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.