The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
Liquid phosphuretted hydrogen (and free hydrogen) is also formed,
together with the phosphine, so that the gaseous product, on escaping
from the water into the air, takes fire spontaneously, forming beautiful
white rings of phosphoric acid. In this experiment, as in that with
calcium phosphide, it is the liquid, P_{2}H_{4}, that takes fire; but the
phosphine set light to by it also burns, PH_{3} + O_{4} = PH_{3}O_{4}.
The same phosphuretted hydrogen, PH_{3}, may be obtained pure, and not
spontaneously combustible, by igniting the hydrates of phosphorous acid
(4PH_{3}O_{3} = PH_{3} + 3PH_{3}O_{4}) and hypophosphorous acid
(2PH_{3}O_{2} = PH_{3} + PH_{3}O_{4}); or, more simply, by the
decomposition of calcium phosphide by hydrochloric acid, because then all
the liquid phosphide, P_{2}H_{4}, is decomposed into non-volatile P_{2}H
and gaseous PH_{3}. Pure phosphine liquefies when cooled to -90°, boils
at -85°, and solidifies at -135° (Olszewski). When phosphorus burns in an
excess[10 bis] of _dry_ oxygen, then only _phosphoric anhydride_,
P_{2}O_{5} is formed. It is prepared by dropping pieces of phosphorus
through a wide tube, fixed into the upper neck of a large glass globe, on
to a cup suspended in the centre of the globe. These lumps are set alight
by touching them with a hot wire, and the phosphorus burns into
P_{2}O_{5}. The dry air necessary for its combustion is forced into the
globe through a lateral neck, and the white flakes of phosphoric
anhydride formed are carried by the current of air through a second
lateral neck into a series of Woulfe's bottles, where they settle as
friable white flakes. Phosphoric anhydride may also be formed by passing
dry air through a solution of phosphorus in carbon bisulphide. All the
materials for the preparation of this substance must be carefully dried,
because it _combines_ with great eagerness _with water_, at the same time
developing a large amount of heat and forming metaphosphoric acid,
HPO_{3}, from which the water cannot be separated by heat. Phosphoric
anhydride is a colourless snow-like substance, which attracts moisture
from the air with the utmost avidity. It fuses at a red heat, and then
_volatilises_. Its affinity for water is so great that it takes it up
from many substances. Thus it converts sulphuric acid into sulphuric
anhydride, and carbohydrates (wood, paper) are carbonised, and give up
the elements of water when brought into contact with it.
[10] The air must first be expelled from the flask by hydrogen, or some
other gas which will not support combustion, as otherwise an
explosion might take place owing to the spontaneous inflammability
of the phosphuretted hydrogen.
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