LOSSES OF MERCURY IN TOXICO- 
 LOGICAL ANALYSES 
 
 BY 
 
 KENYON A. HYLE 
 
 THESIS 
 
 FOR THE 
 
 JJEGREE OF BACHELOR OF SCIENCE 
 
 IN 
 
 CHEMISTRY 
 
 college: OE’ libeijal arts and sciences 
 
 UNIVERSITY OF ILLINOIS 
 
 1922 
 
(a. Co' 
 

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TABLE OF CONTENTS 
 
 Acknowledgement Page 
 
 I Introduction 1-4 
 
 1. Purpose 1 
 
 2. Nature of the prolblem 1 
 
 3. Historical 1-4 
 
 II Experinsental 4-12 
 
 1. Material 4 
 
 2. Preparation of Material 4-3 
 
 3 . Fresenius-Von Baho Method 5-8 
 
 4. Chit tendon and Donaldson Metiiod 8-9 
 
 5. Hal?kins and Swain Method 9-10 
 
 6. New Methods tried 10-12 
 
 III Results and Discussion 13-17 
 
 IV Summary and Conclusions 18 
 
 V Bibliography 19 
 
Digitized by the Internet Archive 
 in 2016 
 
 https://archive.org/detaiis/lossesofmercuryiOOhyle 
 
ACKNOWLEDGEMENT 
 
 I take this opportunity to thank Dr. Beal for the 
 suggestion of this problem, and for his S3mipathetic sup- 
 ervision and guidance in working it out. His friendly 
 suggestions and personal interest have been a source of 
 inspiration to me throughout the work, and if anything 
 of importance has been brought out in this work, it is 
 largely due to the above facts. 
 

 
 
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( 1 ) 
 
 LOSSES OF MERCURY IN TOXICOLOGICAL A^I/lLYSES 
 I. INTRODUCTION 
 
 1 . -PURPOSE 
 
 The purpose of this investigation has been the study and 
 comparison of the three principal methods for the decomposition 
 of organic tissues in the toxicological determination of mercury, 
 in order to determine which of the various methods no\f kno^m and 
 used, will recover the grea,test amount of mercury from organic 
 tissue . 
 
 2.1S.TURE OF THE PROBLEM 
 
 It is a well known fact that mercury salts together with other 
 salts, such as arsenic, are quite volatile, and it is due partly to 
 this fact that no method is now l-:no\m wliich will recover all of a 
 given quantity of m.ercury in a toxicological analysis. It is very 
 important inaa toxicological investigation to know the exact quan- 
 tity of mercuhy which has been administered to cause the death of ' 
 the person in question. Proof that a sufficient quantity of poison 
 has been given to cause death constitutes the chief evidence in 
 legal cases. Therefore it is necessary, in toxicological analyses, 
 to Imow how much mercury is lost in the composition of the organic 
 matter and the subsequent determination of the poison. 
 
 3. -HISTORICAL 
 
 The methods used for the toxicological determination of mercury 
 are comparatively few in number. The chief object in all of the 
 methods is the complete destruction of the organic material. This 
 
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 is necessary in order to free the mercury from organic substances, 
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 before the mercury will go into solution. 
 
 ( 8 ) 
 
 I. ldlESENIUS& VON BABO MET^IOD 
 
 Fresenius and von Babo worked out a method for the determin- 
 ation of arsenic which was published in 1844. This has been adapted 
 for the toxicological analysis of all metallic poisons including 
 mercury. In this metnod the decomposition is carried out by the 
 action of nascent chlorine upon the organic tissue. The chlorine 
 is generated by the action of hydrochloric acid on potassium chlor- 
 ate, both of wiiich are added directly to the tissue, which has been 
 chopped finely and diluted with a little water. The reaction takes 
 place best when heated at the temperature of the steam bath. The 
 decomposition requires several hours. The liquid is filtered off 
 and the mercury precipitated with hydrogen sulphide. The mercury 
 
 may then be determined by any suitable method. 
 
 ( 1 ) / 
 
 II. GAUTIERS METHOD 
 
 Gautier worked out a method for the toxicological determination 
 of arsenic which was published in 1875. This method of decomposition 
 consists of oxidizing the material with concentrated nitric and 
 sulphuric acid at rather high temperatures. To 100 grams of the mat- 
 erial 30-60 grams of pure nitric acid is added. Then one gram of 
 sulphuric acid is put in and the mixture heated until liquif ication 
 is produced. It is then removed from the heat and 8-10 grams of 
 sulphuric acid added. This is then heated again (taking care not 
 to carbonize the mass)and taken from the source of heat. Nitric 
 acid is then poured over the material a little at a time until up 
 

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 on heating to a point where dense white vapors come off, there is 
 left in the casserole a hrovrn thick liquid carhonizahle at the boil- 
 ing temperature of sulphuric acid. V/hen the nitric acid produces 
 scarcely any further oxidation, the acid is driven off by heat, the 
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 (4) 
 
 III.CHITTENDBN & DONALDSON METHOD. 
 
 Chittenden and Donaldson while endeavoring to find a more 
 suitable and accurate method for the toxicological determination 
 of arsenic , worked out a modification of uautier's proceedure , which 
 was published in 1880. They claim its advantage over the method of 
 (lautier because the decomposition is carried out at lower tempera- 
 tures. In this proceedure the sulphuric acid is not added until 
 the nitric acid has practically reduced the organic material to a 
 liquid. This liquid is then watched closely, and when it becomes 
 thick and assumes an orange shade, the casserole is taken from the 
 hot plate and 3 c.c.of concentrated sulphuric acid added while stirr 
 ing constantly. The addition of the sulijhuric acid to this residue 
 rich in nitrous comjx)unds causes nitrous fumes to be given off co- 
 piously, follovt'ed by dense white fumes. The residue is carbonized 
 to a black sticky mass or else a dry char. After heating some more 
 and adding a few c.c, of nitric acid, in order to more completely 
 destroy the organic material, and prevent formation of sulphided, 
 the casserole is removed from the heat. A hard carbonaceous mass 
 free from nitric acid is the result. The arsenic may then be dis- 
 

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 IV. HARKINS AND SWAIN iH^THOD. 
 
 Just as the Chittenden and Donaldson method is a modifica- 
 
 (l) 
 
 tion of Gautier’s so may Harkins’s and Swain’s proceedure he call- 
 ed a modified chittendgn-Donaldson method. The proceedure differs 
 from chittendon - Donalds()n^ method in that the mixture is the cass- 
 erole is removed from the heat just as soon as it htis ’been complete- 
 ly reduced to a liquid. After codling the liquid, about 30c. c. of cnn- 
 centrated sulphuric acid is added and the casserole heated. Great 
 quantities of nitrous fuires are driven off. Y.'hen the liquid begins 
 to get bro^m, nitric acid is added from a dropping funnel, in suff- 
 icient quantity to maintain the brown color, and prevent any further 
 darkening. This is kept up until the liquid in the vessel no longer 
 changes color. This thick liquid is now free from nitric acid and 
 a great deal of sulphuric acid is also gone. It is diluted and evap- 
 orated to a smaller volume and is then ready for the precipitation 
 of mercury. 
 
 All of the above methods were used by the authors for de- 
 tertiination of arsenic, but have since been adapted for mercury 
 and other metallic poisons. 
 
 II .EXPERIMENTAL 
 
 1 . -MATERIAL 
 
 The material used in this work was dried blood. This 
 dried blood was of very low moisture content, so that twenty five 
 grams of the dried material was taken to equal one hundred grams 
 of tissue. In all determinations this amount was used. 
 
 2. PREPARATION OF MATERIAL 
 
 The dried blood after being weighed out roughly, was put 
 
 
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 into "S' veS5'el”'n:iT(r'^STnr^li W£lt0f~ i.dded to form a pasty or soupy mass . 
 This was then allowed to stand, in general , about an hour in order 
 that the blood might become softened and brought to a state as 
 nearly resembling the original condition as possible. 
 
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 compound, since it is the most common of the mercury poisons to be 
 dealt with in toxicological work. By adding the mercuric chloride 
 to the blood mixture in the form of a solution in all cases we felt 
 that we had a fair duplication of toxicological conditions. This 
 solution was of Imown titer, and was retitrated frequently to detect 
 any change in strength which might take place from time to time. 
 
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 order to facilitate the addition of mercury in small amounts to 
 the material. 
 
 After adding the mercuric chloride to the material , the 
 blood mixture was allowed to stand forty eight hours. This gave 
 opportunity for the mercury to thoroughly impregnate the organic 
 matter, and reach a condition somewhat similar to that existing in 
 the animal body, when death and possibly burial follows adciinistra- 
 tion of the poison. It is supposed that mercury forms a mercury 
 albuminoid in the tissue. It is due to this fact that organic m.at- 
 erial must be destroyed before mercury can be determined. After 
 standing this length of time the decomposition may be started accord 
 ing to the method selected. 
 l.-WORK ON THE FRESENIUS-VON BAB^fliETHOD. 
 
 In carrying out the decomposition by this method it was de- 
 cided to vary the proceedure. One set of decompositions was carried 
 out in an open flask, and another set using a reflux condenser. By 
 using the condenser , any mercury which might volatilize with steam 
 would be returned to the flask and thus be determined. By comparing < 
 

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( 6 ) 
 
 the results of zne two“airrerentiy““c6riauctea clecorfiposltlons , the 
 amount of mercury lost hy volatilization might be easily found. 
 
 Following the proceedure of Fresenius-Von Babo thirty 
 c.c. of concentrated hydrochloric acid was added to the mixture 
 followed by from one to two grams of potassium chlorate. The Kjel- 
 dahl flask containing this mexture was then put on the water bath. 
 
 The nascent chlorine coming into contact with the organic material 
 soon began to act. After a short time, when the potassium chlorate 
 was used up, more was gradually added(about .2 to .3 gram at a time). 
 Generally , this amount added about every five to ten minnutes kept 
 an even flow of chlorine. The mixture soon began to get lighter in 
 color. Shaking the flask after addition of each portion of potass- 
 ium chlorate accelerated the decomposition noticeably, by bringing 
 the chlorine into contact with the tissue. The end of the decompo- 
 sition was indicated when the liquid assumed a light straw color, 
 and did not darken on standing, or upon further heating. A little 
 dilute sulphuric acid was then added to precipitate any possible 
 barium or lead and the supernatant liquid was filtered off. The 
 mercury was precipitated from the solution with hydrogen sulphide, 
 after expelling all free chlorine. The gas was allowed to buble 
 through the liquid for one and one half hours while hot. The liquid 
 was then removed from the water bath and the gas allowed to run tin- 
 til the flask cooled. The liquid containing the mercury sulphide 
 precipitate was ccrke^iL and allowed to stand for one day. If at the 
 end of that time an odor of hydrogen sulphide was noticeable in the 
 flask, the precipitate was filtered off. Otherwise , more hydrogen 
 sulphide was passed into the liquid. The black residue of mercury 
 sulphides was then dissolved in nitric acid with a few drops of 
 hydrochloric acid and the resulting solution diluted and filtered. 
 
 This filtrate containing the mercury was then ready for determinatio: >. 
 

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(7) 
 
 The determination was carried out volumetrically, using the 
 (5) 
 
 method of Bauer .Following his proceedure the solution was made alk- 
 aline with ammonia, and a standard solution of potassium cyanide 
 added to the mercuric solution. Five c.c. of potassium iodide was 
 added as an indicator and the excess of potassium cyanide titrated 
 
 with standard N silver nitrate. Each c.c. of N silver nitrate is 
 10 10 
 
 equivalent to .02006 greims of mercury. The potassium cyanide solu- 
 tion was previously titrated against the N silver nitrate solution, 
 
 10 
 
 so that the value of the potassium cyanide solution per c.c. was 
 Imown . 
 
 In carrying out the dujjlicate decomposition with the reflux 
 condenser the potassium chlorate was added by loosening the conden- 
 ser from the flask and dropping in the potassimn chlorate. It was 
 found in running the two sets of decompositions that the liquid in 
 the flask bearing the reflux condenser always reached the final 
 stage before the open flask. Also, less potassium chlorate and acid 
 were necessary than with the open flask, in order to produce the 
 final stage of decomposition. No difficulty was experienced in carry 
 ing out the decompositions according to this method. However, some 
 of the organic matter could not be destroyed by the action of the 
 chlorine. It always remained in the bottom of the flask in the form 
 of a white mealy substance. It was easily filtered off , leaving a 
 clear liquid. The most important source of error seemed to be in 
 not allowing enough time for complete decomposition. If the flask 
 was removed before it had reached the right stage ,flifficulty follow- 
 in precipitating the mercury from the solution. The writer experien- 
 ced this trouble early in the proceedure. Stringy, slimy compounds 
 were thrown down with the mercury when hydrogen sulphide was passed 
 into the solution. These were later dissolved by the nitric and hy- 
 
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( 8 ) 
 
 drochloric acids, with the result that when the anunonia and potassium 
 iodide were added for titration, a murky precipitate clowded the sol- 
 ution and made titration impossible. It was not always possible to 
 filter this off, and even iff possible , presented the objection of 
 removing some of the mercury with the other substances. Therefore, 
 the best way seemed to be to avoid this by thoroughly decomposing 
 the organic matter in the beginning, until the permanent straw color 
 appeared. The time for each decomposition was noted and recorded. 
 
 2. CHITTENDEN /iND DONALDSON METHOD. 
 
 The vrork on this method was confined to a few decomposi- 
 tions only, since the nature of the proceedure suggested great, if 
 not total losses of mercury. 
 
 Following their proceedure, 23 c.c. of pure concentrated 
 nitric acid is added to the blood mexture containing the mercury. 
 
 The mixture contained in a casserole of OGOcc.c. capacity is then 
 heated on a hot plate with occasional stirring. The temperature as 
 mentioned by the authors of this method is 150-160 degrees centi- 
 grade, but v:^ith the blood this temperature was not attained. This 
 would seem to be favorable. Keeping at this temperature , the mass 
 swells, thicken, and changes color. At first a dark brown, it changes 
 slov/ly to a light yellow. It then becomes a liquid. This is heated 
 1 1/2 to 2 hours until it takes on an orange color, or deep yellow 
 shade. At this point, the casserole is removed from the plate and 
 3 c.c. of concentrated sulphuric acid added while stirring vigor- 
 ously. The mixture thickens and gives off nitrous fumes copiously, 
 immediately followed by dense white fumes of sulphur trioxide. ( 
 The residue in the dish is changed into a black sticky mass or else 
 a dry carbonaceous mass. The dish is again placed on the plate and 
 heated for a fevf minutes. Then 8 c.c. of nitric acid is added, drop 
 

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 by drop, in order to more completely destroy the organic matter, and 
 precent the formation of the organic sulphide. After this addition, 
 the casserole is again heated for 15 minutes , after which the cold 
 carbonaceous mass is treated with hot water in successive portions, 
 in order to extract the mercuric sulphate. This water is then evap- 
 orated and the mercury taken up from the residue with concentrated 
 hydrochloric acid. This extract is diluted with water and the mer- 
 cury sulphide precipitated. The precipitate may then be dissolved 
 and titrated as in the first method. 
 
 In following out the above method, the temperatures as 
 stated by the authors exceed those reached in using the blood mix- 
 ture. Since the blood mixture is more fluid than solid tissue the 
 temperature would naturally be lov/er in this case. In extracting 
 the mercury salt from the carbonaceous residue, the water was left 
 in contact with the mass for 24 hours in order to insure complete 
 extraction. No difficulties were encountered in carrying out the 
 proceedure,but it was necessary to watch the mixture very closely 
 before adding the sulphuric acid. It was difficult to detect the 
 change in color because of the red nitrous fumes, which were given 
 off. It was necessary to exercise care in adding the sulphuric acid, 
 in order to prevent any loss by spattering. Affew drops were added 
 at a time and the mixture stirred vigorously during addition. 
 
 3.-W011K ON HARKINS AND SWAIN METHOD. 
 
 In carrying out this proceedure 500 c.c. casseroles were 
 used as the vessels, four determinations were carried out together. 
 This number was found to be convenient, in saving time. One decompo- 
 sition was started and carried to the end of the first stage. It i: 
 was allowed to heat while another was started. 
 

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( 10 ) 
 
 One hundred c.c. of concentrated nitric acid was added to 
 t?ie blood mixture and placed on the hot plate. The mixture begain 
 to swell and required constant stirring to avoid the overrunning 
 of the dish. It changed color from a dark brown to a light yellow. 
 Here the swelling subsided and after a little while became a liquid. 
 This liquid was then allowed to heat for half an hour,'ivhile anotliEr 
 decomposition was started. The rich red liquid was then removed and 
 allowed to cool, after which 30 c.c. of concentrated sulphuric acid 
 w'as added. The casserole was again heated on the hot plate. Great 
 volumes of red nitrous fumes came off. This continued for some time, 
 when the liquid begain to assume a brown color. Here, nitric acid 
 was added, drop by drop, just enough to prevent the darkening of the 
 liquid. This was continued until the thick liquid no longer chang- 
 ed color. The mixture was heated a little longer to drive off some 
 of the thick white sulphur trioxide fumes, in the meanwhile , adding 
 nitric acid occassionally . The casserole was then removed from the 
 heat and allowed to cool, after which the residue was diluted and 
 reevaporated to a smaller volume, in order to eliminate any nitrous 
 fiumes. This solution was then filtered and the mercury precipitated 
 from it in the usual way, and determined. No difficulty was encount- 
 ered in the proceedure. The organic material was completely destroy- 
 ed and good clear solutions were obtained for the titration. In rnn- 
 ning the four decompositions in the manner described it required 
 the entire attention of the writer, and although the work was carr- 
 ied out under the hood the fumes from the dishes were very disagree- 
 able. The time occuppied \ras about one hour. 
 
 4.- NEW iiETHOD TRIED. 
 
 It was decided to modify the Markins -Swain method in 
 such a way as to eliminate the great losses of mercury which neces- 
 

 
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 sarily take place at the higher temperatures produced by adding the 
 sulphuric acid. The first part of the proceedure using the nitric 
 acid was carried out as before, and the mass reduced to a liquid. 
 
 After cooling the mixture it was transferrdd from the casserole to 
 an 800 c.c. Kieldahl flask wliich was fitted with a reflux condenser. 
 
 The mixture was then heated with a bunsen burner to boiling, after | 
 
 i 
 
 having added the sulphuric acid, for about an hour and one half. The | 
 
 j 
 
 red nitrous fumes were driven off from the top of the condenser, | 
 
 \\ 
 
 vdiile the rest of the material which volatilized was condensed and \ 
 returned to the flask. Some carbonization was noticeable as the heat- 
 ing was continued, but the liquid remained a light color. The black 
 flakes of carbon remained on top of the clear liquid. After most of 
 the nitric acid had been driven off, as was shown by the fact that 
 scarcely any red fumes came from the top the condenser , the flask 
 was removed from the heat and allowed to cool. The clear liquid 
 was filtered off and diluted. Since the solution contained mostly 
 dilute sulphuric acid, the passing in of hydrogen sulphide gave rise 
 to a light yellow precipitate of sulphur. This copious precipitate 
 of sulphur obscured the precipitate of mercury sulphide for a few 
 minutes, but it appearred presently on the surface of the solution. 
 After precipitation was complete the sulphur and m.ercuric sulphide 
 were filtered off. The mercuric sulphide was then dissolved with 
 nitric and hydrochloric as previously and titrated. 
 
 It was thought at first that the sulphur might interfere 
 in dissolving the mcrcurj'' sulphide, but the metal was easily separ- 
 ated and the sulphur left undissolved. The solution finally obtain- 
 ed for titration gave no trouble, as it remained clear after adding 
 the various solutions needed for titration. Although this method 
 occuppied a little more time, no disagreeable odors were experienced. 
 
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( 12 ) 
 
 and it required less attention. Any mercery which might have volatil 
 izedwas immediately condensed and carried hack into the f'lask hy 
 the water which was being returned to the flask from the condenser. 
 Therefore, any loss of mercury caused hy volatilization must have 
 occurred in the first part of the process when the decomposition 
 was started with the nitric acid. 
 
 5. -METHOD WITH CONCENTRATED SULPHURIC ACID AND PERCHLORIC ACID. 
 
 It was decided to investigate the action of concentrat- 
 ed sulphuric acid and perchloric acid on organic tissue in the hope 
 that this might prove a means of breaking up the tissue. 
 
 Therefor fifty c.c. of concentrated sulphuric acid was add- 
 ed to the blood mixture and heated on the water bath. A seventy per- 
 cent perchloric acid v»^as obtained and a few c.c. added at a time, 
 but no reaction resulted. The flask was then raised to a higher 
 temperature, and finally to the boiling point of the sulphuric acid, 
 and the perchloric acid was again tried. No results followed and 
 the method was abandoned as unsuccessful!. 
 

 
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(13) 
 
 
 
 III. RESULTS AND DISCUSSION 
 
 
 
 
 
 TABLE I 
 
 
 
 
 Determinations by I’resenius- 
 
 Vonl>abo Method 
 
 
 
 Open 
 
 Flask 
 
 
 
 
 Theor .Hg 
 
 . Time (hr 
 
 s) Det.Hg. 
 
 Hg. loss 
 
 Hg.^ loss. 
 
 1. 
 
 .2316 Gr 
 
 . 5 
 
 .1426 Gr. 
 
 .0890 Gr. 
 
 38.4 1 
 
 2. 
 
 .3088 
 
 4 
 
 .2505 
 
 .0583 
 
 15.6 1 
 
 3. 
 
 .3088 
 
 5 
 
 .2062 
 
 .1026 
 
 33.2 ! 
 
 1 
 
 4. 
 
 .3860 
 
 4 
 
 .3348 
 
 .0512 
 
 13.2 
 
 5. 
 
 .5404 
 
 4 1/2 
 
 .4239 
 
 .1165 
 
 21.2 
 
 6. 
 
 .6780 
 
 3 1/2 
 
 .4580 
 
 .2200 
 
 32.4 
 
 7. 
 
 .7540 
 
 4 
 
 .6326 
 
 .1214 
 
 16.1 
 
 
 
 Condenser Flask 
 
 
 
 Theor .Hg 
 
 Time ( hr 
 
 s) Det.Hg 
 
 iig.lOSS 
 
 lig.^ loss. 
 
 1. 
 
 .2316 
 
 4 
 
 .1174 Gr. 
 
 .1142 Gr. 
 
 49.3 
 
 2. 
 
 .3088 
 
 3 
 
 .2060 
 
 .1028 
 
 33.2 
 
 3. 
 
 .3088 
 
 4 
 
 .2013 
 
 .1075 
 
 34.8 
 
 4. 
 
 .3860 
 
 3 
 
 .2736 
 
 .1124 
 
 29.1 
 
 5. 
 
 .5404 
 
 3 
 
 .3906 
 
 . 1498 
 
 27.7 
 
 6. 
 
 .6780 
 
 2 l/2 
 
 .4136 
 
 .2644 
 
 39.0 
 
 7. 
 
 .7540 
 
 3 
 
 .6076 
 
 .1464 
 
 19.9 
 
 ! 
 
 
 Table I 
 
 shows the 
 
 comparative 
 
 results of 
 
 the two variations 
 
 of 
 
 the Freseniu-Von Babo 
 
 Method. The 
 
 most surprising thing about 
 
 these results 
 
 in the fact 
 
 that the open flask decomposition gave 
 
 the 
 
 smallest loss of mercury in every single case. This seems to 
 
 indicate that 
 
 the losses 
 
 were not caused by volatilization, to any 
 
 extent. It was 
 
 decided to 
 
 investigate the condenser to determine 
 

 
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( 14 ) 
 
 if any volatilized mercury could have sublimed there. It was rinsed 
 thoroughly wilhh water and the washings titrated with a negative re- 
 sult. The only way left, then, to explain the difference in the losses 
 from the same amounts of mercury under the two differently conduct- 
 ed decompositions in in the time 6f decomposition. The table shows | 
 that the open flask decomposition required about an hour longer in | 
 
 each case, to reach the right color. The chlorine will not break up | 
 
 [ 
 
 all of the organic material. There was always a white mealy residue | 
 left in the bottom of the flask. This fatty material resists the | 
 action of the chlorine, so that the losses in mercury may correspond 
 to that held by this solid residue. If this last fatty material 
 could be broken up by some other means and added to the recovered 
 mercury, very little would be lost. The only objection here would be 
 the length of time required to make a determination. 
 
 From the condenser flask the mercury losses increase in 
 weight as the amount of mercury added is increased. The percentage 
 of mercury lost steadily decreases as larger quantities of mercury 
 are determined. In comparing this with the open flask figures , there 
 is a wide variation in the percent of mercury lost. However, if the 
 first and last percents are taken, it corresponds very nicely to the 
 condenser flask figures. The mercury losses show a general increase 
 as the quantity of mercury is increased. 
 
 TABLE II 
 
 Chittenden and Donaldson Method 
 
 
 Theor .Hg 
 
 Det .Hg. 
 
 Hg. loss 
 
 Hg.^ loss 
 
 1. 
 
 .3016Gr. 
 
 .0206 Gr. 
 
 .2810 Gr. 
 
 93.2 
 
 2. 
 
 .5278 
 
 .0186 
 
 . 5092 
 
 96.4 
 
 3. 
 
 .7540 
 
 .0332 
 
 .7208 
 
 95.1 
 
* 
 
 
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 «• a w 1 
 
 9* • 
 
 ii: OXiiic. 
 
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 eotio. 
 
 ..f 
 
 
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 1 . • 
 
 not’?. 
 
 f> WO. 
 
 
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(15) 
 
 The extreme accuracy claimed, for this method by its authors 
 is not verified by these figures. Almost all of the mercury was 
 lost by volatilization at the higher temperature used for carbon- 
 ization* Not enough determinations were Eun to ascertain in what 
 order the losses would follow, but the few in Table II show great ( 
 
 irregularity, depending upon the variations in each decomnosition, | 
 
 i 
 
 The best thing that can be said for this method is that it requires | 
 only a short time to complete a decomposition. | 
 
 TABLE III 
 
 Harkins and Swain Method 
 
 
 Theor .Hg. 
 
 Det .Hg. 
 
 Hg. loss 
 
 Hg.^ loss 
 
 1. 
 
 .2262 Gr. 
 
 .0470 Gr. 
 
 .1792 Gr. 
 
 79.2 
 
 2. 
 
 .3770 
 
 .0540 
 
 .3230 
 
 85.7 
 
 3. 
 
 .4524 
 
 .0860 
 
 .3664 
 
 80.9 
 
 4. 
 
 .5278 
 
 .1097 
 
 .4181 
 
 79.2 
 
 5. 
 
 .6036 
 
 .0560 
 
 .5476 
 
 90.7 
 
 6. 
 
 .6786 
 
 .0320 
 
 . 6466 
 
 95.2 
 
 7. 
 
 .7540 
 
 .1360 
 
 .6180 
 
 81.9 
 
 
 
 
 Av . 
 
 84.6 
 
 The results in lable III show an average loss of mercury 
 to the extent of 84.6 percent of the theoretical. These results 
 show that as the amount of mercury determined increases , the J.osses 
 increase proportionately, and the percentage loss varies from 80 to 
 85 in most cases. This a much lower loss than the (Jhittendon and 
 Donaldson Method, but that was expected since the temperature used 
 here was not so high. 
 

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 t.u .. , 
 
 
 
 
 I 
 
(16) 
 
 TAiiLE IV. 
 
 New Method tried. Modified Harkins and Swain 
 
 
 The or .Hg. 
 
 Det .Hg 
 
 Hg. loss 
 
 Hg.% loss 
 
 1. 
 
 .3016 Gr. 
 
 .0930 Gr. 
 
 .2080 Gr. 
 
 68.9 
 
 2. 
 
 .4524 
 
 .3194 
 
 .1330 
 
 29.4 
 
 3. 
 
 .6016 
 
 .4468 
 
 .1548 
 
 25.7 
 
 It can he seen from the data in Table IV that the losses 
 of mercury are much less in this method than in the Harkins and 
 Swain Method. The losses increase as the amount of mercury added is 
 increases, while the percentages of loss show a gradual decrease. 
 Limited time permitted only the three determinations , hut it is 
 thought that if intermediate quantities of mercury were used, the 
 inteppretation would he the same as sho^m hy the above data. Deter- 
 mination number one seems to show rather too high percentage loss 
 in proportion to numbers two and three. The chief objection which 
 might be advanced against this method is the length of time neces- 
 sary for refluxing the mixture, bux, inasmuch as it requires no at- 
 tention, the time is not really important. The advantage over the 
 Harkins and Swain Method is that no disagreeable fumes have to be 
 encountered. The chief advantage is ,of course, the reduced amount 
 of mercury which is lost by volatilization. The sulphur which is 
 thrown do^m with the mercury on precipitation is really not object- 
 ionable, since the mercury is easily dissolved out of the sulphur 
 
 mass . 
 

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 TABLE V. 
 
 Comparison of Methods 
 
 Method 
 
 Av.Theor .Hg. 
 
 Av.Det .Hg. 
 
 Av .Hg. loss 
 
 Av 
 
 l.Fresenius-Eabo 
 
 .4576 Gr. 
 
 .3498 Gr. 
 
 .1084 Gr. 
 
 24.3 
 
 2.Chitt’n-Don' son 
 
 .5278 
 
 .0261 
 
 .5017 
 
 95.1 
 
 3 .Harkins-Swain 
 
 .5170 
 
 .0744 
 
 .4426 
 
 84.6 
 
 4.Nevsr Method 
 
 .4519 
 
 .2864 
 
 .1655 
 
 41.3 
 
 TalDle V is given for convenience in comparing the general 
 results of the four methods worked on. The average percent loss 
 gives a pretty fair estimate of the value and accuracy of the meth- 
 ods, except in the case of number four. The first determination carr- 
 ied out with this method gave, for some reason or other, quite a high 
 mercury loss. This result was too high to he consistant with the 
 two later determinations as is sho\m hy Table IV. As a consequence, 
 this one high loss inflates the average percentage loss much highrr 
 than it really should be. If we discard this one high loss, the new 
 n:iethod compares very favorably with the Iresenins-Von Babo I>!ethod. 
 
 Of course, the averages given apply to quantities of mercury bettween 
 .25 to .75 gram. It is the belief of the writer that the new m.ethod 
 as described can be improved and developed where m.uch lower losses 
 of mercury will occurr. 
 

 
 
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(18) 
 
 IV.SUI.iJiARY AND CONCLUSIONS 
 
 I. The four possible methods for the toxicological determination 
 of mercury have been reviewed and the three most promising ones 
 investigated. 
 
 II. Losses of mercury in the Fresenius-Von Babo method are not due 
 to volatilization to any extent, but to the undecomposed tissue 
 which is filtered off after decomposition. 
 
 III. The Chitten(?©n-Donaldson method uses too high a temperature for 
 decomposition, thereby volatilizing the greatest percent of the 
 mercury(95^) . 
 
 IV. The Harkins -Swain method uses a lower temperature but the decom- 
 
 p position temperature is high enough to allow great losses of mer- 
 cury. This makes it unsuitable for determination of small quan- 
 tities of mercury 
 
 V. Disagreeable fumes are encountered in this method. 
 
 VI. The new method tried gave much smaller mercury losses than either 
 the Ciiittenden-Donaldson or Harkins-Swain methods. 
 
 VII. The new method compares very favorably with the Fresenius-Von 
 Babo method 
 
 VIII. It can be developed so as to give much lower losses. 
 
 IX. Of the four known methods Fresenius-Von Babo method gives the 
 smallest losses, and seems to be the most suitable for determin- 
 ing small quantities of mercury in organic tissue.lt is better 
 because it 
 
 1. Uses a comparatively low temperature. 
 
 2. Gives no disagreeable odors. 
 
 3. Uses only one acid. 
 
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(19) 
 
 V. BIBLIOGRAPHY 
 
 1. Bulletin de la Societe chimique 24,250. 1875 
 
 2. Traite de Toxicologie 1,494. 1852 
 
 3. Filhol- Thesis Paris 1848 
 
 4. American Chemical Journal Vol.II No. 4. 1880 
 
 5. Berichte 54B pp.2079 -1921 
 
 6. Journal American ChemicJil Society 30,928 
 
 7. Treadwell-Hall Vol.II pp.720 1918 
 
 8. Annalen der chemie und Pharmazie 49,306- 1844