Hydriodate of Potass causes in solutions of corrosive sublimate a beautiful pale scarlet precipitate, which rapidly deepens in tint. The precipitate is the biniodide of mercury. This is a test of great delicacy when skilfully used, as it acts where the salt forms only a 7000th of the solution (Devergie). Care must be taken, however, not to add too much of the test, because the precipitate is soluble in an excess of the hydriodate, or too little, because the precipitate is also soluble in a considerable excess of corrosive sublimate.
The action of hydriodate of potass is not liable to any important ambiguity: no other iodide resembles in colour the biniodide of mercury. It is not a certain test, however, when other salts exist in solution along with corrosive sublimate. Chloride of sodium, nitrate of potass, and probably also other neutral salts possess the power of dissolving the precipitate. Sulphuric and nitric acids, even considerably diluted, oxidate and dissolve the mercury, and disengage iodine, which colours the fluid reddish-brown. When corrosive sublimate is dissolved in coloured vegetable infusions or animal fluids, the hydriodate of potass cannot be relied on, the colour of the precipitate being altered, as in infusion of galls, or the action of the test being suspended altogether, as by milk.
Protochloride of Tin causes first a white precipitate, which, when more of the test is added, gives place to a grayish-black one. In very diluted solutions the colour struck is grayish or grayish-black from the beginning. In such solutions Devergie has found it useful to acidulate with hydrochloric acid before adding the test. The chemical action here is peculiar. The white powder thrown down at first is protochloride of mercury; a part of the chlorine of the bichloride of mercury having been abstracted by the protochloride of tin, which becomes in consequence the bichloride. On more of the test being added these changes are repeated, the chlorine is removed from the protochloride of mercury, and metallic mercury falls down. This test is one of extreme delicacy, affecting solutions which contain only an 80,000th of salt. It is prepared by acting on tin powder or tinfoil with strong hydrochloric acid aided by a gentle heat. The solution must be kept carefully excluded from the air; otherwise bichloride of tin is formed, which does not act at all on the solution of corrosive sublimate.
The protochloride of tin is not liable to any fallacy. Neither is it liable to be suspended in its action by the co-existence of other saline substances. It causes precipitates with almost all animal and most vegetable fluids. But when corrosive sublimate is present, even in very small proportion, the precipitate is always darker than when no mercurial salt exists in solution, and frequently has its proper grayish-black tint. This property, as will presently be seen, is the foundation of a process for the detection of mercury in all states of admixture with organic matters.
Nitrate of Silver causes a heavy white precipitate, the chloride of silver, which darkens under exposure to light. This is a test for the chlorine of the corrosive sublimate, but not for the mercury, and is a necessary addition to the three former tests in order to determine how the mercury is kept in solution. It acts with very great delicacy.
It is of no use, however, when chlorine or hydrochloric acid is present either free or combined with other bases. It is not of use, therefore, in animal fluids and vegetable infusions, because very many of them, besides organic principles which form white precipitates with this test, contain a sensible proportion of hydrochlorate of soda.
Although the preceding liquid reagents when employed conjunctly are amply sufficient for determining the presence of corrosive sublimate in a fluid, many other tests hardly less characteristic and delicate have been used by medical jurists. These will now be shortly mentioned.
1. Lime-Water throws down the binoxide of mercury in the form of a heavy yellow powder. The precipitate first thrown down is lemon-yellow, an additional quantity of the test gives it a reddish-yellow tint, and a still larger quantity restores the lemon-yellow. This test is characteristic, but not so delicate as those already mentioned.—2. Caustic Potass has precisely the same effect as lime-water, except that the tint of the precipitate is always yellow—3. Caustic Ammonia causes a fine, white, flocculent precipitate of intricate composition, commonly called precipitate. It is a very delicate test; but ammonia likewise causes a white precipitate in other metallic solutions.—4. Carbonate of Potass causes a brisk-red precipitate, by virtue of a double decomposition, the precipitate being carbonate of mercury.—5. The Ferro-cyanate of Potass causes at first a white precipitate, the ferro-cyanide of mercury. The precipitate becomes slowly yellowish, and at length pale-blue, owing, it is believed, to the admixture of a small quantity of iron with the corrosive sublimate.—6. A polished plate of Copper immersed in a solution of corrosive sublimate becomes in a few seconds tarnished and brownish; and in the course of half an hour a grayish-white powder is formed on its surface. This powder, according to Orfila,[[837]] is a mixture of calomel, mercury, and a copper amalgam. If it is wiped off, and the plate then rubbed briskly where tarnished, it assumes a white argentine appearance.—7. A little Mercury put into a solution of corrosive sublimate is instantly tarnished on the surface; the solution in a few seconds becomes turbid, a heavy grayish precipitate is formed, and in no long time with the aid of agitation the whole corrosive sublimate is removed from the solution. The powdery precipitate is a mixture of finely divided mercury and calomel; the former being derived from the surface of the mercury, and the latter produced by the corrosive sublimate uniting with a larger proportion of the metal to form the protochloride.—8. A solution of Albumen causes a white precipitate, which is soluble in a considerable excess of the reagent. The nature of this precipitate will be discussed presently.—A slip of Gold aided by galvanism, becomes silver-white in the solution, in consequence of the formation of an amalgam. When the solution is concentrated, it may be thus tested by simply putting a few drops on a bit of gold, and touching the gold through the solution with an iron point, as recommended by Mr. Sylvester and Dr. Paris.[[838]] When the solution is very weak, a different method is necessary, and a process for the purpose has been proposed by M. Devergie, which appears so delicate, accurate, and at the same time simple, a mode of detecting traces of mercury in very weak solutions, as to deserve detailed notice. A thin plate of gold, and another of tin, a few lines broad, and two or three inches long, being closely applied to one another by silk threads at the ends, and then twisted spirally, this galvanic pile is left for twenty-four or thirty-six hours in the solution previously acidulated with muriatic acid; upon which the gold is found whitened, and mercury may be obtained in globules by heating the gold in a tube. Distinct indications may be obtained by this method, where the corrosive sublimate forms but an 80,000th of the water.[[839]] For facility of application, an important condition is, that the quantity of fluid should not exceed three or four ounces, because in a larger quantity the pile of the size stated above cannot remove the whole mercury. Somewhat similar to this is the galvanic method of Mr. Davy of Dublin. He proposes to place the suspected solution in a platinum crucible with hydrochloric acid, diluted with its own weight of water, to excite galvanic action by immersing in the fluid a plate of zinc, and to sublime and collect the reduced mercury, by washing the crucible, heating it over a spirit-lamp, and condensing the mercurial vapours on a plate of glass placed over the mouth of the crucible.[[840]]
Of the Tests for Corrosive Sublimate when mixed with Organic Fluids and Solids.
The process for detecting corrosive sublimate in mixtures of organic fluids and solids, such as the contents of the stomach, is now to be described. But some remarks are previously required on the chemical relations subsisting between this poison and various principles of the vegetable and animal kingdoms.