Treatise on Poisons by Sir Robert Christison
5. _Of Corrosive Sublimate._
1059 words | Chapter 111
Corrosive sublimate (oxymuriate, corrosive muriate, bichloride of
mercury), is by far the most important of the mercurial poisons, as it
is both the most active of them, and the one most frequently used for
criminal purposes. It is commonly met with in the form of a heavy,
snow-white powder, or of small, broken crystals, or in white, compact,
concave, crystalline cakes. It is permanent in the air; but in the
sunshine is slowly decomposed, a gray insoluble powder being formed. It
readily crystallizes, and the common form of the crystals is the
quadrangular prism. Its specific gravity is 5·2. Its taste is strongly
styptic, metallic, acrid, and persistent; and its dust powerfully
irritates the nostrils. It is soluble, according to Thenard, in 20,
according to Orfila, in 11 parts of temperate water, and in thrice its
weight of boiling water. Its solution faintly reddens litmus. It is more
soluble in alcohol than in water, boiling alcohol dissolving its own
weight, and retaining when it cools, a fourth part. It is also very
soluble in ether, so that ether will remove it from its aqueous
solution. Corrosive sublimate may become the subject of a medico-legal
analysis in three states. It may be in the solid form; it may be
dissolved in water along with other mineral substances; and it may be
mixed with vegetable and animal fluids or solids.
_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.
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