Of the Tests for Corrosive Sublimate in the solid state.
Corrosive sublimate in the solid state is distinguished from other substances by the action of the heat, and the effects of solution of caustic potass. Subjected to heat alone it sublimes in white acrid fumes; and if the experiment is made in a little tube, it condenses again unaltered in a crystalline cake. Treated with solution of caustic potass, it becomes yellow, the binoxide being disengaged, and hydrochloric acid uniting with the potass, as may be proved by nitrate of silver, after filtration and neutralization with nitric acid. The yellow colour of the binoxide which is separated in this process distinguishes corrosive sublimate from calomel, which is also decomposed by the potass solution, but yields a black protoxide. Caustic soda has the same effect. Not so caustic ammonia: Ammonia blackens calomel, but does not change the colour of corrosive sublimate, as it forms with it a white triple salt, commonly called white precipitate.
The process here described is the best and simplest method of determining chemically the nature of corrosive sublimate in its solid state. But two other tests may also be mentioned, as they have been a good deal used. A very good test is the process of reduction with potass, by which globules of mercury are sublimed, and a chloride of potassium left in the flux, as may be proved by the action of nitrate of silver on the solution of the flux previously neutralized with nitric acid. This test alone will not distinguish corrosive sublimate from calomel: The solubility of the former must be taken into account.—Another satisfactory test is the solution of protochloride of tin. Corrosive sublimate, when left for some time in this solution, first becomes grayish-black, and ere long its place is supplied by globules of mercury,—the chlorine being entirely abstracted by the protochloride of tin, which consequently passes to the state of a bichloride. Calomel is similarly affected.
Of the Tests for Corrosive Sublimate in a state of Solution.
Two processes may be mentioned for the detection of corrosive sublimate in mineral solutions,—a process by reduction, and a process by liquid tests.
Reduction process.—In order to procure mercury in its characteristic metallic state from a solution of corrosive sublimate, the following plan of procedure will be found the most delicate and convenient. Add to the solution, previously acidulated with hydrochloric acid if very weak, a little of the protochloride of tin, which will be seen presently to be a liquid reagent of great delicacy. If the solution is not darkened there is not present an appreciable quantity of mercury. If mercury is present a bluish-gray or grayish-black precipitate falls down, owing to the chemical action already particularized. After ebullition, this precipitate is to be allowed to subside, first in a tall glass vessel suited to the quantity of the solution, and afterwards in the small glass tube, Fig. 7, the superincumbent fluid being previously decanted off as far as possible. After it has subsided in the tube, the remaining fluid is withdrawn with the pipette, Fig. 8; water is poured over it; and this is withdrawn again after the precipitate has subsided a third time. The bottom of the tube is then cut off with a file, and the moisture which remains is driven off with a gentle heat. When this is accomplished, the powder, which is nothing else than metallic mercury, sometimes runs into globules. Should it not do so, the bit of tube is to be broken in pieces and heated in the tube, Fig. 1, when a brilliant ring of fine globules will be formed. If the globules are too minute to be visible to the naked eye, the tube is to be cut off with the file close to the ring; and the globules may then be easily made to coalesce into one or more of visible magnitude by scraping the inside of the tube with the point of a penknife.
This process is not recommended as preferable to the plan by liquid reagents which is next to be mentioned, and which is both more easily put in practice, and at the same time quite as satisfactory. It is related chiefly because it forms the ground-work of a process for detecting mercury in mixed animal or vegetable fluids. It will be remarked that the process does not prove with what acid the mercury was combined in the solution. But this is a defect of little consequence; for the only other soluble salts of mercury ever met with in the arts, namely, the nitrate, acetate, and cyanide, are too rare to be the source of any material fallacy; and are besides all equally poisonous with corrosive sublimate.
Process by Liquid Tests.—The process by liquid reagents consists in the application of several tests to separate portions of the solution. The tests which appear to me the most satisfactory are hydrosulphuric acid gas, hydriodate of potass, protochloride of tin, and nitrate of silver.
1. Hydrosulphuric acid gas transmitted in a stream through a solution of corrosive sublimate causes a dark, brownish-black precipitate, the bisulphuret of mercury. When the solution is not very diluted, the gas forms a whitish or yellowish precipitate before the blackening commences,—an effect which, according to Pfaff, distinguishes the salts of the peroxide of mercury from all other metals that are thrown down black from their solutions by sulphuretted-hydrogen.[[835]] The cause of this is that the particles of sulphuret first formed acquire a thin covering of corrosive sublimate by that property which chemists of late have termed superficial attraction. Hydrosulphuric acid is a very delicate test of the presence of mercury. It will detect corrosive sublimate, where its proportion is only a 35000th of the solution.[[836]]
This test is not alone sufficient, unless reliance be placed on Pfaff’s criterion, which is rather a trivial one; for hydrosulphuric acid occasions a black precipitate in other metallic solutions, for example, in solutions of lead, copper, bismuth and silver. In mixed organic fluids its action is not liable to be prevented; but the precipitate formed is often kept intimately suspended, as in the instance of milk. It may be conveniently used in the form of hydrosulphate of ammonia. This test produces a dark-brown precipitate, which is said to pass slowly to a bright cinnabar red; but I have not been able to observe any transformation of the kind.