Skip to content

Chapter XLVIII: Section I: Of the Chemical Tests for the Compounds of Arsenic (2)

Text size

_Process of Reinsch._—This is the simplest and easiest of all. Remove in the first place any white or gray powder which can be detached from the mixture; and either subject it to the process of reduction by charcoal or soda-flux, as described at p. 203, or dissolve it in boiling distilled water and subject the solution to the three liquid reagents, p. 207, or if there be enough, examine it in both ways. If arsenic be thus obtained, it is seldom necessary to proceed any farther. But if not, cut all soft solids into small fragments, add distilled water if necessary, then add hydrochloric acid to the amount of a tenth of the whole mixture, and more if the subject of analysis be decayed and ammoniacal, so that there may be a decided excess of acid. Boil gently for an hour, or until all soft solids be either dissolved or broken down into fine flakes and grains. Filter through calico; bring the filtered fluid again to the boiling point; and then proceed as described for Reinsch’s method in simple arsenical solutions [p. 214].

The only important precaution to be attended to in employing this process is to take care that the water, hydrochloric acid, and calico are free of accidental impregnation with arsenic. This is guarded against by applying the process to them in the first instance. I have lately employed this method of analysis with success in two medico-legal cases where the bodies had been buried for several months, and where the quantity of arsenic must have been very minute. Satisfactory evidence was obtained from a sixth part of the stomach, and also from the same proportion of the liver.

_Process of Marsh._—The chief difficulties in applying the process of Marsh to complex organic mixtures arise from the tendency of oxide of arsenic to adhere with obstinacy to some organic principles in the solid state, and from the liability of the gas disengaged in the apparatus to raise organic fluids in a fine froth, which breaks up slowly, and is therefore apt to pass over into the exit-tube. Many contrivances have been devised, to meet these difficulties, especially by the French chemists and toxicologists, whose attention was turned earnestly to the subject by the investigations carried on in certain late criminal trials of great interest and importance. The various devices now alluded to were subjected to trial in 1841 by a Committee of the French Institute; who came to the opinion that the following method suggested by MM. Flandin and Danger is the most convenient and comprehensive.[533]

Heat the organic matter with a sixth of its weight of strong sulphuric acid; when complete solution has taken place, concentrate the fluid to a friable almost dry charcoal; add a little concentrated nitric acid gradually to this when cold, and again evaporate to dryness; then act on the residue with boiling distilled water, and a solution of a reddish-brown colour is obtained, which may be used in such an apparatus as that of Döbereiner without risk of obstruction from froth.—The arseniuretted-hydrogen, thus disengaged along with the hydrogen gas, is to be submitted to the succession of tests described in speaking of Marsh’s process for detecting arsenic in a state of simple solution [p. 212].

This method of investigation is exceedingly precise and conclusive. The sulphuric acid aided by heat destroys organic matter sufficiently to prevent frothing in the apparatus and dissolves out arsenic from a state of combination with organic principles; and nitric acid afterwards converts any arsenic in the half-charred mass into the soluble arsenic acid. It has been employed with success in various medico-legal proceedings in France. It answers well for detecting oxide of arsenic in the viscera, muscles, and other parts of the body into which the poison has been conveyed through absorption.

_Process by Hydrosulphuric Acid._—This method may be employed in two ways, according as the object is merely to prove the presence of oxide of arsenic, or to ascertain also its quantity.

a. If proof of its presence be all that is wanted, cut any soft solids into small pieces, add distilled water if necessary, boil for half an hour, let the decoction cool, and filter it. Add a little acetic acid to the filtered fluid, and if any precipitate form, filter again. Evaporate to dryness, first by ebullition, afterwards over the vapour-bath. Dissolve the residuum again in repeated portions of boiling distilled water, and filter the solution. If it be not acid to litmus-paper add more acetic acid, and transmit hydrosulphuric acid gas through the fluid until an excess be indicated by the sense of smell after agitation, Then expel the excess of gas by boiling; and if the precipitate of sulphuret of arsenic do not subside readily add a little of a strong solution of hydrochlorate of ammonia, which will facilitate subsidence. When the precipitate has fallen to the bottom, withdraw the supernatant fluid with the pipette, Fig. 8; and replace it with a little boiling distilled water. Lastly, collect the precipitate on a filter, and proceed as by the reduction process with soda-flux for oxide of arsenic, in a state of simple solution.

This method answers very well for ordinary cases where the quantity of arsenic is not extremely minute. But I have met with instances in medico-legal practice where the process of Reinsch, as well as that of Marsh, succeeded in detecting the poison in sources to which the method by hydrosulphuric acid had been applied without avail; because apparently the organic matter existing in solution prevented the action of the gas, or, as Orfila thinks, because boiling water will not in all circumstances remove oxide of arsenic from the textures of the animal body which are impregnated with it. In particular I doubt whether this method is sufficiently delicate to detect arsenic in those organs and textures into which it has been conveyed in cases of poisoning through absorption into the blood.—Another objection is its tediousness. The first filtration, if the substance to be examined be the stomach or its contents, may take two days; and one way or another the analysis can seldom be completed within four days. Reinsch’s process may be brought to a conclusion in two hours or less, even in the most difficult circumstances.

b. The last process to be mentioned, is one based, like the previous one, upon the precipitation of arsenic in the form of sulphuret, but with very material modifications, the purpose of which is to enable the analyst to separate the whole arsenic in a state of purity, so as to ascertain the exact amount of the poison in the mixture. This method has been recently proposed by Drs. Fresenius and von Babo.[534]

Cut any soft solids into small pieces, put the whole into a porcelain basin, add as much hydrochloric acid as equals the probable weight of the dry matter in the mixture, and then water enough to form a thin pulp. Heat the basin over the vapour-bath, adding every five minutes about half a drachm of chlorate of potass, and stirring frequently, until the liquid become clear-yellow, homogeneous, and thin. Add now two drachms more of the chlorate; filter through linen, washing the residuum on the filter with boiling water; concentrate to a pound; add a strong solution of sulphurous acid till its odour predominates, and expel the excess of it by heat. The liquid is now ready for the transmission of hydrosulphuric acid gas, which should be transmitted in a slow stream for twelve hours. Wash away any sulphuret adhering to the tube by means of ammonia, and add the solution to the principal liquid; which is next to be left at a gentle heat about 80° F., in a vessel covered with paper, till the sulphureous smell entirely disappear. The precipitate, which contains organic matter as well as sulphuret, is then to be collected on a paper filter, washed, and dried with the filter over the vapour-bath. The animal matter is next destroyed, and the sulphuret converted into arsenic acid, by dropping on it fuming nitrous acid till the whole is moistened, drying the product thoroughly over the vapour-bath, moistening the residuum with concentrated sulphuric acid, heating the mixture again in the vapour-bath for two or three hours, and raising the heat afterwards gradually in a sand-bath to 300° F., till a charred brittle mass be obtained. This is to be heated over the vapour-bath with twenty parts of distilled water, filtered, and washed with boiling water on the filter till what passes through ceases to redden litmus. The solution, which ought to be colourless, is next acidulated with hydrochloric acid, and treated as formerly with hydrosulphuric acid gas. When the sulphuret has been collected on a small filter, diluted ammonia is to be sent through the filter as long as it dissolves any sulphuret, and is to be received in a weighed porcelain basin, in which the ammonia and water are to be driven off at a temperature not exceeding 212°. The sulphuret which is alone left may now be weighed by again weighing the basin; and one grain of sulphuret is equivalent to 0·803 of a grain of oxide of arsenic.—The authors add an elaborate process for obtaining from this the whole arsenic by reduction. But such a proceeding is unnecessary. It is sufficient in medico-legal inquiries to ascertain by the simpler method given above [p. 204], that it does yield by reduction with soda-flux a true arsenical crust, and that this yields by oxidation white, sparkling crystals with triangular facettes.

After a comparative trial of the most esteemed process, Drs. Fresenius and von Babo state that they found the one now described as delicate as any other, and the only method by which the quantity of oxide of arsenic can be ascertained with accuracy.—The hydrochloric acid used at the commencement enables the water to dissolve compounds of arsenic which water alone will not act on; and it farther facilitates solution by breaking up or dissolving organic textures. The addition of chlorate of potash prevents the escape of oxide of arsenic during the subsequent evaporation; which is apt to happen when hydrochloric acid is present. The subsequent addition of sulphuric acid converts arsenic acid into arsenious acid, in which shape the sulphuret of arsenic is more readily formed by the action of hydrosulphuric acid gas, when organic matter co-exists in the solution. The steps for destroying organic matter thrown down with the sulphuret at its first formation require no further commentary: They are the most important particulars in the process for its main object,—the determination of the quantity of pure sesqui-sulphuret, and, through it, of the sesquioxide originally in the subject of analysis.

_Of certain alleged Fallacies in the case of Organic Mixtures._

Before taking leave of the detection of arsenic in organic mixtures, it is necessary to notice certain alleged fallacies in the way of every process, arising from arsenic obtaining admission into the subject of analysis through other means than its intentional addition or its introduction as a poison into the body. This topic, one of paramount importance in medico-legal chemistry, has lately undergone careful investigation during and since the notorious trial of Madame Lafarge. The results are the following:—

It has been alleged that arsenic may obtain accidental admission into the subject of analysis, 1, because the reagents used in the processes may be adulterated with arsenic; 2, because the material of the apparatus may contain it; 3, because it may have existed in antidotes administered during life; 4, because it sometimes forms a constituent part of the human body in the natural state; and 5, because it exists in the soil of some churchyards.

1. _Arsenic may exist as an adulteration in some reagents._—It must be apt to occur in _sulphuric acid_, when that substance is prepared with pyritic sulphur, which commonly contains some sulphuret of arsenic; and it has actually been found in abundance in the acid by various experimentalists, and in England for the first time by Dr. Rees.[535] It may be detected by transmitting hydrosulphuric acid gas through the diluted acid; and it may be effectually removed in the same way,[536] the acid being afterwards filtered in a funnel whose throat is filled with asbestus, and the excess of gas being expelled by heat.—_Hydrochloric acid_ may contain arsenic, because it may have been prepared with an arsenicated sulphuric acid. The impurity may be detected and removed in the same way as in that substance. Nitric acid seems not apt to be similarly adulterated;[537] but it may be tested by Marsh’s process, after neutralizing the acid with potash, and adding more sulphuric acid than is required to decompose the nitre thus formed. _Zinc_ occasionally contains a little arsenic, which will be evolved in Marsh’s process. Dr. Clark of Aberdeen says zinc is scarcely ever free of a trace of arsenic; and it has been occasionally detected by others. Orfila, however, very seldom found so much as to be discoverable by Marsh’s test applied continuously for a great length of time.[538] A committee of the French Institute came to the same conclusion.[539] M. Jaquelain, acting under the directions of Professor Dumas, could not detect an atom in any French specimen of zinc, or its carbonate or silicated oxide, as met with in commerce.[540] Lastly, Mr. Brett satisfied himself that no British or foreign zinc he could obtain indicated the presence of arsenic by a process capable of detecting a 5000th of that metal in zinc.[541] It is an obvious inference from all these inquiries that no difficulty can be experienced in obtaining zinc so pure as to exhibit not a trace of arsenic by Marsh’s method. Neither is there any difficulty in obtaining sulphuric, muriatic, and nitric acid free of that adulteration.

But at the same time it is equally obvious, that in medico-legal analyses, unless the reagents used be previously known to be free of arsenic, they ought invariably to be subjected in the first instance to the process, whatever it may be, which the analyst proposes to employ for detecting arsenic in a suspected substance.

2. _Arsenic may be present in some articles of chemical apparatus._—Arsenic has been detected in the metal of cast-iron pots,[542] which Orfila and others have proposed to employ in certain analyses on the large scale, as, for example, when the poison is sought for in the whole soft solids of the human body. It is denied, however, that any of that arsenic can be dissolved out of cast-iron by the process which has been followed in such circumstances.[543]

The primary fact, and the qualification of it, are in my opinion of equally little medico-legal importance. It is not likely that such enormous masses of material will ever be operated on again, as those which were made use of in some late, French trials, and for which great iron pots were found indispensable;—because it has been proved that absorbed arsenic is chiefly to be met with in particular organs or secretions, such as the liver and urine. Besides, a false importance has been attached to the enthusiastic analyses of the whole human carcase, with which some French chemists have been astounding the minds of the scientific world, as well as the vulgar, on the occasion of certain late trials for poisoning. I confess I could not find fault with a jury, who might decline to put faith in the evidence of poisoning with arsenic, when the analyst, after boiling an entire body, with many gallons of water, in a huge iron cauldron, making use of whole pounds of sulphuric acid, nitric acid, and nitre, and toiling for days and weeks at the process, could do no more than produce minute traces of the poison. What man of common sense will believe, that, with such bulky materials and crude apparatus, it is possible to guard to a certainty against the accidental admission of a little arsenic? At all events I am much mistaken if any British jury would condemn a prisoner on such evidence,—or any British chemist find fault with them for declining to do so.

3. _Arsenic may have existed in antidotes administered during life._—It is now generally known, that the only chemical antidote for arsenic is the hydrated sesquioxide of iron. But this substance appears occasionally to contain a little arsenic, obviously derived from the compound of iron whence the oxide is prepared.[544] Such an adulteration must be rare in what is prepared by the ordinary processes, according to which the oxide of arsenic ought to remain in solution. The only effectual mode, however, of guarding against this source of error, when the antidote has been administered, is to examine a portion of the stock whence the patient was supplied, by dissolving it in an excess of sulphuric acid, and subjecting it to Marsh’s test.

4. _Arsenic sometimes exists naturally in the human body._—This startling proposition was first advanced by M. Couerbe, and by Professor Orfila soon afterwards.[545] The latter subsequently stated, that it exists only in the bones, and not in any of the soft solids.[546] It is now clear, however, that both of these experimentalists must have committed an error. Orfila himself admits that his early researches are vitiated by the subsequent discovery of arsenic in some kinds of sulphuric acid;[547] and all recent attempts by others to obtain his results have failed. Thus MM. Flandin and Danger could not detect arsenic in any part of the human body, when it had not been administered:[548] Pfaff was unable to detect an atom of it in the bones of man or the lower animals by Orfila’s own process:[549] Dr. Rees was equally unsuccessful:[550] and in 1841 a committee of the French Institute, who superintended the performance of an analysis in three cases by Orfila, reported that he failed in every instance to find a trace of arsenic, by a process which could detect a 65th part of a grain intentionally mixed with an avoirdupois pound of bones.[551]

There is the strongest possible presumption, therefore, that human bones never contain any arsenic. And besides, supposing they did, the source of fallacy would be utterly insignificant; for, when it becomes necessary to search for arsenic absorbed into the textures of the body, it is never necessary to have recourse to the bones.

5. _Arsenic may exist in the soil of churchyards._—This proposition too was first announced by Professor Orfila, who found a little in the churchyard of Villey-sur-Tille, near Dijon, and of the Bicêtre, Mont-Parnasse, and New Botanic Garden at Paris.[552] And although MM. Flandin and Danger afterwards denied they could ever find any,[553] a committee of the Parisian Academy of Medicine reported that Orfila proved before them the accuracy of his statement.[554] But the arsenic exists in a state in which it cannot be dissolved out by boiling water: It has been hitherto separable only by boiling the churchyard mould with concentrated sulphuric acid. Hence it cannot pass by percolation through a coffin into a body; and consequently it becomes a source of fallacy only when the coffin has been broken up in the course of time, and the mould lies in actual contact with the organs to be analysed.[555]

It plainly appears, then, that most of the fallacies alleged against the validity of the evidence derived from the discovery of arsenic within the human body in cases of poisoning have no real existence; and that those which are real can easily be provided against by simple and obvious precautions.

3. _Arsenite of Copper_.

The arsenite of copper [Scheele’s-green, Mineral-green] deserves notice, because it is in use as a pigment, and has actually been used as a poison. Dr. Duncan once detected it in pills, given to a pregnant female with the view of procuring abortion; in Paris it has been detected in sweetmeats, having been used to give them a fine green colour;[556] and Mr. Ainley of Bingley in Yorkshire informs me he found it to constitute a pigment sold by London pastry-cooks under the name of emerald-green for colouring preserves, and which in his practice had proved poisonous to children who had eaten apple-tarts coloured with it.

It is a compound of arsenious acid and deutoxide of copper, is sold in powder or pulverulent cakes, and has a pale grass-green colour. Its nature may be ascertained by heating it in a glass tube. Crystals of oxide of arsenic sublime, and oxide of copper remains, which, on being dissolved in nitric acid, yields a fine violet-blue solution with ammonia.

The mineral-green of the shops, however, is seldom arsenite of copper. The substance sold in Edinburgh under that name, although believed by colourmen to be a preparation of arsenic, is not the arsenite of copper, but a mixture of hydrated oxide of copper and carbonate of lime; which will be mentioned more particularly under the head of the poisons of copper.

_Process for Organic Mixtures._—The suspected mixture is to be heated with a little hydrochloric acid and well stirred. The arsenite being thus dissolved, the solution is to be allowed to cool and then filtered. A stream of hydrosulphuric-acid gas will now cause a dark-brown or yellowish-brown muddiness or precipitate, which is a mixture of sulphuret of copper and sulphuret of arsenic. The precipitate being separated after boiling, and properly cleansed by the process of subsidence and affusion, or if it is large, by washing on a filter, the two sulphurets are to be separated by ammonia, which dissolves sulphuret of arsenic but leaves the sulphuret of copper; and the sulphuret of arsenic may be recovered from the filtered fluid by expelling the ammonia with heat. The sulphuret of arsenic is next to be reduced as directed at page 211; and the sulphuret of copper examined as recommended under the head of copper.

4. _Arsenite of Potass_.

This salt is an object of some importance to the medical jurist, as it forms the basis of a common medicine, Fowler’s Solution, or the Tasteless Ague Drop. This preparation contains in every ounce four grains of arsenious acid. It has a brownish-red colour, and an odour of lavender. It is strongly alkaline to litmus. When acidulated with hydrochloric acid, hydrosulphuric-acid gas causes in it a dirty brownish-yellow precipitate; and Reinsch’s process will detach arsenic from it upon copper in a state capable of being subjected to the usual tests [see p. 214].

5. _Arseniate of Potass._

This substance is so rarely met with as to be an object of little consequence to the medical jurist: nevertheless I have found in the course of reading two instances of poisoning with it. A very dangerous and tedious case has been related by Professor Bernt, which arose from too great a quantity having been given medicinally by an ignorant druggist;[557] and a case of accidental poisoning with it has been related in the London Medical Repository.[558] A singular account too has been published of the accidental poisoning of seven horses with it at Paris. They all died, most of them with the symptoms and morbid appearances of well-marked inflammation of the alimentary canal.[559]

When solid it forms tetraedral prismatic crystals, acuminated by four planes. It is very soluble in water, fuses at a red heat, and on cooling concretes into a crumbly, foliaceous mass, having a pearly lustre. It is easily known by the effect of the process of reduction—of the nitrate of silver, the salts of copper, and sulphuretted-hydrogen. Heated with charcoal in a tube it gives off metallic arsenic in the usual manner; but a stronger heat is required than for the reduction of the arsenious acid. Dissolved in water and treated with nitrate of silver it yields a brick-red precipitate, the arseniate of silver. With the salts of copper its solution gives a pale bluish-white precipitate, the arseniate of copper. With sulphuretted-hydrogen gas, preceded by acidulation with muriatic acid, and transmitted for a considerable length of time, it yields the yellow sulphuret of arsenic. When in solution it yields arsenic both by Reinsch’s process and the method of Marsh.

6. _The Sulphurets of Arsenic._

In the arts various substances are known which contain a compound of sulphur and arsenic. In the first place, two pure sulphurets are known in chemistry and in painting, the one of a fine orange colour, and known by the name of realgar, the other of a rich sulphur-yellow, and termed orpiment. Secondly, the name of orpiment is familiarly given to a pigment in more general use than either of the former, which has a less lively colour, and consists of pure orpiment with a large admixture of arsenious acid. Lastly, orpiment also forms a great proportion of another common pigment, King’s yellow.

The orange-red sulphuret (realgar, risigallum, Σανδαραχη, sandaracha), is chiefly a natural production. It is solid, of a bright orange-red colour, and composed of small shining scales, so soft as to be scratched with the nail. It is composed of one equivalent of metal and one of sulphur. Its best chemical characters are the disengagement of metallic arsenic when it is heated in a tube with potass or the black flux; and its undergoing sublimation unchanged when heated alone in a tube.

The yellow sulphuret (orpiment, auripigmentum, αρσενικον), is both a natural production, and the result of many chemical operations. The sulphuret thrown down from solutions of arsenic by sulphuretted-hydrogen is quite conformable in physical and chemical characters with the natural orpiment. Natural orpiment, when in mass, consists of broad scales of much brilliancy and of a rich yellow colour. It is composed of two equivalents of metal and three of sulphur. Its most striking chemical characters are the same with those of realgar, from which it is distinguished chiefly by its colour.

It has been stated by Hahnemann in his elaborate work on Arsenic, that the pure sulphurets are somewhat soluble in water,—that native orpiment is soluble in 5000 parts of water with the aid of ebullition, and that artificial orpiment by precipitation is soluble in 600 parts.[560] Hahnemann, however, was mistaken in supposing that the water dissolved these sulphurets. It does not dissolve, but decomposes them. Very lately M. Decourdemanche has found that, by slow action in cold water, and much more quickly with the aid of heat, the arsenical sulphuret is decomposed by virtue of a simultaneous decomposition of the water, hydrosulphuric acid being evolved and an oxide of arsenic remaining in solution. And he has farther remarked, that this change is promoted by the presence of animal and vegetable principles dissolved in water.[561] These facts are interesting, as they explain certain apparent anomalies to be noticed presently in the physiological properties of the sulphurets.

The common orpiment of the shops is not a pure sulphuret like the natural orpiment, but a much more active substance, a mixture of orpiment and arsenious acid. It is made by subliming in close vessels a mixture of sulphur and oxide of arsenic. It is met with in the shops in two forms, in that of a fine powder possessing a yellow colour with a faint tint of orange, and in that of concave masses composed of layers of various tints of white, yellow and orange, commonly also lined internally with tetraedral white pyramidal crystals. Till lately it was accounted a variety of sulphuret, and some ingenious conjectures were made as to the cause of its superior energy over the other sulphurets as a poison. But M. Guibourt has proved that it always contains oxide of arsenic, and is commonly impregnated with it to a very large amount, some parcels containing so much as 96 per cent.[562] The inner surface I have often seen lined with large crystals of pure oxide. In a very interesting account by Dr. Symonds of Bristol, describing the case of Mrs. Smith, for whose murder a woman Burdock was executed in that city a few years ago, it is stated that artificial orpiment was the poison given, that death took place in a very few hours, and that a sample from the druggist’s shop where the poison was bought contained on an average 79 per cent. of oxide of arsenic.[563]

Another impure sulphuret, a good deal used in painting, and a favourite poison in this country for killing flies, is King’s yellow. It is sold in the form of a light powder or in loose conical cakes. It has an intense sulphur-yellow colour. This substance is soluble, though not entirely, in water, both cold and warm, and forms a colourless solution, from which, on cooling, or by evaporation, a yellow powder separates. In this respect it differs essentially from the pure sulphurets. The solution is not acted on by reagents in the same way as the solution of arsenious acid. Lime-water and hydrosulphuric acid have no effect on it, the ammoniacal nitrate of silver causes a copious dirty brown, and the ammoniacal sulphate of copper a scanty, dirty lemon-yellow precipitate. I have not seen any account of the mode of preparing it or an analysis of its composition. But according to my own experiments it contains a large proportion of sulphuret of arsenic, a considerable proportion of lime, and about 16 per cent. of sulphur. Its nature is best shown by the following method of analysis. Let the powder be agitated in diluted ammonia till the colour becomes white. The filtered fluid contains the sulphuret of arsenic, which, on addition of an acid, falls down, and may be separated and reduced in a tube with the black flux. The remaining white powder, well freed from adhering sulphuret by washing, is next to be agitated in diluted acetate or hydrochloric acid and again filtered. The solution on being neutralized precipitates abundantly with oxalate of ammonia and the alkaline carbonates, showing that lime was taken up by the acid: and, as the acid operates without effervescence, the lime must have been in the caustic state. The powder which remains after the action of the acid will be found to fuse with a gentle heat and to burn almost entirely away with a blue flame, emitting sulphureous vapours. These experiments make it obvious that King’s yellow contains sulphuret of arsenic, caustic lime, and free sulphur; and in all probability the lime exists in the form of a triple sulphuret of lime and arsenic.

All the preparations containing the sulphuret of arsenic are interesting to the medical jurist, but particularly the two impure sulphurets last mentioned. The King’s yellow above all should be carefully studied, because on account of its frequent employment as a fly-poison it has been the source of fatal accidents. It was likewise taken intentionally a few years ago in this city, and proved fatal in thirty-six hours. Dr. Duncan also, while he was Professor of Medical Jurisprudence, met with an instance of an attempt to poison by mixing King’s yellow with tea; and at the Glasgow Spring Circuit of 1822 a woman was tried for poisoning her child with it.

_Process for Organic Mixtures._—If sulphuret of arsenic be present in such mixtures in appreciable quantity, the particles, owing to their intense yellow colour, will be visible in any mass which has not the same tint. From this state of admixture they may be removed by adding caustic ammonia which dissolves sulphuret of arsenic; and the solution, on being acidulated with muriatic acid, will deposit the sulphuret sufficiently pure for undergoing the process of reduction.

Sulphuret of arsenic sometimes exists in small quantity in the stomach, although the poison was given in the form of oxide; for a portion of the oxide is subject to be converted into the sulphuret by hydrosulphuric acid gas evolved in the stomach after death.[564] In every instance of the kind yet carefully examined a large proportion of the oxide has remained unacted on, although the intense colour of the mixed sulphuret makes it appear as if that were the only compound present.

7. _Arseniuretted-Hydrogen._

This compound presents the form of a colourless gas, possessing a fetid garlicky odour, a density of nearly 2·7, and great virulence as a poison. It is mentioned here, because accidental poisoning with it has happened occasionally within a few years, chiefly owing to the occasional adulteration of sulphuric acid with arsenic, and the liability of the arsenic to form arseniuretted-hydrogen when such sulphuric acid is used to prepare hydrogen gas. Dr. O’Reilly has mentioned a melancholy instance of a young chemist losing his life in this way.[565] Dr. Schlinder of Greifenberg has related another, which did not prove fatal.[566] And it is well known that the German chemist Gehlen lost his life by accidentally breathing arseniuretted-hydrogen while engaged in examining its chemical properties.[567] It is an inflammable body; and its presence in any other gas is easily detected by burning it according to the method of Marsh.

Comments

Log in to leave a comment.

Treatise on PoisonsChapter XLVIII: Section I: Of the Chemical Tests for the Compounds of Arsenic (2)

0%23 min left in chapter