Chapter XLVII: Section I: Of the Chemical Tests for the Compounds of Arsenic (1)

Metallic arsenic has an iron-gray colour, a specific gravity of 8·308, and a crystalline fracture. It is very brittle. It has a strong tendency to oxidate, so that it undergoes this change in air, in water, and even in alcohol. In air, particularly when moist, it becomes rapidly tarnished, a black powder being formed, which some have regarded as a regular protoxide.[488]—When exposed to heat, metallic arsenic is usually said to sublime at the temperature of 356° F.; but according to some late experiments by Dr. Mitchell of Philadelphia this does not happen under a low red heat, luminous in the dark.[489] In close vessels it condenses unchanged; but when heated in the open air, it passes to the state of white oxide, and rises in white fumes. This substance is a sesquioxide, consisting of two equivalents of metal and three of oxygen. Another oxide likewise exists, which contains two equivalents of metal and five of oxygen, and, possessing strong acid properties, is denominated arsenic acid. The sesquioxide and arsenic acid unite with bases, and produce compounds which, with the exception of those they form with the alkalis, are mostly insoluble. Metallic arsenic unites with sulphur in two proportions, forming an orange-red and a sulphur-yellow compound. The compounds of arsenic have very little chemical action with vegetable and animal principles.

Of the compounds which arsenic thus forms, those which it will be necessary to particularize are the following:—1. The protoxide of Berzelius, or _fly-powder_. 2. The arsenious acid, or _white arsenic_. 3. The arsenite of copper, or _mineral green_. 4. The arsenite of potass as contained in _Fowler’s solution_. 5. The arsenite of potass; 6. The various sulphurets, pure and impure, namely, _realgar_, _orpiment_, and _king’s yellow_; and 7. Arseniuretted-hydrogen gas.

_Of the Tests for Fly-powder._

This substance is rarely known as a poison in Britain, but is a familiar poison in France and Germany, under the names of _Poudre à mouches_, and _Fliegenstein_. Of late it has been occasionally used in Scotland for poisoning rats.

It is a fine grayish-black powder, formed by exposing powdered arsenic for a long time to the air; but it also frequently contains fragments of the metal. It is usually considered by chemists to be a mixture of metallic arsenic and its white oxide.

It is acted on by water, the white oxide being found ere long in solution by its proper tests. Oxidation and solution, however, are also effected upon pure metallic arsenic in the same manner. A thousand grains of water take up a grain in the course of half an hour when boiled on the metal.[490]

A very simple and decisive test for fly-powder is derived from the effect of heat. If it is heated in a tube two substances are sublimed, first a white crystalline powder, and then a bright metallic crust, the former being the white oxide, the latter the metal. The metallic crust thus formed possesses physical properties, which distinguish arsenic from all other substances, capable of being sublimed by a low heat: The surface next the tube is very like polished steel, being a little darker in colour, but equal in brilliancy and polish; and the inner surface is either brilliantly crystalline to the naked eye, like the fracture of cast-iron, or has a dull grayish-white colour, but appears crystalline before a common magnifying lens of four or five powers. If these characters be attended to, particularly the appearance of the inner surface, it appears to me scarcely possible to mistake for an arsenical crust any other substance which can be sublimed by any of the methods for subliming arsenic.

If a farther test should be desired, it is only necessary, as was first proposed by Dr. Turner of London,[491] to chase the crust up and down the tube with the spirit-lamp flame till it is all oxidated, when little octaedral crystals of adamantine lustre are formed, on which, either with the naked eye or with the aid of a common lens, triangular facettes may be distinguished.

The niceties to be attended to in applying the preceding tests will be considered presently under the head of the next compound, the sesquioxide.

2. _Of the Tests for Arsenious Acid._

Arsenious acid, the sesquioxide, or white oxide of arsenic, usually called white arsenic, or simply arsenic, is the most common and important of all the arsenical preparations.

It is met with in the shops in two forms,—as a snow-white gritty powder, and in solid masses generally opaque, but sometimes translucent. When newly sublimed it is in translucent or even almost transparent masses of a vitreous lustre, conchoidal fracture and sharp-edged. By keeping it becomes opaque and white. The nature of the change has not been determined; but some alteration is certainly effected, for Guibourt, who has examined both varieties with care, found that the opaque variety is more soluble in water than the other. He adds that the former is alkaline, the latter acid, in its action on litmus paper; but I have always found the opaque variety acid.[492] The powder soon becomes analogous to the opaque variety of the oxide in mass.

The oxide of arsenic has a specific gravity of 3·729, according to the experiments of Dr. Ure,—of 3·529 when opaque, according to Mr. Alfred Taylor, and 3·798, when translucent. Very incorrect notions prevail as to its taste. It was long universally believed to be acrid,[493] and is described to be so in many systematic works and express treatises; but in reality it has little or no taste at all. The reader will find some details on this point in a paper I published in the Edinburgh Medical and Surgical Journal.[494] In the present work it is sufficient to observe, that I have repeatedly made the trial, and seen it made at my request by several scientific friends, and that, after continuing the experiment as long, and extending the poison along the tongue as far back, as we thought safe, all agreed that it had scarcely any taste at all,—perhaps towards the close a very faint sweetish taste. It appears to me that the experiments made on that occasion might have set at rest the question as to the taste of arsenic, and corrected an important error long committed by systematic authors in chemistry as well as medical jurisprudence. And accordingly in this country the truth is generally known.[495] Professor Orfila, however, continues to repeat the error; for even in the last edition of his Toxicologie he says it has “a rough, not corrosive, slightly styptic taste, perceptible not for a few seconds, but persistent, and attended with salivation.”[496] These sensations must be either imaginary or the indications of an organ peculiarly constituted. It is impossible to make satisfactory experiments with safety on its impressions on the back of the palate. But we may rest assured that in general it makes no impression there at all; for it has been often swallowed unknowingly with articles of food. Not a few have in such circumstances noticed merely its grittiness, and thought there was sand in their food. Two instances only am I hitherto acquainted with, where an acrid sensation would seem really to have been experienced in the act of eating or swallowing. In one of these, noticed in Rust’s Journal, the individual who was poisoned, could not finish the poisoned dish on account of its unpleasant, very peppery taste.[497] In the other case, which was lately communicated to me by Mr. Hewson of Lincoln, the individual, who was poisoned by arsenic dissolved in his tea-kettle,—happening in the first instance to wash his mouth with the water,—observed at the time to his daughter, that it had a very odd taste; which subsequently was called a burning taste. These facts, however, are evidently not altogether satisfactory. It is not improbable that, in an _ex post facto_ description, the reporters, as others in the same circumstances have clearly done[498], confounded the subsequent inflammation with mere taste in the act of chewing or swallowing. At all events it is absolutely certain that the great majority of people who have been poisoned with arsenic remarked in taking it either no taste at all, or merely a roughness owing to the gritty condition of its powder.

The oxide of arsenic when subjected to heat is sublimed at 380°, or, according to Dr. Mitchell, 425° F.[499] and condenses in the form of a crystalline powder, which, if the operation is performed slowly and on a small quantity proportioned to the size of the tube, evidently consists of little, adamantine octaedres.—When it is mixed with carbonaceous matter and heated, it is reduced, and the metal is sublimed. This constitutes the test of reduction, which, when conducted with due care, may be rendered singly a certain proof of the presence of arsenic.

Water dissolves it. Its solubility is a point of some medico-legal importance; for a doubt may arise whether the quantity of a solution that has been swallowed contained a sufficient dose to cause severe symptoms or death. Different statements have gone forth on this head. Klaproth found, that a thousand parts of temperate water take up only two parts and a half,—and that a thousand parts of boiling water take up 77·75 parts or a thirteenth, and retain on cooling 30 parts or a thirty-third of their weight.[500] Guibourt found a difference between the transparent and opaque varieties; for a thousand parts of temperate water dissolved in thirty-six hours 9·6 of the transparent, 12·5 of the opaque variety; and the same quantity of boiling water dissolved of the transparent variety 97 parts, retaining 18 when cooled, but of the opaque variety took up 115 and retained on cooling 29.[501] More lately Mr. Alfred Taylor observed that temperate water, simply poured on the opaque oxide and left for seventy-two hours, contained one grain in a thousand, but if often agitated, 8·5 grains; that boiling water, occasionally agitated for the same period, contained 9·27 or 9·54 grains; that water, boiling gently for an hour dissolved 31·5, and on cooling and resting for three days retained 17; that with violent ebullition for an hour, it took up 46·3, and retained 24·7 grains on cooling and resting for three days; that a saturated boiling solution after six months contained 24 or 26 grains; and that a saturated boiling solution of the transparent oxide contained 46 or 47·5 grains, and on cooling and resting for two days retained 18·7 or 13·4 grains.[502] It is impossible to account for these discrepancies; for all the experimentalists conducted their investigations with care, and with a view to the medico-legal question stated above. Hahnemann farther remarked, that at the temperature of the blood a thousand parts of water dissolve ten parts with the aid of ten minutes’ agitation;[503] and Navier, that boiling water kept for an hour on it, and decanted off in the way an infusion is usually made, dissolves 12·5 grains in every thousand.[504]

Its solubility is impaired by the presence of organic principles. When mixed with mucus or milk it dissolves, according to Hahnemann, with great difficulty; and I have found that a cup of tea, left beside the fire at a temperature of 200° for half an hour upon two grains of the oxide, does not take up entirely even that small quantity. An important consequence of the fact now mentioned is, that when swallowed in the solid state, little or no arsenic may be found in the fluid contents of the stomach. In a case which occurred to Scheele three grains of solid arsenic were found in the contents, but hardly a trace in solution.[505] It would be wrong, however, to suppose that it is never found in the fluid contents. For, not to mention the observations of others, I have myself often detected it in the fluid part of the stomach in persons poisoned by arsenic.

The solution of oxide of arsenic in boiling water yields minute crystals on cooling, which, when their form is defined, are octaedres. In this state, on account of its whiteness and brilliancy, it exceedingly resembles pounded sugar. By spontaneous evaporation I have procured in twelve months fine octaedres nearly as large as peas. These do not become opaque by keeping, like the sublimed masses.

A difference of opinion prevails as to the action of the oxide on vegetable colours. This is a matter of no great consequence to the medical jurist; but it is right not to leave a disputed point without some notice. Guibourt says the transparent variety faintly reddens litmus, while the opaque variety faintly restores to blue litmus previously reddened.[506] My own experiments are at variance with these statements: I have always found that the solution of the powder, which is of the opaque variety, faintly reddens litmus, and does not alter reddened litmus.

The remaining chemical properties of the oxide, which it is necessary for the medical jurist to know, will be mentioned under what is now to be said of the principal test by which its presence may be ascertained. Under this head will be noticed, first the tests for the solid oxide, secondly, those for its solution, and lastly, the method of detecting it when mingled with vegetable or animal solids and fluids, such as the contents and tissues of the stomach.

_Of the Tests for Arsenic in the solid state._

The most characteristic and simple test for oxide of arsenic in its solid state, either pure or mixed or combined with inorganic substances, is its reduction to the metallic state.

Various methods have been at different times proposed for employing the test of reduction. In the ruder periods of analytic chemistry we find Hahnemann recommending a retort as the fittest instrument, and stating ten grains as the least quantity he could detect.[507] Afterwards Dr. Black substituted a small glass tube, coated with clay and heated in a choffer; and in this way he could discover a single grain.[508] In a paper published in the Edinburgh Medical and Surgical Journal, I showed how to detect a sixteenth of a grain; and afterwards even so minute a quantity as a hundreth part of a grain.[509]

The process is performed in a glass tube; which, when the quantity of the oxide is very small, should not exceed an eighth of an inch in diameter, and may be conveniently used of the form first recommended by Berzelius, and represented in Fig. 3.—The best material for reducing the oxide is recently ignited charcoal, if the quantity of suspected substance be very small. For when any of the ordinary alkaline fluxes is used, more than half of the arsenic is retained, probably in the form of an arseniuret of the alkaline metalloid. But when the quantity of matter for analysis is considerable, charcoal is inconvenient, as it is apt to be projected up the tube on the application of heat; and an alkaline flux is on that account preferable. For this purpose soda-flux,—made by grinding crystals of carbonate of soda with an eighth of their weight of charcoal, and then heating the mixture gradually to redness, so as to drive off all water,—is better than the more familiar black flux, which contains carbonate of potash; because the latter attracts much moisture when kept for some time.—If the quantity operated on is large it should be mixed with the flux before being introduced into the tube; if it is small, it may be dropped into the tube and covered with charcoal. The materials are to be introduced along a little triangular gutter of stiff paper, if the tube is large; but with a small tube it is preferable to use the little glass funnel represented in Fig. 2, to which a wire is previously fitted, for pushing the matter down when it adheres. The material should not be closely impacted. Heat is best applied with the spirit-lamp, first to the upper part of the material, with a small flame, and then to the bottom of the tube, the flame being previously enlarged. A little water, disengaged in the first instance, should be removed with a roll of filtering paper, before a sufficient heat is applied to sublime the metal. As soon as the dark crust begins to form, the tube should be held steady in the same part of the flame. With these precautions a well defined crust will be procured with facility.

The characters of the crust have been mentioned already under the head of fly-powder (p. 199). They are distinct even in crusts weighing only a 300th of a grain. A crust of this weight, a tenth of an inch broad and four times as long, may show characteristically all the physical characters of an arsenical sublimate a hundred times larger.

The fallacies to which the test has been supposed to be liable (excluding at present that part of it which consists in the oxidation of the metal, and which renders it quite unimpeachable), are the following.— Dr. Paris says he has known an instance where a person, “by no means deficient in chemical address, mistook for it a deposit of charcoal,”[510] and I have known the same mistake happen in the hands of one of my pupils, a beginner in the study of medico-legal chemistry. The outer surface of a charcoal crust may be mistaken for arsenic by a careless person; but with ordinary care it is quite impossible to err if the inner surface be examined, for that of charcoal is brown, powdery, and perfectly dull.—It has been suggested to me and has been stated in print,[511] that the preparations of antimony yield by reduction a sublimate resembling closely an arsenical crust. But in consequence of repeated trials I am certain that no preparation of antimony, reduced either by charcoal or the black flux with the fullest red heat of the blowpipe will yield any metallic sublimate; and the same facts were observed by the late Dr. Turner.—It has even been said by Mr. Donovan that the action of the flux on glass which contains lead causes a stain similar to an arsenical crust.[512] If it be meant by this observation, that the lead contained in the glass usually gives that part of the tube which contains the flux a glimmering appearance and impairs its transparency, the author is correct: but it is impossible that a sublimate can be so formed.—Dr. Mitchell of Philadelphia in an elaborate paper on the process of reduction seems to consider the crust undistinguishable from that formed in similar circumstances by cinnabar.[513] Crusts of cinnabar, however, do not present the peculiar character possessed by the internal surface of arsenic.—Zinc, it is said, may be sublimed in its metallic state; but the sublimation of zinc requires a full white heat; which in the process for arsenic cannot be generated.—Tellurium, cadmium, and potassium sublime at a lower heat; but these metals are so exceedingly rare, that it is quite unnecessary to particularize the characters of their sublimates.—Lastly, it is said that a crust may be produced from arsenic contained in the glass of the tube. A few years ago MM. Ozanam and Idt of Lyons detected arsenic in the remains of a body which had been seven years interred; but subsequently M. Idt imagined he had discovered that the glass used in the analysis contained arsenic, and yielded it by the process of reduction. He accordingly retracted his original opinion; and the person accused of administering the poison was acquitted. An extended inquiry, however, was in consequence undertaken by the Parisian Academy of Medicine at the request of the French government. And the result was that no arsenic could be detected in the glass tubes used by MM. Ozanam and Idt; and that although arsenic is sometimes used in glass-making, and a trace of it may be retained in some opaque glasses or enamels, it cannot be detected by any process of analysis in any of the clear glass met with in commerce,[514] the whole arsenic being volatilized during the manufacture of the glass.

It may therefore be safely laid down that the appearances exhibited by a well-formed arsenical crust, even in the minute quantity of a 300th part of a grain, are imitated by no substance in nature which can be sublimed by the process for the reduction of arsenic.

But should farther evidence be required as to the nature of the crust, this may be obtained by subjecting it to oxidation by heat.

The best method of doing so is to heat the ball containing the flux deprived of arsenic, to attach a bit of glass tube to its end, and to draw this gently off in the spirit-flame, taking care to prevent the flux being driven forward on the crust. This being done, the whole crust, or, if it is large, a portion of it, is to be chased up and down the tube with a small spirit-lamp flame till it is all converted into a white powder. In order to show the crystalline form of the powder distinctly, let the flame be reduced to the volume of a pea by drawing in the wick, and let the part of the tube containing the oxide be held half an inch or an inch above it. By repeated trials sparkling crystals will at length be formed, which are octaedres,—the crystalline form of arsenious acid. The triangular facettes of the octaedres may be sometimes seen with the naked eye, though the original crust was only a fiftieth of a grain or even less; and they may be always seen with a lens of four powers, the tube being held between the eye and a lighted candle or a ray of sunshine, either of which is preferable to diffuse daylight for making this observation.—For the success of the oxidation test it is indispensable that the inside of the tube be not soiled with an alkaline flux: because the alkali would unite with the oxide. It is also requisite not to heat the tube suddenly to redness before the oxide is sublimed; because then the oxide is apt to unite with the glass, forming a white, opaque enamel. The physical characters of the sublimed oxide are so delicate and precise, that they may be accurately distinguished, even when those of the metallic crust are obscure, owing to its minuteness. Sometimes too, the metal may be so scanty that it is oxidated at once in the act of subliming, and never presents the appearance of a metallic crust. Although the characters of the crystalline oxide in either of these cases are very precise and distinctive, it may be right to subject it to a farther test when the metal is not previously exhibited with its characteristic properties. For this purpose it is sufficient to cut away with a file the portion of the tube which contains the sublimate, to boil it in another tube with a few drops of distilled water till the sublimate disappear, and then to test the solution with one of the fluid tests to be presently described, the ammoniacal nitrate of silver.

After all that has been recently written as to the old and newer processes for detecting arsenic, I must nevertheless avow my conviction, that for solid arsenic no test is, for medico-legal purposes, at once so satisfactory, convenient, and delicate as the test of reduction, especially with the addition of the supplementary test of oxidation. That other methods are still more delicate may be readily granted. But where the suspected substance is in the solid form, what possible occasion can there be for a method more delicate than one which will detect a 300th part of a grain? A method ten times less so would meet every case in actual practice.—A variety of supplementary tests have been proposed. But they are all greatly inferior in facility, or conclusiveness, or both, to the process of oxidation, and ought therefore to be expelled from medico-legal practice,—not even excepting the alliaceous odour of metallic arsenic in the act of subliming, a character, the fallaciousness of which was long ago pointed out by myself as well as others, and to which a preposterous importance has been attached in some late inquiries. The reader will find in the last edition of this work an attempt to estimate the value of various tests supplementary to that of reduction. This disquisition is now omitted, as it seems no longer necessary.

_Of the Tests for Oxide of Arsenic in Solution._

Oxide of arsenic in a state of solution may be detected in one of four ways; by what are called the liquid tests; by precipitating it with one of these, and subliming metallic arsenic from the precipitate, which method is usually termed the reduction process; by Marsh’s method, which consists in disengaging it in the form of arseniuretted-hydrogen gas, and decomposing the gas by combustion; or by the method of Reinsch, in which metallic arsenic is deposited on the surface of copper, and then separated by heat for farther examination.

_Process by Liquid Reagents._—The first method is by the employment of several liquid tests, which cause in the solution peculiar precipitates. Many such tests have been proposed; but the most characteristic and precise are _hydrosulphuric acid_, _ammoniacal nitrate of silver_, and _ammoniacal sulphate of copper_. The indications of each of the three tests must concur, otherwise, in a medico-legal case, no one can be entitled to speak with certainty to the existence of arsenic. But when they do concur, the evidence is unimpeachable. When this method of analysis is followed, corresponding experiments ought always to be made with the water that is used for diluting or otherwise preparing the subject of examination, or with distilled water, if the article be already sufficiently aqueous. This precaution is necessary on account of the risk of accidental impregnation of the water or other reagents with arsenic.[515]

_Hydrosulphuric acid_ [sulphuretted-hydrogen] is obtained by decomposing proto-sulphuret of iron with diluted sulphuric acid in such an apparatus as is represented at Fig. 5. And the gas may be either applied directly to the suspected fluid, or condensed in distilled water, and thus kept in store for occasional use in the liquid shape. Before applying this test, the suspected fluid must be acidulated with acetic or hydrochloric acid; because an excess of alkali prevents the action. And if an acid be indicated by litmus in the fluid, neutralization, or slight supersaturation, with potash must be effected, before adding acetic or hydrochloric acid; for if the acidity should happen to be owing to an excess of sulphuric or nitric acid, the test is decomposed, and yellowish-white sulphur deposited.—These precautions being taken, hydrosulphuric acid occasions a sulphur-yellow or lemon-yellow precipitate. If the arsenical solution, however, be very weak, a yellow colour merely is struck, because the precipitate, which is sesqui-sulphuret of arsenic, is dissolved by the excess of the test; but it separates after ebullition, or a few hours’ exposure to the air. Co-existing animal and vegetable principles sometimes enable the fluid to retain a minute portion even after ebullition, so as to acquire a yellow milkiness; but they do not in any case prevent the test from producing the yellow colour. Acidulation with acetic or hydrochloric acid favours its subsidence in all cases; and according to Mr. Boutigny, alkaline sulphates, muriates and nitrates have the same effect.[516] Hydrosulphuric acid is so delicate as to act on the oxide in a hundred thousand parts of water. The proper colour of the precipitate is lemon or sulphur-yellow; which, when vegetable or animal matter is present, acquires a shade of white or brown.

It is not liable to any material fallacy. The salts of cadmium yield with it precipitates nearly of the same colour: but they are exceedingly rare; and the precipitate, unlike sulphuret of arsenic, is insoluble in ammonia.—The salts formed by selenic acid, if decomposed by another acid, also yield yellow precipitates; but these salts are extremely rare.—The salts of peroxide of tin give a dirty grayish-yellow precipitate; which however ammonia turns brown.—A lead solution acidulated with hydrochloric acid gives at first a yellow precipitate; but this becomes brownish-black when more gas is transmitted.[517] The contents of the human intestines sometimes yield a yellowish precipitate though no arsenic be present; and it is dissolved, like sulphuret of arsenic, by ammonia.[518] The tartrate of antimony and potash (tartar-emetic) does not form, as was once thought, any source of fallacy, the antimonial precipitate having always a tint of orange-red; besides it is not, like sulphuret of arsenic, soluble in carbonate of ammonia.—Other fallacies exist, unless the test be used with the precautions mentioned above. But these need not enumeration here.

_Ammoniacal nitrate of silver_ is prepared by precipitating the oxide of silver by means of ammonia, from a solution of nitrate of silver or lunar caustic in ten parts of water, and then redissolving the precipitate nearly, but not entirely, by adding gradually an excess of ammonia. When thus prepared, it causes, even in a very diluted solution of the oxide of arsenic, a lively lemon-yellow precipitate of arsenite of silver; which passes to dark brown under exposure to the light.—The action of this test is prevented by nitric, acetic, citric, or tartaric acid in excess, particularly by the first and last. It is also prevented by an excess of ammonia; and in very diluted solutions by the nitrate of ammonia. These facts will suggest the necessity of certain obvious precautions. Its action is obscured by the co-existence of various salts, which singly cause a white precipitate with nitrate of silver; for the yellow colour is then much lessened in intensity. The only one of these requiring special notice, because it occurs in very many of the fluids which are likely to be subjected to the researches of the medical jurist, is common sea-salt, the chloride of sodium. The best way of getting rid of the difficulty is to use in the first instance, not the ammoniacal nitrate, but the simple nitrate of silver, as long as any white precipitate falls down, to add a slight excess of that test, and then, after subsidence, to drop in ammonia. No arsenic is thrown down by the first steps of this process; but if any be present, it is subsequently thrown down in the form of the yellow arsenite of silver, on the addition of ammonia. This simple mode of getting rid of chloride of sodium was first proposed by Dr. Marcet.[519]—Ammoniacal nitrate of silver is of no use as a test for a moderately diluted solution of the oxide of arsenic, if vegetable or animal matter be present; either the colour of the precipitate is essentially altered, or no precipitate is formed at all.[520]

If the presence of arsenic is to be inferred only when the full lemon-yellow colour of the precipitate is developed, this test is not liable to any material fallacy. The presence of a phosphate, a serious obstacle according to an old way of using the silver test, is not a source of fallacy in the instance of the ammoniacal nitrate; for the yellow phosphate of silver is so soluble in the ammonia of the test, that it is not thrown down unless the phosphatic solution is very strong.—The silver test, which is extremely delicate, was proposed by Mr. Hume, a chemist of London; and in its improved state was suggested by the late Dr. Marcet. Various foreign authors have fallen into the error of supposing that nitrate of silver without an alkali precipitates oxide of arsenic: without an alkali, pure nitrate of silver gives no precipitate, or at most a bluish-white or yellowish-white haze when both solutions are strong.

_Ammoniacal sulphate of copper_ is prepared by the same process with the last test, sulphate of copper being substituted for nitrate of silver. It is a test of very great delicacy. It causes in solutions of the oxide of arsenic an apple-green or grass-green precipitate of the arsenite of copper. The particular tint is altered apparently by trifling circumstances; but after the precipitate has stood some hours it always assumes a tint intermediate between apple-green and grass-green. The operation of this test is prevented by hydrochloric, nitric, sulphuric, acetic, citric, and tartaric acids in excess; and also by an excess of ammonia. These difficulties are obviated by manifest precautions. It is also prevented, according to Hünefeld, by muriate, nitrate, and sulphate of ammonia;[521] and by almost all vegetable infusions and animal fluids, when the oxide of arsenic is not abundant: these difficulties cannot be obviated. Even when not prevented by such fluids, its operation is often obscured, the precipitate not possessing its characteristic colour.

Ammoniacal sulphate of copper is more open to fallacies than the silver test. Of these the most important is that in some organic fluids it strikes a green precipitate, like the arsenite of copper, though arsenic be not present.[522] The solution of bichromate of potass is turned green but not precipitated by it.

On reviewing all that has now been stated regarding the liquid tests for arsenic, it will appear that there is no single test on which absolute reliance can be placed; but that the fallacies to which they are liable are generally remote, and each of them applicable to one test only. Hence if each of the three reagents, applied with due care, gives a precipitate of the characteristic tint, the proof of the presence of arsenic is decisive.

This particular view of the indications of the liquid tests, however obvious it may seem, has been often overlooked by the numerous chemists and medical jurists who have written for and against them. The antagonists of the tests have been content with proving how so many fallacies lie in the way of each, that no dependence can be put in any one of them: They have not considered that the fallacies attached to one are obviated by the conjunct indications of the others.

I am of opinion therefore that the analysis for arsenic by liquid reagents has been unjustly neglected in the present day. It is an exceedingly convenient method, and one of extreme delicacy, because by using small tubes it is easy to operate with precision on very minute portions of a suspected fluid. It is also perfectly conclusive, so far as chemical knowledge now goes. On a remarkable trial a few years ago in this country, a distinguished chemist, who, as witness for the prisoner, was made by counsel to throw discredit on the liquid tests individually, nevertheless admitted to the counsel for the prosecution, that no other substance in nature but arsenic could produce the same effects as it with the whole three tests in succession.

_Reduction process._—The process by reduction of arsenic to the metallic state, as applied to the poison in a state of solution, consists in separating the whole arsenic by a liquid test in such a state as to admit of the precipitated compound being subjected to the process of reduction and sublimation. The best method of the kind is a modification of one described by me in 1824.[523] This consists in throwing down the whole arsenic in the form of sulphuret by means of hydrosulphuric acid, converting the sulphuret by the process of reduction to the metallic state, and oxidating the metal thus procured. The hydrosulphuric acid is preferred to other liquid reagents, because the precipitate it forms, while possessing a very characteristic colour, is also more bulky than those caused by the other tests, and is therefore more easily collected,—and because its action is not liable to be prevented or obscured by so many disturbing causes. The steps of the process are the following:—

The fluid to be examined must be acidulated with acetic or hydrochloric acid. If the fluid be neutral or alkaline, the acid may be added at once. If on the other hand the fluid redden litmus, and the acid be either unknown or a mineral acid, potash must first be added in a slight excess, and then the alkali must be supersaturated with acetic or hydrochloric acid. The reasons for these precautions are stated under hydrosulphuric acid as a liquid reagent. The fluid being thus prepared, it is subjected to a stream of hydrosulphuric acid gas for ten or fifteen minutes. The first portions of the gas turn the arsenical solution to a bright lemon-yellow colour, and the subsequent portions throw down a yellow flocculent sulphuret of arsenic. If the proportion of oxide in solution is small, a yellowness or yellow milkiness only is caused, owing to the sulphuret being soluble in an excess of hydrosulphuric acid. But on expelling that excess by boiling, a distinct precipitate and colourless fluid are produced. The precipitate is then to be collected thus. The precipitate is allowed to subside, and the supernatant fluid being withdrawn, the remainder is poured into a filter. When all the fluid has passed through, the portions of precipitate on the upper part of the filter are washed down to the bottom. The filter is then gently compressed between folds of bibulous paper, and the sulphuret removed with the point of a knife before it dries, and dried in little masses on a watch-glass by the side of a chamber-fire, or still better in a vapour-bath. In this way it is very easy to collect a twenty-fifth part of a grain of the sulphuret. Another method which takes more time, but will enable the least skilful person to collect extremely small quantities, is to allow the sulphuret to subside in the original fluid in which it is formed, to pour off the supernatant liquid, and pour the remainder into a small glass tube, Fig. 7. After the precipitate has thoroughly subsided, the supernatant liquid is to be withdrawn, and its place filled up with boiling water. The operation of alternate subsidence and affusion being repeated a sufficient number of times, the last portions of water should be gently driven off by heat, and wiped off the inside of the tube as the drops condense on it. Finally, the bottom of the tube, with the precipitate attached, is to be cut away with the file, and broken into small fragments with the view of preserving the whole sulphuret for the process of reduction. The sulphuret having been collected in either of these ways, it is now to be dropt into the tube, Fig. 3, and covered by means of the funnel, Fig. 4, with soda-flux. The process in other particulars is the same with that for reducing solid oxide of arsenic.

This method of investigation gives extremely precise results, because it presents the poison successively in three distinct forms, as sulphuret, metal, and crystallized oxide, all of which possess very prominent and characteristic external properties. It is also a method which is capable of detecting very minute quantities of oxide of arsenic. And it has the advantage over the process by liquid reagents of being applicable to organic fluids. It was accordingly followed in most medico-legal researches until the recent discovery of the methods of Marsh and Reinsch.

In order to render it quite satisfactory, it is necessary to go through the steps of the analysis at the same time with distilled water, lest any of the reagents used should accidentally contain arsenic.

_Process of Marsh._—This method consists in disengaging arsenic from the solution in the form of arseniuretted-hydrogen gas, burning the gas in such way as to obtain either metallic arsenic or oxide of arsenic, and subjecting the product to various tests.

I have called this beautiful method of analysis Marsh’s process, because it appears to me that injustice has been done its discoverer both by himself and those who have since investigated the subject, when they denominated it merely a test. Medico-legal analysis stood in no need of a new test for arsenic, but very much of an easy and infallible method of detaching minute quantities of it in a state of purity from simple and compound fluids, so as to admit of its being accurately examined. It is this important object, and not strictly speaking a new test, that has been attained through means of the discovery of Mr. Marsh.

His discovery consists in the observation, that, if hydrogen gas be disengaged by the action of sulphuric acid or zinc in a fluid containing arsenic dissolved in any form, arseniuretted-hydrogen gas is disengaged along with the hydrogen; and that if the two gases be burnt together in a fine flame, metallic arsenic is deposited on a white porcelain surface held in the flame, and oxide of arsenic if the porcelain be held immediately above it.[524] The production of a brilliant mirror-like crust in the former case, and of a white powdery one in the other, constituted Marsh’s test as originally proposed; and it was at first conceived to furnish unimpeachable evidence of the detection of arsenic. Afterwards many inquirers, and among them the discoverer himself, became satisfied that certain fallacies stand in the way of a conclusion based on such simple premises. Various supplementary tests were in consequence proposed. And at length it seems to be agreed, that the proper mode of applying Marsh’s discovery is to employ a succession of tests, of which that originally pointed out by him is the first. A vast variety of methods of analysis founded on this principle have been proposed by British and continental chemists. It would be tedious and unprofitable to discuss or even to state them here. The reader will probably be satisfied with a reference to the most important of them[525] and with a description of that process, which appears to me, from repeated trials in medico-legal practice, to be at once most convenient, delicate, and conclusive.

Let the liquid to be examined be introduced into a Döbereiner’s lamp [Fig. 10], or an apparatus constructed with a bottle and a funnel upon the same principle [Fig. 11]; and dilute the liquid with distilled water, until the lower cavity of the apparatus be nearly full, leaving space however for the tube of the funnel, a fragment of zinc, and some sulphuric acid. Put in a cylinder or rod of zinc, _a_; and then add sulphuric acid until a moderate effervescence ensue. Close the junction of the two vessels, and then, allowing a little gas to escape at _c_, shut the stop-cock, and let the gas fill the vessel A, by driving the liquid up into B. Having meanwhile fitted by a cork to the exit-tube, _c_, the glass tube, _d e_, which is loosely stuffed with raw cotton at the end _d g_, and has a bent plate of copper or tinned iron hung over it at _f_,—open the stop-cock, allow a little gas to escape so as to expel the air in _d e_, and then kindle the gas at _e_, which must be contracted to a capillary opening. Keep the flame low, and hold the surface of a white porcelain vessel across the middle of it for a few seconds. If no stain be produced on the porcelain, there is no arsenic in the fluid. If a stain be formed, regulate the escape of gas by the stop-cock so that the fluid may not rise above the middle of the lower vessel of the apparatus, and apply the heat of a spirit-lamp flame to the tube _d e_ on the left hand of the plate _f_, the purpose of which is to prevent the heat being communicated beyond that point. By and by, if there be arsenic in the fluid, a brilliant metallic ring will appear beyond _f_, owing to decomposition of arseniuretted-hydrogen gas. As soon as the crust is thick enough to present its properties characteristically, withdraw the spirit-lamp; place the tube _e h_ so that the flame at _e_ shall be completely within the ball, _i_; let the tube incline very slightly in the direction from _k_ to _l_; and allow a stream of cold water to trickle down upon the portion _k l_, which should be wrapped in a single layer of calico. Oxide of arsenic will gradually condense, partly in white powder or minute sparkling crystals in the ball and between _i_ and _k_, and partly between _k_ and _l_ in the form of a solution, which collects at the bend _l_. The solution which may be increased in quantity by boiling a little distilled water upon the powder in the ball and bend _i k_, is then to be subjected in small portions to the three liquid reagents, ammoniacal nitrate of silver, ammoniacal sulphate of copper, and hydrosulphuric acid.

Some experience is required to apply this process successfully. But with due attention it furnishes conclusive evidence with great delicacy and precision. A solution containing only a millionth part of oxide of arsenic will part with it readily in the form of arseniuretted-hydrogen; and the slightest trace of that gas in the hydrogen is indicated by the method recommended above.—The process is compounded of Mr. Marsh’s original discovery, the supplementary test of reduction in the exit-tube recommended by Berzelius,[526] and the formation and examination of the oxide proposed by myself.[527]—With certain precautions and modes of manipulating, it is applicable to the most complex organic fluids, as well as to simple solutions.

The discovery of Mr. Marsh had not been long made before the test in its original simple form was found liable to divers important fallacies. It appeared, for example, that antimony yields very nearly the same appearance of metallic crust and of white powder, according to the position of the porcelain in the flame; that some porcelains glazed with oxide of zinc are similarly stained by a flame of simple hydrogen gas; that a great variety of metallic salts, if spirted up into the exit-tube, undergo reduction in the flame, and cause imitative stains on the porcelain; that iron-salts seems to form stains from the same chemical action as what occurs in the case of arsenic; and that certain compounds of phosphorous acid with ammonia and animal matter, or even mere animal matters themselves, will in some circumstances produce a stain more or less similar to that which is occasioned by arsenic.

There is no doubt, that the resemblance of most of these spurious stains to an arsenical crust has been much exaggerated. But still the similarity is sufficient to satisfy every impartial judge, that the mere production of a brilliant metallic, or white powdery stain, or both, upon porcelain, is not conclusive evidence of the detection of arsenic in medico-legal inquiries. It is strong presumptive evidence; and the non-production of such stains is absolute proof that arsenic is not present. But in order to obtain irrefragable proof of its presence, the substance which forms the crusts and stains must be subjected to farther examination. And such is the object of the supplementary methods in the process detailed above. That process is perfectly free of fallacy. No substance yet known but arsenic can yield the succession of phenomena which have been detailed. My opinion farther is, that the process may be safely simplified by withdrawing Berzelius’s supplementary test of reduction in the exit-tube, and retaining the test of oxidation only, with the examination of the oxide by liquid reagents. I have retained the former in deference to the opinion expressed by a committee appointed by the French Institute, who examined the whole subject with unwearied zeal, but who, it may be observed, seem never to have had in their view the check-test of oxidation; which, with the consecutive tests, is superior in conclusiveness to the check of reduction only.

_Reinsch’s process_, like the former, has been inconveniently called a new test for arsenic. The fact discovered by Dr. Reinsch is valueless as supplying a mere test; but it forms the ground-work of the best process of all yet proposed for the detection of arsenic in solution. The discovery is, that arsenic in solution is deposited in the metallic state upon copper-leaf, when the fluid is acidulated with hydrochloric acid, and heated till it boils gently or is about to do so; and that by heating the copper gently in a glass tube the arsenic is sublimed from it in the form of oxide or metal according to the quantity present.[528]

This method is so simple and easy as scarcely to require any detailed explanation. The fluid should contain about a tenth of its volume of hydrochloric acid. It must be heated near ebullition before the copper is introduced, otherwise the copper becomes tarnished, though arsenic be not present. Copper-leaf, or copper-plate worn thin by the action of diluted nitric acid, or fine copper gauze, is the best form for use. In the feeblest solutions ten or fifteen minutes elapse before arsenic is visibly deposited, and forty minutes should be allowed for strong deposition; but in strong solutions, the action takes place in a few seconds. The result is a thin, brittle brilliant, steel like coating of metallic arsenic. As soon as the deposit is formed, the copper is to be removed, dried with a gentle heat, cut into small shreds, and heated with a spirit-lamp in the smallest glass tube that will conveniently contain the whole; upon which a metallic ring of arsenic is sometimes sublimed, but more generally a ring of small sparkling crystals. These are first to be examined as to their form with a common pocket lens; and then dissolved in boiling distilled water, after shaking out the copper, so that a solution may be obtained and subjected to the liquid reagents, especially the ammoniacal nitrate of silver as being the readiest and most delicate. In all medico-legal inquiries it is necessary to perform a preliminary experiment with distilled water and the hydrochloric acid used, lest the acid contain arsenic.

The process here described is one which I have followed with great facility, certainty and despatch in several medico-legal cases.[529] It is extremely delicate; for it will detect at least a 250,000th part of arsenic in solution; and it removes from the fluid every particle of arsenic, because none can be afterwards discovered by means even of Marsh’s method. It is not subject to any fallacy. The mere formation of a brilliant coating on the copper is not evidence of arsenic being present; for as Reinsch himself ascertained, solutions of bismuth, tin, zinc, and antimony produce a coating more or less similar to an arsenical one. But the farther steps of the process entirely put aside all these sources of error. The non-formation of a metallic tarnish of copper, however, is perhaps not absolute proof of the absence of arsenic. For, according to a late statement by Drs. Fresenius and Von Babo,[530] “all nitrates, and various salts of mercury and other metals, render the separation of arsenic by copper difficult or even impossible.” The authors of this objection, although the paper is otherwise elaborate and detailed, have not given any particulars in illustration of so important a criticism.

_Of the Tests for Oxide of Arsenic in Organic Mixtures._

The present is by far the most important of the conditions under which it may be necessary to search for arsenic in medico-legal cases; for in nine cases out of ten the subject of analysis is either some article of food or drink, the contents or tissues of the stomach, or the textures of other organs of the body into which the poison has been carried by absorption.

Accordingly much attention has been paid to this subject for some years past, and many valuable methods of analysis have been suggested, more especially since the recent discovery that arsenic, like many other poisons, undergo absorption, and is diffused by the circulation throughout the body generally. It was proved by me in 1824,[531] that the tests for arsenic, at that time in general use, are so fallacious when applied to complex organic mixtures as to be unfit for medico-legal investigations except merely as trial-tests; and a process was proposed, which has since undergone various modifications from others as well as myself. This process, in the form in which it was adopted in the last edition of the present work, is still applicable to a great proportion of cases; and indeed a recent modification of it has been thought by Drs. Fresenius and von Babo to be superior even yet to every other in all circumstances.[532] But two new methods are at present generally preferred, and probably not without reason. At least they have been much employed and with great success in numerous medico-legal researches, where the quantity of arsenic was to all appearance extremely small, and the subject of examination most complex and troublesome to bring within the sphere of analysis. And in particular they have been successfully employed to detect arsenic in those organs of the human body into which it can obtain admission only through the medium of absorption.

In the following statement I shall describe four processes only, that of Reinsch, by which the arsenic is first separated as a crust on copper,—that of Marsh, who first detaches it in the form of arseniuretted-hydrogen,—my own method, which consists in obtaining in the first instance a sulphuret of arsenic,—and that of Drs. Fresenius and von Babo, which has the same foundation.