Water dissolves it. Its solubility is a point of some medico-legal importance; for a doubt may arise whether the quantity of a solution that has been swallowed contained a sufficient dose to cause severe symptoms or death. Different statements have gone forth on this head. Klaproth found, that a thousand parts of temperate water take up only two parts and a half,—and that a thousand parts of boiling water take up 77·75 parts or a thirteenth, and retain on cooling 30 parts or a thirty-third of their weight.[[500]] Guibourt found a difference between the transparent and opaque varieties; for a thousand parts of temperate water dissolved in thirty-six hours 9·6 of the transparent, 12·5 of the opaque variety; and the same quantity of boiling water dissolved of the transparent variety 97 parts, retaining 18 when cooled, but of the opaque variety took up 115 and retained on cooling 29.[[501]] More lately Mr. Alfred Taylor observed that temperate water, simply poured on the opaque oxide and left for seventy-two hours, contained one grain in a thousand, but if often agitated, 8·5 grains; that boiling water, occasionally agitated for the same period, contained 9·27 or 9·54 grains; that water, boiling gently for an hour dissolved 31·5, and on cooling and resting for three days retained 17; that with violent ebullition for an hour, it took up 46·3, and retained 24·7 grains on cooling and resting for three days; that a saturated boiling solution after six months contained 24 or 26 grains; and that a saturated boiling solution of the transparent oxide contained 46 or 47·5 grains, and on cooling and resting for two days retained 18·7 or 13·4 grains.[[502]] It is impossible to account for these discrepancies; for all the experimentalists conducted their investigations with care, and with a view to the medico-legal question stated above. Hahnemann farther remarked, that at the temperature of the blood a thousand parts of water dissolve ten parts with the aid of ten minutes’ agitation;[[503]] and Navier, that boiling water kept for an hour on it, and decanted off in the way an infusion is usually made, dissolves 12·5 grains in every thousand.[[504]]
Its solubility is impaired by the presence of organic principles. When mixed with mucus or milk it dissolves, according to Hahnemann, with great difficulty; and I have found that a cup of tea, left beside the fire at a temperature of 200° for half an hour upon two grains of the oxide, does not take up entirely even that small quantity. An important consequence of the fact now mentioned is, that when swallowed in the solid state, little or no arsenic may be found in the fluid contents of the stomach. In a case which occurred to Scheele three grains of solid arsenic were found in the contents, but hardly a trace in solution.[[505]] It would be wrong, however, to suppose that it is never found in the fluid contents. For, not to mention the observations of others, I have myself often detected it in the fluid part of the stomach in persons poisoned by arsenic.
The solution of oxide of arsenic in boiling water yields minute crystals on cooling, which, when their form is defined, are octaedres. In this state, on account of its whiteness and brilliancy, it exceedingly resembles pounded sugar. By spontaneous evaporation I have procured in twelve months fine octaedres nearly as large as peas. These do not become opaque by keeping, like the sublimed masses.
A difference of opinion prevails as to the action of the oxide on vegetable colours. This is a matter of no great consequence to the medical jurist; but it is right not to leave a disputed point without some notice. Guibourt says the transparent variety faintly reddens litmus, while the opaque variety faintly restores to blue litmus previously reddened.[[506]] My own experiments are at variance with these statements: I have always found that the solution of the powder, which is of the opaque variety, faintly reddens litmus, and does not alter reddened litmus.
The remaining chemical properties of the oxide, which it is necessary for the medical jurist to know, will be mentioned under what is now to be said of the principal test by which its presence may be ascertained. Under this head will be noticed, first the tests for the solid oxide, secondly, those for its solution, and lastly, the method of detecting it when mingled with vegetable or animal solids and fluids, such as the contents and tissues of the stomach.
Of the Tests for Arsenic in the solid state.
The most characteristic and simple test for oxide of arsenic in its solid state, either pure or mixed or combined with inorganic substances, is its reduction to the metallic state.
Various methods have been at different times proposed for employing the test of reduction. In the ruder periods of analytic chemistry we find Hahnemann recommending a retort as the fittest instrument, and stating ten grains as the least quantity he could detect.[[507]] Afterwards Dr. Black substituted a small glass tube, coated with clay and heated in a choffer; and in this way he could discover a single grain.[[508]] In a paper published in the Edinburgh Medical and Surgical Journal, I showed how to detect a sixteenth of a grain; and afterwards even so minute a quantity as a hundreth part of a grain.[[509]]
The process is performed in a glass tube; which, when the quantity of the oxide is very small, should not exceed an eighth of an inch in diameter, and may be conveniently used of the form first recommended by Berzelius, and represented in Fig. 3.—The best material for reducing the oxide is recently ignited charcoal, if the quantity of suspected substance be very small. For when any of the ordinary alkaline fluxes is used, more than half of the arsenic is retained, probably in the form of an arseniuret of the alkaline metalloid. But when the quantity of matter for analysis is considerable, charcoal is inconvenient, as it is apt to be projected up the tube on the application of heat; and an alkaline flux is on that account preferable. For this purpose soda-flux,—made by grinding crystals of carbonate of soda with an eighth of their weight of charcoal, and then heating the mixture gradually to redness, so as to drive off all water,—is better than the more familiar black flux, which contains carbonate of potash; because the latter attracts much moisture when kept for some time.—If the quantity operated on is large it should be mixed with the flux before being introduced into the tube; if it is small, it may be dropped into the tube and covered with charcoal. The materials are to be introduced along a little triangular gutter of stiff paper, if the tube is large; but with a small tube it is preferable to use the little glass funnel represented in Fig. 2, to which a wire is previously fitted, for pushing the matter down when it adheres. The material should not be closely impacted. Heat is best applied with the spirit-lamp, first to the upper part of the material, with a small flame, and then to the bottom of the tube, the flame being previously enlarged. A little water, disengaged in the first instance, should be removed with a roll of filtering paper, before a sufficient heat is applied to sublime the metal. As soon as the dark crust begins to form, the tube should be held steady in the same part of the flame. With these precautions a well defined crust will be procured with facility.
The characters of the crust have been mentioned already under the head of fly-powder (p. [199]). They are distinct even in crusts weighing only a 300th of a grain. A crust of this weight, a tenth of an inch broad and four times as long, may show characteristically all the physical characters of an arsenical sublimate a hundred times larger.