Poisons, Their Effects and Detection: A Manual for the Use of Analytical Chemists and ExpertsBlyth, Alexander Wynter
Science
Poisons, Their Effects and Detection: A Manual for the Use of Analytical Chemists and Experts
Blyth, Alexander Wynter
Poisons
2. =The Production of Phosphine= (PH₃).--Any method which produces
phosphine (phosphuretted hydrogen), enabling that gas to be passed
through nitrate of silver solution, may be used for the detection of
phosphorus. Thus, Sonnenschein states that he has found phosphorus in
extraordinary small amount, mixed with various substances, by heating
with potash in a flask, and passing the phosphine into silver nitrate,
separating the excess of silver, and recognising the phosphoric acid by
the addition of molybdate of ammonia.[317]
[317] Sonnenschein, _Handbuch der gerichtlichen Chemie_, Berlin, 1869.
The usual way is, however, to produce phosphine by means of the action
on free phosphorus of nascent hydrogen evolved on dissolving metallic
zinc in dilute sulphuric acid. Phosphine is formed by the action of
nascent hydrogen on solid phosphorus, phosphorous acid, and
hypophosphorous acid; but no phosphine can be formed in this way by the
action of hydrogen on phosphoric acid.
Since it may happen that no free phosphorus is present, but yet the
first product (phosphorous acid) of its oxidation, the production of
phosphine becomes a necessary test to make on failure of Mitscherlich’s
test; if no result follows the proper application of the two processes,
the probability is that phosphorus has not been taken.
Blondlot and Dusart evolve hydrogen from zinc and dilute sulphuric acid,
and pass the gas into silver nitrate; if the gas is pure, there is of
course no reduction; the liquid to be tested is then added to the
hydrogen-generating liquid, and if phosphorous or hypophosphorous acids
be present, a black precipitate of phosphor-silver will be produced. To
prove that this black precipitate is neither that produced by SH₂, nor
by antimony nor arsenic, the precipitate is collected and placed in the
apparatus to be presently described, and the spectroscopic appearances
of the phosphine flame observed.
3. =Tests Dependent on the Combustion of Phosphine= (PH₃).--A hydrogen
flame, containing only a minute trace of phosphorus, or of the lower
products of its oxidation, acquires a beautiful green tint, and
possesses a characteristic _spectrum_. In order to obtain the latter in
its best form, the amount of phosphine must not be too large, or the
flame will become whitish and livid, and the bands lose their defined
character, rendering the spectrum continuous. Again, the orifice of the
tube whence the gas escapes must not be too small; and the best result
is obtained when the flame is cooled.
M. Salet has proposed two excellent methods for the observation of
phosphine by the spectroscope:--
(1) He projects the phosphorus-flame on a plane vertical surface,
maintained constantly cold by means of a thin layer of running water;
the green colour is especially produced in the neighbourhood of the cool
surface.
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