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
Marsh's test is based upon the reduction of arsenious and arsenic acids
by nascent hydrogen, and the subsequent transformation of these bodies
into water and arsenetted hydrogen, a compound from which the arsenic
can be readily isolated. When pure hydrogen is generated in a flask
having two openings, one of which is provided with a perforated cork
through which a safety-tube passes, the other with a tube bent at a
right angle and drawn out to a small point at the free extremity, the
evolved gas, if ignited, burns with a pale non-luminous flame. The air
should be completely expelled from the apparatus before igniting the
gas. Upon bringing a cold porcelain saucer in contact with the point of
the flame, only water is formed. If, however, a small quantity of a
solution containing arsenious or arsenic acids is introduced into the
apparatus by means of the safety-tube, arsenetted hydrogen is produced.
This gas burns with a bright flame, yielding fumes of arsenious acid. In
case a large amount of the poison is present, it can be recognized by
the appearance of the flame, and by inclining a glass tube towards it
upon which a portion of the arsenious acid becomes deposited. These
indications are, however, not distinguishable in presence of only a
small amount of arsenic, and the following distinctive properties of the
gas should be verified:
1st. At an elevated temperature it is decomposed into its two
constituent elements.
[Illustration: Fig. 5.]
[Illustration: Fig. 6.]
2nd. The combustibility of the constituents differs: the arsenic being
less combustible than the hydrogen, begins to burn only after the
complete consumption of the latter body has taken place. For this reason
the flame (Fig. 5) is composed of a dark portion _O_ and a luminous
portion _I_, which surrounds the first. The maximum temperature exists
in _O_ at the point of union of the two parts of the flame. Owing to an
insufficient supply of oxygen, the complete combustion of the arsenic in
this part of the flame is impossible, and if it be intersected by the
cold surface _A B_, that body is deposited as a brown spot, possessing a
metallic lustre. The metallic deposit originates, therefore, from the
decomposition of the arsenetted hydrogen by heat and from its incomplete
combustion. If the spot is not large, it fails to exhibit a metallic
lustre; an experienced chemist, however, will be able to identify it by
the aid of proper tests. Spots are sometimes obtained when the substance
under examination does not contain the least trace of arsenic. These may
be caused by antimony or by a portion of the zinc salt in the generating
flask being carried over by the gaseous current. This difficulty is
remedied by giving the apparatus the form represented in Fig. 6. _A_ is
the flask in which the gas is generated. The delivery-tube _I_ connects
with a second tube _H_, filled with asbestus or cotton; this is united
by means of a cork with a third tube _C_, made of Bohemian glass. The
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