Legal Chemistry: A Guide to the Detection of Poisons, Examination of Tea, Stains, Etc., as Applied to Chemical JurisprudenceNaquet, Alfred
Science
Legal Chemistry: A Guide to the Detection of Poisons, Examination of Tea, Stains, Etc., as Applied to Chemical Jurisprudence
Naquet, Alfred
Chemistry, Forensic; Poisons
The materials supposed to contain arsenic are boiled in water which
has been rendered strongly alkaline by the addition of pure potassa. The
fluid is then filtered, an excess of hydrochloric acid added, and a
current of sulphuretted hydrogen conducted through it. If arsenic be
present in the suspected fluid, it is soon precipitated as a yellow
sulphide. In dilute solutions the formation of the precipitate fails to
take place immediately, and only a yellow coloration of the fluid is
perceptible; upon slightly boiling the solution, however, the
precipitation of the sulphide is soon induced. The precipitate is
collected on a filter, well washed with boiling water, and then removed,
if present in a quantity sufficient to admit of this operation. It is
next dissolved in ammonia,[B] and the solution so obtained subsequently
evaporated to dryness on a watch-glass. The residue of sulphide of
arsenic is placed in a tube closed at one end containing nitrate of
potassa in a state of fusion: it is decomposed by this treatment into a
mixture of sulphate and arsenate of potassa, the reaction being
completed in about fifteen minutes. The mixture is now dissolved in
water, and lime water added to the solution: a precipitate of arsenate
of lime is formed, which is separated from the fluid by filtration,
dried, mixed with charcoal, and introduced into a second tube. A few
pieces of charcoal are then placed in the tube adjoining the mixture and
exposed to a red heat, the part of the tube containing the arsenical
compound being also heated. By this operation the arsenic acid is
reduced to arsenic, which is deposited upon the cold portion of the tube
in the form of a metallic mirror. This mirror is then identified by
subsequent reactions. The method just described is no longer in use,
although the precipitation of the arsenic by sulphuretted hydrogen is
still often resorted to in its separation from the other metals with
which it may be mixed. The destruction of the organic substances is,
however, accomplished by means of chlorate of potassa and hydrochloric
acid. To insure the complete precipitation of the arsenic, it is
advisable to conduct sulphuretted hydrogen through the solution, at a
temperature of 70° for twelve hours, and then allow the fluid to remain
in a moderately warm place, until the odor of the gas is no longer
perceptible, the vessel being simply covered with a piece of paper. The
precipitate is next freed from the other metals possibly present, as
directed in the general method of analysis, collected on a filter, and
dissolved in ammonia. The ammoniacal solution is evaporated on a watch
crystal, as previously described, and the residuary sulphide reduced to
metallic arsenic. This reduction is effected by a process somewhat
different from the one previously mentioned: the residue is fused, in a
current of carbonic acid gas, with a mixture of carbonate of soda and
cyanide of potassium. The apparatus employed is represented in Fig. 3:
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