Legal Chemistry: A Guide to the Detection of Poisons, Examination of Tea, Stains, Etc., as Applied to Chemical JurisprudenceNaquet, Alfred
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Legal Chemistry: A Guide to the Detection of Poisons, Examination of Tea, Stains, Etc., as Applied to Chemical Jurisprudence
Naquet, Alfred
Chemistry, Forensic; Poisons
A general method for effecting the detection of alkaloids was first
proposed by _Stas_. Since the publication of this method, modifications
to it have been recommended by _Otto_, and by _L. Uslar_ and _J.
Erdman_. Other processes have been suggested by _Rodgers_ and _Girwood_,
by _E. Prollius_, and by _Graham_ and _Hofman_. The latter will
doubtless become general in their application; but up to the present
time they have been employed exclusively in the detection of strychnine.
Dialysis has also been recently applied in the separation of alkaloids.
[L] Colchicine, picrotoxine and digitaline.
STAS'S METHOD.
This method is based upon the facts: (_a_), that the acid salts of the
alkaloids, especially those containing an excess of tartaric or oxalic
acids, are decomposed by caustic alkalies and by the bicarbonates of
soda and potassa; (_b_), that the alkaloids, when liberated in this
manner, are combined with a certain amount of water which determines
their solution in ether, although, in a desiccated state they may be
insoluble in this menstruum; (_c_), that they may be extracted from
their aqueous solutions by agitation with ether.
Stas's original method is as follows: The suspected substances, if
organs are contained, are cut into fine shreds, then mixed with absolute
alcohol, 0.5 to 2. grammes of tartaric or oxalic acid added and the
whole introduced into a flask and heated at a temperature of 60° to 75°.
When quite cold, the mixture is filtered, and the undissolved portion
remaining on the filter washed with absolute alcohol, the washings being
added to the filtrate. The alcoholic solution is evaporated, either by
placing it under a bell-jar connected with an air-pump, or by passing a
current of air, having a temperature not exceeding 35° over it, until
reduced to a quarter of its original volume: the complete expulsion of
the alcohol being then rendered certain. If insoluble matter separates
during this operation, the concentrated fluid is passed through a
moistened filter, the water used in washing the residue being united to
the filtrate which is then evaporated to dryness by aid of the air-pump
or by placing the fluid in a bell-jar over concentrated sulphuric acid.
When the evaporation is completed, the residue is treated with absolute
alcohol, the alcohol allowed to evaporate at the ordinary temperature of
the air, and the second residue dissolved in the smallest possible
amount of water. The fluid thus obtained is placed in a test-tube, and a
concentrated solution of bicarbonate of soda added so long as
effervescence takes place. Ether is then added, the mixture thoroughly
shaken, and after it has remained at rest for some time, a small portion
of the supernatant ether removed and evaporated on a watch-glass: the
residue obtained will consist of the alkaloid present. Two cases are now
possible: the alkaloid is a solid, or it is a liquid and is volatile.
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