190 chloride . . . . . . . . . 161
stannic . 387 dichloride . . . . . . . . 161
Stannous . . 387 dioxide. . - - -> . 148
thallous . . 431 salts, double . . . . . . . 287
thallic . 431 tetrachloride . . . . . . , 161
titanic . 362 trioxide . . . . . . . . . 150
zincic . . . . . 332 U11'68, ºr º e º 'º - © . 662
Sulphides . . . . . . 262-265 Sulphuretted or hepatic waters . 207
definition, natural history, prepara- hydrogen . . . . . 224-226
tion, 262; properties, 263-264; —action of, on sulphides . . . . 264
tests, 264; estimation, 265. hyposulphuric acid . . . . . 159
Sulphidic acid . . . . . . . . 224 Sulphuric acid 47, 151-157
Sulphite, acid . . . . . . . . 302 —synonyms, history, natural his-
argentic . gº tº . 273 tory, 151; preparation, 151-153:
baric . . . . . . . . . . 273 varieties, 153-154; impurities and
indic . * s e s . .338 tests for the impurities of sul-
platinous . . . . . . . . 405 phuric acid, 154; purification,
plumbic . - 4 16 154; properties, 155-157; uses,
sodic . . . . . . 301 157.
Sulphites . . . . . . . . 273 —table showing the percentage of
definition, preparation, properties, real, corresponding to various
tests, uses, 273. specific gravities of aqueous sul-
Sulpho- or thio- ethers . . . . . . 641 phuric acid . . . . . . . . . . 727
Sulphocyanic acid, preparation and —has no action on nitric acid . . 117
properties . . . . . . 516 —anhydrous . . . . . . . 150
reactions . . . . . 524, 630 —Nordhausen . . . . . . . .356
Sulphocyanate, ammonic . 516 —protohydrate of . . . . . . . . 151
mercuric . e & . 516 —and water, table showing the heat
plumbic . . 516 and condensation resulting from
potassic . . . . . . . . . 516 mixtures of . . . . . . . 156
Sulphocyanates, tests for the . . . 624 —action of, on oxysulpho salts . 274
Sulphocarbonic acid . . . . . 182 — —on organic matters . . . . 507
Sulphochloride of phosphorus . . . 141
Sulphodithionic acid . . . . . . 139
Sulphomolybdic acid . 409
Sulpho-phenyl-urea . . 662
Sulpho-platinates . . . 4.08
Sulpho-sulphates . 271-272
Sulpho-sulphuric acid . . . . . 158
Sulphotrichloride (phosphoric) . 141
anhydride • * 150-151
—synonyms, 150; preparation, pro-
perties, 151.
oxide . . . . . . 150
——a dehydrating agent . 506
Sulphurous acid . 150
—tests, uses. a d - . 150
—a powerful reducing agent . . 506
INDEX. 777
I?A GTE PAGE .
Sulphurous—continued. Terminations . . . . . . . . 21
and sulphuric acids . 103 | Terpinole . . . . . . . . . 550
anhydride . . . . . . 148 || Tetra-allyl-ammonic hydrate . . . 661
—synonyms, history, natural history, Tetrabromide, silicic . . . . . 189
preparation, 148; properties, 148-150 | Tetrabromobenzene . . . . . . 540
waters . . . . . . . . . . . 207 | Tetrabutyl-ammonic hydrate . . 660
Sulphuryl, chloride of . . 149 | Tetrachloride of iodine . . . . . 91
dibromide . . . . . . . . 162 carbonic . . 180, 532
dichloride . . . . . . . . 161 dibismuthous . . 373
hydroxyl chloride . . 162 iridic . . 436
Supersaturated solution . . . . . 202 manganic * - - . 329
Sweat . . . . . . . . 720-721 silicic . . . . . . . . . 188
Sycocerylic alcohol . . . . . . 569 sulphur . - . 16 l
aldehyde. • * * * . 645 | Tetrachlorides. e - - . 257
Symbols (chemical) and formula . . 23 Tetrachlorobenzene . . . . . . 540
Tetrachloromethane . . . . . . 532
Tetradecane e - - . 528
T. Tetrafluoride, silicic. . . . 189
Tetrahydric pyrophosphate . . . 134
Tables of specific gravities, weights Tetramethyl-ammonic hydrate . 660
and measures, etc. . 726-732 | Tetramethylbenzene . 537
analytical º 440-462 | Tetramyl-ammonic hydrate . 660
Tallow . . . . . . . . . . 634 | Tetramylene . . . . . . 533
Tannic acid . . . . . . . . 636 | Tetrane . . * * * . 528
reactions . . . . . . . . . 630 Tetramitride, trititanic . . 362
Tannin . . . . . . . . . . 586 | Tetraphenylethylene . . . . . 547
Tanning, mode of . . . . . . 637 | Tetrasulphide, molybdic . 409
Tannins . * * * - 636-637 | Tetrathionates . . . . . . . 274
special reactions . . . . . 636 | Tetrathionic acid - . 160
Tar, coal . . . . . . 500 synonyms, history, preparation,
wood . . . . . . . . . . 502 properties, 160.
Rangoon, or rock oil . . 548 || Tetrethyl-ammonic hydrate . . . 660
‘‘Tartar ’’ of the teeth . 708 || Tetrethylenic glycol. . . . . . 575
Tartar emetic . . . . . . .297 Tetriodide, silicic . . . . . . 189
Tartaric acid - . 491, 621-623
—natural history, 621 ; commercial
preparation, varieties, 622; pro-
perties, 622-623.
—reactions - . . 629
series, acids of the . 621-623
Tartrate, potassic . . . . . . .297
potassic antimonious . . .297
Tartrates, double . . 287
Tartronic acid . 621
Taurin * * . 710
Taurocholic acid . , 710
Tawing, mode of . . . . 637
Teeth, composition of the . 692
Tellurates e - e. . 271
Telluric acid . . . . . . . . 165
oxide . . . . . . . . . . 165
Tellurides * * * * . 265
Tellurite . . . . . . . . . 164
Tellurium 164-165
history, natural history, properties 164
compounds of tellurium and oxygen 164
Tellurous oxide . . . . . . . 164
Temperature, standard . . . . . 33
average, of the air in England . . 96
influence of, on solubility . 202
Terchloride of formyle . . 532
of iodine . . . . . . . . . 91
Terebene * * * * * . 550
Terebenthene . . . . . . . 550
Terephthalic acid. . . . . . 538, 624
Tetroleic acid . it - & . . 611
Tetroxide, chromous dichromic . . 358
dibismuthic . . . . . . 373
Initrogen . . 110
ruthenic . - * - . . . .382
triplumbic . . . . . . . . 55
Tetrylic acid . (802-603
Thallic chloride . 431
iodide . 431
oxide . . 431
salts . . 432
sulphate . . 43 l
sulphite . . . 431
Thallium e Լ a we 430-432
history, natural history, extrac-
tion, properties, 430.
compounds of . 431-432
reactions of the . . . . 432
chlorides of . . . . . . . . 431
oxides of . . . . . . . . 431
sulphide of . . . . . . . . 432
Thallous carbonate . . . . . . 431
chloride . . . . . . . . . 431
iodide . . . . . . . . . 431
nitrate . . . . . . . 431
oxide . . . . . . . . . 431
phosphates . . . . . . . . 431
salts . . . . . . . . . . 432
sulphate . . . . . . . . . 432
sulphide . . . . . . . . . 431
Thebaine . . . . . . . . . 652
778
INDEX,
IPAGE PAGE
Theine . . . . . . . . . . 653 Tolane . . . . . . 546, 547
Thénard's blue . . . . . . . .333 Toluene . . . . . 537, 541
Theobromine . . . . . . . . 653 preparation, properties . . . . 541
Thermometer, table for converting Toluic acid. . . . . . . . . 612
degrees of the Centigrade into Toluidine 661, 665
degrees of Fahrenheit's scale . 734 || Toluyene . . . . . . . . 546
wet and dry bulb . . . . . 99 || Toluylic alcohol . . . . . . . 569
Thermotic properties of bodies, Tolylamine . . . . . . . . 661
changes in the . . . . 4 || Topaz . . . . 340, 341
Thiacetic acid . . . . . . . . 602 || Torula cerevisiae. 484, 486
Thio-alcohol . . . . . . . . 526 | Tragacanthin . & © . 589
Thio-ethers . . . . . . . . 641 | Trachyte . . . . . . . . . 343
Thionyl, chloride of . 149, 161 Trehalose . . . . . . , 583-584
Thialdine . . . . . . . . . . 663 | Triadelphic type . . . . . . . 466
Thionuric acid . . . . . . . 717 | Triallylamine . . . . . . . . 661
Thiosulphate, argentic . . . . . 418 Triannines . . . . . . 662-663
calcic. is a g 158, 318 Triamyl stibine . . . . . . . 667
sodic . . . . . . . . . . 158 Triamylamine . . . . . . . 660
Thiosulphates or sulpho-sulphates 271-272 | Triamylene * * * . 533
'Thiosulphuric acid . . . . 158 | Triargentic phosphate . . . . . 418
Thorinum . . . . . . . . . 347 | Triatomic acids, amides of . . . 673
Thymol . 572 | Tribasic acid . ſº tº gº . 253
Thymotic acid. tº º º . 614 phosphoric acid . 135
Thymylcarbonic acid . . . . . 614 Sulphate . . . . . . . . . . 372
Thymylic alcohol 569, 672 | Tribenzylamine . . . . . . . 661
Time of combination, affinity mea- Triborethyl . . . . . . . . 669
sured by the . . . 17 | Tribromacetic acid . . . . . . 602
Tin . . . . . . . . 383-388 Tribromide, silicic . 189
history, natural history, prepara- Tribromobenzene. & . 540
tion, 383; properties, 383-384; Tributylamine. . . . . . . . 660
impurities, 384; uses, 384-385. Tricalcic phosphate . 31S, 322
compounds of . . . . 385 Tricarballylic acid . . . . . . 625
—and oxygen . 385-387 series, acids of the . . . . . 625
—and sulphur . tº 387-388 | Trichloracetic acid . . . . . . 602
reactions of the Salts of . . 452 Trichloride or Terchloride of phos-
pyrites . 387 phorus. . . . . . . 139
salt . . . . . . . . . . 386 | Trichloride, carbonic . 181
bichloride and tetrachloride of , . 387 silicic. . 188
binoxide of . . . . . . . . 386 | Trichlorides . 257
disulphide of . . . . . . . 387 Trichlorobenzene. . 540
protochloride of e & . 386 | Trichloromethane 532–533
protosulphide of . . . . . . .387 preparation, 532-533 ; properties,
protoxide of . . . . . . . . 385 uses, 533.
sesquioxide of . is tº º . 386 Tricupric nitride. . 370
sesquisulphide of . . . . . . 387 | Tricymylamine . 661
“Tin prepare liquor ’’ of the calico- Tridecane . . 528
printer . . . . . . . . 386 Triethylamine. & . 660
Titanic acid . . . . . . . . 362 Triethyl arsine . . . . . . . 667
anhydride . . . 361, 362 bismuthine . , 667
chloride . . . . . . . . . .363 carbinol . is tº a ge 559
fluoride . . . . . . . . . 362 phosphine . . . . . . . . 666
oxide . . . . . . . . . . 362 stibine . . . . . . . 667
sulphide . . . . . . . . . 362 | Triethylenic glyco . . . . 575
Titanous chloride. . . . . . . 363 Trifluoride, arsenious . . . . . .395
oxide . . . . . . . . . 362 | Trihydric phosphate . . . . . . 135
Titanium . . . . . 361-363 | Trihydride, phosphorus . . . . 221
history, natural history, prepara- Triiodate, potassic . . . . 278
tion, properties . . . . 361 | Triiodide, silicic . , 189
compounds of titanium . 362 | Triiodomethane . tº gº , 532
—of titanium and oxygen . . . 362 | Trilithic phosphate . . . 308
—of titanium and chlorine . . 363 | Trimellitic acid . . . . . . 626
—reaction of . . . 363 | Trimercuric sulphate . . . . . 423
protoxide of . . . . 362 | Trimethyl arsine . . . . . . . 666
sesquioxide of . . . . 362 | Trimethylbenzenes . . . . . . 537
tetrachloride of. . . . . . . 363 | Trimethylcarbinol . . . . . , 559
INDEX. 779
PAGE PAGE
Trimethylamine . . 660 Uranium—continued.
Trimethyl phosphine º . 666
Trimethyl stibine . . . . . . 667
Trioxide, nitric & ... 108
nitrogen . ... 108
Trioxides * * . 242
Trioxybenzoic acid : . 615
Trioxycarballylic acid . 625
Triphenylbenzene . . . . . . . . . 647
Triphenyl-rosaniline (aniline blue) . 665
Triplumbic tetroxide . . . . . , 55
Tripotassic arsenite . . 284
Trisodic aluminate . 340
Trisodic phosphate . . . . . . 28i
Trisulphide, dipotassi . 294
distannic . . . . . . . . 385
molybdic . 409
Trisulphodithionic acid . . . . . . . 160
Trisulphuretted hyposulphuric acid 160
Trithionates . . . . . . . . .274
Trithionic acid * * * . 159
synonyms, history, preparation,
properties . . . . . . 16
Trititanic tetranitrido . . . . . 362
Trixylylamine . . . . . . 661
Tungstates . . . 270-271, 433
definition, 270; uses . . . . . 271
Tungsten . . . . . 432-433
natural history, preparation, pro-
perties, 422; oxides of tungsten,
432-433; the tungstates . . 433
Tungstic acid . . . . . 433
anhydride . 433
Tungstous oxide . . 432
Turmeric . . 679
Turnbull’s blue 517, 520
Turner's yellow . . . . . 414
Turpene series . 536, 549-55 l
Turpenes . . 49
Turpentine, English, from the Scotch
fir . . . . . . . . 549
French, from the Pinus maritima . 549
Venice, from the larch . . . . 549
isomers and polymers of . . . 552
oil of, and its allies 549-551
Turpeth mineral . tº º . . 423
Twaddell's hydrometer, degrees on . 732
Types, doctrine of . . . . . . 33
U.
compounds of uranium . . . . 337
—reactions of . . . . . . . . 337
atomic weight of . . . . . . 723
oxychloride. . 337
Ultramarine, native and artificial . 343
|Umber . tº ºr . 344
Undecane . . . . . . . . . 528
Unit of volume . . . . . . . .35
Uramil . . . . . . . . . . 717
Uranates . . . . . . . . . 337
Uranic nitrate . . . . . . , 337
oxide. . . 337
Uranium 336-337
history, natural history, prepara-
tion, 336; properties, 336-337;
uses, 337, -
Uranous chloride . . 337
oxide . * * * * . 337
Uranyl oxide . . . . . . . . 337
Urate of ammonia . . . . . . 719
of Soda . . . . 716
Urea . 49, 654, 662, 694, 714-715
constitution, 714; preparation,714-
715; properties, 715.
tests for . . . . . . . . . 676
Uric acid º . 715–717, 719
preparation, 716; properties, 716;
some products of the oxidation
of uric acid, 716-717.
Teactions . . . . . 628
Urinary calculi 719-720
Urine . . e 712-720
composition, 712-713; properties,
713; constituents, 714-719.
average composition of normal, and
average quantity of the various
constituents excreted in twenty-
four hours . . . . . . . 712
spirit of . . . . . . . . . 218
W.
Valerianic acid wº . 603
Valeric acid . . . . . 603
aldehyde. . 643
Valero-lactic acid . 605
Valerylene . - 536
Walylene . 536
Vanadates . g . . 284
Vapor density . . . 474-475
—determination of vapor densities
475-477
—application of the facts deduced
from the ultimate analysis, and
from the determination of the
vapor densities of organic bodies 477
—of phosphorus, arsenic, mercury,
zinc and cadmium . . . . . 37
Vapor, aqueous, table of the tension of 736
Warwicite . . . . . . . . . 328
Veget-albumen . . . . . . . 688
Vegetable chemistry . . . 683-687
Venetian red . . . . . . . . 354
Veratrine * * * * *
Winegar, French wine . . . . . 491
English malt . . . . . . . 492
spirits of . . . . . . . .
springs of volcanic districts. . . 151
Vinic alcohol • * * *
Vinous fermentation. . . . . . 4S4
Vinylic series . *
alcohol . . . . . . . . . 568
Viridine . . . . . . . . . 662
Wiscous fermentation . . . . . 4S5
Vitality, influence of, on chemical
action . . . . . . . . . 14
780 INDEX.
- PAGE - PAGE
Vitellin . . 689 || Wine, spirits of . . . . . . . 564
Vitriol . . . 151 | Wine-making, alcoholic fermenta-
green. 269, 356 tion in & tº º º . 490
white 269, 332 Witherite (baric carbonate) . 31.4
II'OI). . 356 || Wolfranium . . . . . . . 432
lead . 415 || Wood, products of the distillation of 501
oil of . e - e. . 151 || Wood or pyroxylic spirit . 562
spirit or essence of . 151 || Woody matter º . 685
Vitriolic acid . . 151
phlogisticated . . 148
Volatile alkali . 218 X.
Volume . 30
Vulcanite . 556 | Xanthin 654, 679, 719
Xylene . . . . . 537
Xylenol . 569
W. Xylic acid . . 612
Xylidic acid . 624
Wad . . 328 Xylidine . . 661
Water • * * - s g 195-208 Xylilic acid . 612
—history, natural history, prepara- alcohol . 569
tion, 195; composition, 195- Xylylamine . 661
197; properties, 197-206.
common (rain, spring and well,
lake and marsh, and river) 200-207 Y.
mineral waters. . . 207
SCöl . . . . . 207-208 || Yeast, a complicated ferment . . 486
for drinking purposes . 208 || Yellow, chrome . . . . . . . 360
of constitution . . 205 Yellow coloring matters . . . . 678
of crystallization . . 205 || “Yl” and “Yle,” the terminations. 22
molecule of . - - is . 46 || Yttrium . . . 346
as a natural disinfectant. . 493
action of, on
—alcohol . 564 Z.
—alkaloids . . 649
—bone . 693 Zaffre . 333
—bromates . . 278 Zeolites . . . 343
—carbonates . 285 | Zinc . . . . . . . . 330-333
—chlorates. . 278 history, natural history, 330; pre-
—chlorides. . 258 paration, 330-331 ; properties,
—fluorides . . 261 uses, 331.
—iodates . 278 compounds of . . . 332-333
—iron . 352 reactions of the salts of . 449
—lead . 411 | Zincic acetate . . 601
—the metals . 245 ammonic chloride . . 332
—nitrates . .276 amylide . . 670
—the oxides e e . 243 carbonate . 333
—oxides of nitrogen . . 114 chloride . - e. . 332
—phosphorus . 128 —a dehydrating agent . . 506
—silicates . . .286 cyanide . . . . . 511, 513
—Sulphates. º . 268 ethide . . 670
—nitric peroxide on . . I 11 methide . . 670
in blood . • . 703 oxide . . . . . 332
in urine . . . . . . . . . 714 Sulphate . . 56, 269, 332
Weights and measures, table of Eng- sulphide . . . . . 332
lish . . . . . . . . . 732 Zirconic chloride . . 347
Weld, or luteoline . 678 fluoride . . 347
White lead, preparation of . 416 Zirconium . . . . . . . 347
White precipitate . 426 Zymotic or ferment diseases . 487
T} tº
** {
ºwº-
-
º .
P 2 & 1916
By the same Author.
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