Treatise on Poisons by Sir Robert Christison

is to be withdrawn, and its place filled up with boiling water.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. _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