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PROVINCIAL

MEDICAL & SURGICAL JOURNAL.

EDITED FOR THE

PROVINCIAL MEDICAL AND SURGICAL ASSOCIATION,

BY

ROBERT J. N. STRE ETEN, M.D.,

SECRETARY TO THE ASSOCIATION.

18 4 4.

LONDON: JOHN CHURCHILL, PRINCES STREET, sono.

WORCESTER: DEIGHTON AND CO., HIGH STREET.

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PROVINCIAL

MEDICAL & SURGICAL JOURNAL.

EDITED BY ROBERT J. N. STREETEN, M.D.

ON ARSENIC AS A POISON; ITS TESTS AND | should be filtered. This is a tedious process. When ANTIDOTE.

you have obtained a clear solution, animal matter may

often be deposited by adding strong acetic acid, which By E. J. SHEARMAN, M.D., ROTHERHAM. coagulates the casein. Neutralize this acid with potass

or ammonia, and then try the sulphuretted hydrogen Read before the Sheffield Medical Society,

test. If this does not act, all you have to do is, slowly March 7, 1844.

to evaporate the solution to dryness in a porcelain dishi, Arsenic is a substance so commonly used for crimis redissolve it in distilled water, and when cold, filter. nal purposes, and 80 little under the control of any This process, several times repeated, eventually gets chemical substance as an antidote, that it is very desir- | rid of the whole of the animal matter. able to establish some certain mode of detecting and I had an opportunity of proving this a few years . showing it so clearly that medical practitioners may be since, in the case of a cow belonging to a nobleman in able to swear, most positively, as to its existence or not. the neighbourhood, which had been evidently poi

The late trial of Madame Lafarge, in France, although soned. Mr. Peach, our eminent veterinary surgeon, the chemical and physiological parts of it were con was called in, who not being willing to give an opinion ducted by some of the first men of the age, terminated as to what was the poison, his lordship begged of me in such a manner as to convince most English chemists to try to ascertain it. At that time the stomach and its that the proof of arsenic having existed in the body of contents had been buried a day or two, and I had to pick on Lafarge, was not established in so distinct a manner as out any part that appeared inflamed to operate upon, would have carried conviction in this country; and, as

The animal matter in this case was very large, but by I took great interest in it whilst it lasted, I was led to

attending to the above rules, I obtained a sufficient attend to the subject.

quantity of arsenic to have convinced, as I then thought, In order to show the existence of arsenic in a court

the most sceptical of its presence. I showed the crust of justice in England, we should be enabled to prove

I procured to Mr, West, of Leeds, who said there was the following facts so satisfactorily, that a jury may

no substance but arsenic capable of showing that .. not only see, but perfectly understand them.

appearance. Ist. The metal should be produced either from the

When a clear solution is obtained, with but a small.', contents of the stomach, intestines, or urine, if the

portion of animal matter in it, the ammoniacal nitrate patient should survive; or, if dead, from those and

dl of silver gives a lively lemon-yellow precipitate the some part of the body.

| arsenite of silver, 'The ammoniacal sulphate of copper : 2nd. We should be able to prove that the animal

gives an apple or grass-green precipitate--the arsenite , substances experimented upon were the excretions, I hudrogen oas through this solution, previously neu

of copper. And the transmission of sulphuretted and parts of the patient's body only; unmixed with tralized, and then slightly acidulated with acetic acid, ?, any other matter.

throws down an abundant sulphur-yellow precipitate 3rd. We must also prove that the tests we use to the sulphuret of arsenic. show the existence of arsenic have not a particle of . It is the best plan to boil the last precipitate in the arsenic in themselves; and this requires great caution,

fin because a skilful advocate might make a guilty pri

solution a few minutes, which drives off the excess of

sulphuretted hydrogen gas, and allows the whole of soner appear innocent, owing to this omission.

the sulphuret of arsenic to deposit. This is to be 4th. As antimony, bismuth, tin, zinc, lead, tellurium, collected on a filter; dried on a watch glass; introcadmium, selenium, and potassium, sublime in a some duced into the bottom of a bulbed tube, and covered what similar manner to arsenic, and may be mistaken with black flux, or what is perhaps better, freshly for it; it is quite necessary for an inexperienced eye to ignited charcoal. The tube is then to be heated by guard against such a mistake.

a spirit lamp, first at the part just above where the . It is therefore my intention, in as simple and clear flux is, and then gradually below, so as to sublime the

a manner as I possibly can, to endeavour to show that metallic arsenic all round the tube; which forms a arsenic can be tested from the most minute particle, brilliant polished metallic appearance, that cannot be so clearly that an unscientific person cannot mistake easily mistaken when once seen: and which I once heard it; and, also, that this can be done easily, without given in evidence as the only proof of arsenic in one using any chemical substance known to contain of our courts of justice :--the fallacy of which opinion arsenic.

I think I shall be able to prove. The most common and efficacious manner of proceed. The metallic arsensic should afterwards be oxidized ing, when the contents of the stomach, or a decoction by the heat of the spirit lamp and the oxygen of the of the stomach, liver, &c., in distilled water, is to be air, and driven up the tube, so as to allow it to form operated upon, is that recommended by Dr. Christison. octohedral crystals of arsenious acid, with triangular The first point is to get rid of the animal matter. After facettes. boiling for half an hour in distilled water, the solution In estimating the process which I have now

No. 1, April 3, 1944,

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described, an English jury would wish to know, before the remaining hydrogen being set free. This arsenthey condemned a fellow creature to death, if there iuret of copper may be easily sublimed in a glass is no other mode of detecting and proving arsenic; and tube; when the whole of the arsenious acid will be if no other substance gives the same crystals as deposited in thick brilliant clusters of octohedral arsenious acid ?

crystals on the tube. This gap was, in a degree, filled up, by Marsh's The objection urged against Marsh's apparatus, hydrogen test; where hydrogen gas is generated from will, of course, equally apply to this, in being obliged zinc, sulphuric acid and water, and the suspected sub- to use zinc for the generation of hydrogen. stance in solution added' to it; if arsenic be present, J. There is another test which I think deserves more hydrogen has such an affinity for it, that it will com- | attention than it has yet met with-viz., the decompobine with the whole of it very quickly. The sition of distilled water by galvanism, to which the susarsenietted hydrogen being ignited,' the metallic | pected solution is added, with pure sulphuric acid, arsenic is, deposited on porcelain or glass, which collecting the hydrogen from the negative pole or can be seen in rhomboidal crystals with a powerful zincode of Smee's battery, igniting it, and examining microscope.

the stain left in a glass tube open at both ends. If The only objection to this test is, that you are

there is the smallest particle of arsenic, the hydrogen obliged to use zinc, which is known often to contain

will combine with it, and you then have a stain of arsenic: and, although it shows the most minute

metallic arsenic with rhomboidal crystals; which you portion of arsenic that can possibly be exhibited, yet,

may oridize, collect, and dissolve in water; go through how can you swear that, after the first layer of zinc

the fluid tests, reduce the sulphuret in a tube, and subis oxidized, there may not be some arsenic in the next ?

lime it into arsenious acid again. This is the most for we know that arsenic runs in veins of the zinc ore.

delicate test known, and is perfectly free from the

charge of using any substance in which arsenic can The next test I would describe is that beautiful one

erist; on which account I think it the most valuable of Professor Reinsch, modified by Christison, which

of them all, and the one to which I would this evening is well suited for detecting arsenic in animal and vege- 1 particularly direct the attention of the Society. table substances. Mix the suspected matter with I have likewise combined this mode of producing distilled water: add at least two drachms of pure arsenietted hydrogen with Ellis's plan of testing it by hydrochloric acid to every eight ounces of fluid. Put the oxides of copper, and have succeeded in obtaining a few bits of very thin and bright copper plate into it, I decided crystals of arsenious acid by it; thus doing boil for half an hour, and the arsenic will be gradually away with the necessity of using zinc. deposited on the copper plates. We have here for the most likely substance to be mistaken for analysis, animal matter in solution with arsenious acid | arsenic by any of these tests is antimony, because by heat, hydrochloric acid, water and copper. As far

antimony sublimes into the same kind of crystals as as I can ascertain at present, the following is the larsenic does. But by attending to the following result. The water and arsenious acid are both decom. | rules the two substances may, I think, be easily posed : the oxygen of the water unites with the distinguished. copper, forming oxide of copper : the hydrogen of Metallic arsenic sublimes at a heat of 356° without the water unites with the metallic arsenic, forming liquifving into rhomboidal crystals ; arsenious acid arsenietted hydrogen, which is decomposed by the sublimes at 380°, into octohedral crystals ; metallic oxide of copper the metallic arsenic of the arsenietted

antimony sublimes not under 810°; and on cooling, hydrogen forming a coat on the oxide of copper; / acquires a highly lamellated texture, and yields octowhile the free hydrogen goes to combine with auother hedral crustais like arsenic. After you have obtained portion of the oxygen of the arsenious acid, and a deposit of the suspected metal in a glass tube, if you forms water: thus accounting for the gradual coating I heat the tnbe gradually hu a spirit lamn: should the

coating heat the tube gradually by a spirit lamp; should the of the copper with arsenic. The hydrochloric acid

metal be arsenic, it sublimes on the cool part of the unites with the ammonia of the animal matter as it

al matter as it tube into octohedral crystals ; which can be dissolved is decomposed by the heat, forming hydrochlorate of in water, and tested by the three fluid tests. If it is ammonia ; and, if in excess, remains free in the solu- mtir

olu. | antimony, it first produces dense white fumes, and an tion. These arsenietted copper plates are to be

o be amorphous white powder is deposited; and the heat taken out. cut into small chips, introduced into a I being kept up, the tube is lined with a white crust, bulbed tube, and exposed to a low red heat over a

which is insoluble in water. spirit lamp, and the arsenious acid is sublimed in

By this method, both arsenic and antimony may be octohedral crystals with triangular facettes. These

tested at the same time. Arsenic will be sublimed in may be rendered more distinct if you turn out the

oxide at the cool part of the tube : antimony remaining copper chips, close the tube with the finger, and chase at the bot mort the oxide up and down with the lamp. By dissolving In the reduction test with sulphuretted hydrogen this oxide in distilled water, you may go through the

gas, it should be carefully remembered that the sulwhole of the former tests.

phurets of antimony, tin, selenium, cadmium, and A very easy mode of ascertaining the exact weight tellurium, have nearly the same yellow colour, and are of arsenic in any given quantity of fluid, would be to deposited in the same manner as the sulphuret of previously weigh the dry glass tube before introducing | arsenic; and when reduced to their metallic state the arsenietted copper chips, and to weigh it again with black flux, they not only give an appearance so after the arsenious acid is sublimed; the copper being much like arsenic, that it requires a very practised removed, the increase in weight would give the quantity eye to distinguish each-if even that be possible, but of arsenic.

tellurium and cadmium also exhale a garlic odour, like A most ingenious, scientific and elegant mode of arsenic. detecting arsenic has lately been introduced by Robert L. Thompson, Esq., has shown that antimoniuretted Ellis, Esq., of University College, London; to whose hydrogen when ignited, not only gives a stain very polite attention I am indebted for his apparatus, made similar to arsenietted hydrogen, but also that the entirely of glass, in which I have now the pleasure of smell of both are very similar, and suggests the folexhibiting his plan. He has discovered that the oxides | lowing mode of distinguishing them :-Dissolve the of copper have such affinity for arsensic, that by crust left on the glass by a drop of nitric acid : evapomerely passing arsenietted hydrogen over them, a rate it to dryness, and a white powder will be left in double decomposition takes place; caloric is given either case : add now, a little weak solution of nitrate out; the oxygen of the copper uniting with part of of silver, and expose it to the fumes of ammonia from a the hydrogen, forms water, which is seen in the glass stopper. Antimony will give a white precipitate, process; the arsenic of the arsenietted hydrogen and arsenic a yellow floculent one. In answer to uniting with the copper, forms arseniuret of copper :' the above objection, Marsh proposed the following ARSENIC AS A POISON.

ingenious plan :-Moisten the porcelain or glass with a l oxide of iron, and then killed them within a short drop of water, and hold it an inch above the flame of time. The stomachs have shown patches of inflammathe jet of burning hydrogen: the arsenic, if any, will tion, but no arsenious acid could be detected by be oxidized at the time the hydrogen is undergoing Reinsch's method, the copper plates having merely a combustion, and is dissolved in the water as arsenious scaly deposit of iron upon them; nor could arsenious acid; which can be proved by adding a drop of a acid be detected in any other way. This is a strong solution of nitrate of silver to it, which gives a lively presumption that the whole of the arsenic was reduced lemon-coloured precipitate, while the colour of anti- to its metallic state. So that, from the results of my mony will not be changed. But I have so repeatedly own experiments, and the accounts I have read of the found phosphuretted hydrogen give the same resulls, that successful use of the hydrated per-oxide of iron as an I cannot think this test can be depended upon. antidote to arsenic in the human subject by many prac

The question then comes-how can a witness swear titioners, I am induced to place great reliance on this most positively that a substance is arsenic, and nothing | substance. else? And how can he convince an unscientific jury

In the 1st vol. of the London Medical Gazette, for of thal fact? I think, only in the following manner :

| 1841-2, page 116, is a communication from the celeIst. By producing the metal and showing its crystals.

brated Dr. Beck, containing an account of no less than 2nd. Ředucing it to the oxide, and showing ils cryslals.

| twenty-nine successful cases of recovery from poisoning 3rd. From these crystals going through all the fluid

i by arsenic, by the prompt use of the moist hydrated tests.

| per-oride of iron in the human species. And I could 4th. Reducing the sulphuret again to its metallic

I point out more, which I have observed related in the state, then to the oxide, and again going through the

journals. fluid tests.

The last edition of the Edinburgh Pharmacopæia 5th. And if this be shown clearly, with all the

gives a very good formula for preparing this antidote, before mentioned tests, it will be impossible for any

under the name of “Ferrugo." It can be kept good, advocate to mislead a jury.

and fit for use, in stoppered bottles, covered with There is no substance but antimony that will form

water. I respectfully beg to suggest to my medical

brethren, that they provide themselves with a proper crystals like arsenic, which can be mistaken for

for supply of it, so as to be ready in a moment. A tablearsenic by any other test.

spoonful should be given in plenty of water, every five It is not at all necessary here, to describe the symp- minutes, to an adult; and a dessert-spoonful to a child, toms attending poisoning by arsenic; but I would until relief from the urgent symptoms is obtained. It remark that there may be a great deal of injury done is perfectly inert if kept dry. Dr. Golding Bird has by improper interference with the stomach pump, in mentioned that the hydrated per-oxide of iron may consequence of the softening of the sub-mucous be extemporaneously prepared, by adding one ounce of cellular tissue from acute inflammation. As far as liquor potassæ, to half an ounce of tincture of sesquiI have been able to collect from the best writers on chloride of iron. This may be almost always obtained this subject, the following is the most successful model in a short time from any druggist. of managing these cases. If called in immediately I have never tried the moist hydrated per-sulphuret after arsenic has been swallowed, use the stomach of iron, but have no doubt it may act as an antidote, pump at once: inject large quantities of milk; or, if by reducing the oxide of arsenic to a sulphuret, which not at hand, mucilage or groat gruel, and withdraw is much less poisonous. The hydrated per-oxide, I it again repeatedly. Or if the stomach pamp is not should think, acts by the free hydrogen combining ready, and vomiting does not exist in consequence of with the oxygen of the arsenic, forming water, and the effect of the arsenic, it should be promoted (in leaving metallic arsenic, which is insoluble and inert, a case where there will be no legal inquiry instituted) ( behind. by giving a large dose of sulphate of zinc immediately, The carbonate of iron is mentioned as another antishortly followed by copious doses of the moist hydrated dote, but I should prefer the others. per-ocido of iron, in water or milk, until you can pro- The stomach pump should never be used after the cure it. But when the life of a fellow-creature will depend upon the evidence given as to the chemical

| arsenic has had time to act on the mucous membrane,

as it is very liable to penetrate through all the coats of proof of arsenic having been exhibited, it was suggested by Dr. Pavell, the President, that either sulphate of

the stomach.

Arsenjetted hydrogen gas is the most destructive copper or mustard should be used as an emetic, instead

mode of introducing arsenic into the system. Several of zinc, to prevent the possibility of an advocate

deaths have been recorded from it; and I would having it in his power to say that zinc had been used in any form. Although pure crystallized sulphate of

mention, with the most sincere regret, the state into

which it has brought a most intelligent and valued zinc could not possibly contain arsenic, I think this

pupil of mine. He is the inventor of the present mode is a very proper precaution.

of gilding and silvering by galvanism. Zinc is most The only antidotes which have been discovered for extensively used in the works which he has superinarsenic are the moist hydrated per-oxide of iron, and tended, and he has so long breathed an atmosphere the moist hydrated per-sulphuret of iron. A few years of arsenietted hydrogen gas there, and in his private ago I tried the effect of the hydrated per-oxide of iron experiments, that it brought on a peculiar kind os eple on six dogs of the same age. I gave each of them ten lepsy, much like what is described by Dr. Christison, grains of oxide of arsenic in various forms. The first which has latterly been gradually increasing; and his was killed with it in four hours. In the second, I intellect, which was once one of the brighest, is now allowed balf an hour to elapse before I gave the iron : reduced nearly to fatuity. he died. To the third I gave the iron with the arsenic: There are a few more observations closely connected he never had a symptomn of poisoning. The fourth I with this subiect, which I should have taken the liberty killed with the iron, as it was not well prepared. The of making, but I fear this paper will be considered on 5th took the iron a quarter of an hour after the arsenic: long already. It now only reinains for me.co

thank he was very ill several days, but perfectly recovered. you for so patiently listening to this very The 6th took it half an hour after the arsenic, and I digest of so important a subject; ana."

errors I died the following day. I examined the stomachs of I have either committed or omitted, should all the dogs that died, and found them exhibit the

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professional brethren to attend more minutely to the highly injected diffuse red appearance so well described subiect, and point them out, I shall with great place

sure by Drs. Hope, Carswell, and Roupell, in their plates. receive their reproof and instruction. I have lately given dogs and rahhite lara dorne ns!

en daarmihed in this naner.

hould lead

TL.

-I.

-C.L.

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