Treatise on Poisons / In relation to medical jurisprudence, physiology, and the practice of physic

by Sir Robert Christison

Process for Organic Mixtures.—Various processes have been proposed for detecting corrosive sublimate in organic mixtures. The first I shall mention is one proposed by myself in former editions of this work. It is a double one; of which sometimes the first part, sometimes the second, sometimes both may be required. The first removes the corrosive sublimate undecomposed from the mixture, which may be accomplished when its proportion is considerable; the second, when the proportion of corrosive sublimate is too small to admit of being so removed, separates from the mixture metallic mercury; and the analyst will know which of the two to employ by using the protochloride of tin as a trial-test in the following manner.

A fluid mixture being in the first instance made, if necessary, by dividing and bruising all soft solids into very small fragments, and boiling the mass in distilled water, a small portion is to be filtered for the trial. If the protochloride of tin causes a pretty deep ash-gray or grayish-black colour, the first process may prove successful; if the shade acquired is not deep, that process may be neglected, and the second put in practice at once.

First branch of the Process.—In order to remove the corrosive sublimate undecomposed, the mixture, without filtration, is to be agitated for a few minutes with about a fourth part of its volume of sulphuric ether; which possesses the property of abstracting the salt from its aqueous solution. On remaining at rest for half a minute or a little more, the etherial solution rises to the surface, and may then be removed by suction with the pipette (Fig. 8). It is next to be filtered if requisite, evaporated to dryness, and the residue treated with boiling water; upon which a solution is procured that will present the properties formerly mentioned as belonging to corrosive sublimate in its dissolved state. This branch of the process is derived from one of Orfila’s methods.

Second branch of the Process.—If the preceding method should fail, or shall have been judged inapplicable, as will very generally be the case, the mixture is to be treated in the following manner. In the first place, all particles of seeds, leaves, and other fibrous matter of a vegetable nature, are to be removed as carefully as possible. This being done, the mixture, without undergoing filtration, is to be treated with protochloride of tin as long as any precipitate or coagulum is formed. If there were solid animal matters in the mixture, besides being cut and carefully bruised as directed above, they should also be brought thoroughly in contact with the salt of tin by trituration. The mixture, even if it contains but a very minute proportion of mercury, will acquire a slate-gray tint, and become easily separable into a liquid and coagulum. The coagulum is to be collected, washed and drained on a filter; from which it is then to be removed without being dried; and care should be taken not to tear away with it any fibres of the paper, as these would obstruct the succeeding operations. The mercury exists in it in the metallic state for reasons formerly mentioned.

The precipitate is next to be boiled in a moderately strong solution of caustic potass contained in a glass flask, or still better in a smooth porcelain vessel glazed with porcelain; and the ebullition is to be continued till all the lumps disappear. The animal and vegetable matter, and oxide of tin united with them, will thus be dissolved; and on the solution being allowed to remain at rest, a heavy grayish-black powder will begin to fall down in a few seconds. This is chiefly metallic mercury, of which, indeed, globules may sometimes be discerned with the naked eye or with a small magnifier.

In order to separate it, leave the solution at rest under a temperature a little short of ebullition for fifteen or twenty minutes, or longer, if necessary. Fill up the vessel gently with hot water without disturbing the precipitate, so that a fatty matter, which rises to the surface in the case of most animal mixtures, may be skimmed off first with a spoon, and afterwards with filtering paper. Then withdraw the whole supernatant fluid, which is easily done on account of the great density of the black powder. Transfer the powder into a small glass tube, and wash it by the process of affusion and subsidence till the washings do not taste alkaline. Any fibrous matter which may have escaped notice at the commencement of the process, and any lumpy matter which may have escaped solution by the potass, should now be picked out. The black powder is the only part which should be preserved. If the quantity of powder is very minute, an interval of twelve hours should be allowed for each subsidence, and the tube represented in Fig. 7 should be used.

Lastly, the powder is to be removed, heated, and sublimed, as in the last stage of the process described in page [293], for detecting corrosive sublimate in a pure solution.

The second branch of this process is very delicate. I have detected by it a quarter of a grain of corrosive sublimate mixed with two ounces of beef, or with five ounces of new milk, or porter, or tea made with a liberal allowance of cream and sugar. I have also detected a tenth part of a grain in four ounces of the last mixture, that is in 19,200 times its weight.

It may be applied successfully and without difficulty to a very large majority of medico-legal cases. The only difficulty in the way of applying it to all organic mixtures whatever arises from the occasional presence of some vegetable matters, such as seeds, leaves, ligneous fibre and the like, which are insoluble in caustic potass, and which may therefore be left behind with the mercurial precipitate, and obstruct the subsequent sublimation of the metal. This difficulty may be sometimes got rid of, as recommended above, by picking such matters out of the mixture before the protochloride of tin is added. No mercury is lost by so doing, for none of it is united with these vegetable matters: corrosive sublimate does not form any chemical compound with them as it does with other vegetable matters soluble in caustic potass, and with the soft animal solids. When the particles are too small to admit of being thus removed, or cannot be afterwards removed during the process of washing the black powder, which is left after the action of potass—the analyst must be content with the increased facility of sublimation derived from the abstraction of other vegetable and animal admixtures, and take care to use a tube of greater length and with a larger ball than usual. If the sublimate is too much obscured by empyreumatized matter to exhibit distinctly its metallic, globular appearance, the portion of the tube is to be broken off, and scraped, washed, and boiled with a little rectified spirit in a tube. If the globules do not then become visible, a second sublimation will render them distinct. This supplemental operation, however, will be very seldom required; and the process given above will be found to apply to a great majority of instances.

Various objections brought against this process by reviewers and others were noticed in previous editions of this work. The result of the investigation is, that, though not by any means a perfect process, it is one of the most convenient and certain, and least fallacious of all yet proposed. The first step for separating corrosive sublimate by ether in the undecomposed state,—which is borrowed from a suggestion of Professor Orfila, will seldom succeed; for the poison is seldom present in sufficient quantity.