The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
_Phosphonium iodide_, PH_{4}I, may be prepared, according to
Baeyer, in large quantities in the following manner:--100 parts of
phosphorus are dissolved in dry carbon bisulphide in a tubulated
retort: when the mixture has cooled, 175 parts of iodide are added
little by little, and the carbon bisulphide is then distilled off,
this being done towards the end of the operation in a current of
dry carbonic anhydride at a moderate temperature. The neck of the
retort is then connected with a wide glass tube, and the tubulure
with a funnel furnished with a stopcock, and containing 50 parts of
water. This water is added drop by drop to the phosphorous iodide,
and a violent reaction takes place, with the evolution of hydriodic
acid and phosphonium iodide. The latter collects as crystals in the
glass tube and the retort itself. It is purified by further
distillations; more than 100 parts may be obtained. Baeyer
expresses the reaction by the equation P_{2}I + 2H_{2}O = PH_{4}I +
PO_{2}; and the compound PO_{2} may be represented as phosphorous
phosphoric anhydride: P_{2}O_{5} + P_{2}O_{3} = 4PO_{2}. As a
better proportion we may take 400 grams of phosphorus, 680 grams of
iodine, and 240 grams of water, and express the formation thus: 13P
+ 9I + 21H_{2}O = 3H_{4}P_{2}O_{7} + 7PH_{4}I + 2HI (Chapter XI.,
Note 77).
Phosphonium iodide and even phosphine act as reducing agents in
solutions of many metallic salts. Cavazzi showed that with a
solution of sulphurous anhydride phosphine gives sulphur and
phosphoric acid.
_Phosphuretted hydrogen, or phosphine_, PH_{3}, is generally prepared by
the action of caustic potash on phosphorus.[10] Small pieces of
phosphorus are dropped into a flask containing a strong solution of
caustic potash and heated. Potassium hypophosphite, H_{2}KPO_{2}, is then
obtained in solution; gaseous phosphuretted hydrogen is evolved:
P_{4} + 3KHO + 3H_{2}O = 3(KH_{2}PO_{2}) + PH_{3}.
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