The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
[4] The thermochemical determinations for phosphorus and its compounds
date from the last century, when Lavoisier and Laplace burnt
phosphorus in oxygen in an ice calorimeter. Andrews, Despretz,
Favre, and others have studied the same subject. The most accurate
and complete data are due to Thomsen. To determine the heat of
combustion of yellow phosphorus, Thomsen oxidised it in a
calorimeter with iodic acid in the presence of water, and a mixture
of phosphorous and phosphoric acids was thus formed (was not any
hypophosphoric acid formed?--Salzer), and the iodic acid converted
into hydriodic acid. It was first necessary to introduce two
corrections into the calorimetric result obtained, one for the
oxidation of the phosphorous into phosphoric acid, knowing their
relative amounts by analysis, and the other for the deoxidation of
the iodic acid. The result then obtained expresses the conversion
of phosphorous into hydrated phosphoric acid. This must be
corrected for the heat of solution of the hydrate in water, and for
the heat of combination of the anhydride with water, before we can
obtain the heat evolved in the reaction of P_{2} with O_{5} in the
proportion for the formation of P_{2}O_{5}. It is natural that with
so complex a method there is a possibility of many small errors,
and the resultant figures will only present a certain degree of
accuracy after repeated corrections by various methods. Of such a
kind are the following figures determined by Thomsen, which we
express in thousands of calories:--P_{2} + O_{5} = 370; P_{2} +
O_{3} + 3H_{2}O = 400; P_{2} + O_{5} + a mass of water = 405. Hence
we see that P_{2}O_{5} + 3H_{2}O = 30; 2PH_{3}O_{4} + an excess of
water = 5. Experiment further showed that crystallised PH_{3}O_{4},
in dissolving in water, evolves 2·7 thousand calories, and that
fused (39°) PH_{3}O_{4} evolves 5·2 thousand calories, whence the
heat of fusion of H_{3}PO_{4} = 2·5 thousand calories. For
phosphorous acid, H_{3}PO_{3}, Thomsen obtained P_{2} + O_{3} +
3H_{2}O = 250, and the solution of crystallised H_{3}PO_{3} in
water = -0·13, and of fused H_{3}PO_{3} = +2·9. For hypophosphorous
acid, H_{3}PO_{2}, the heats of solution are nearly the same (-0·17
and +2·1), and the heat of formation P_{2} + O + 3H_{2}O = 75;
hence its conversion into 2H_{3}PO_{3} evolves 175 thousand
calories, and the conversion of 2H_{3}PO_{3} into 2H_{3}PO_{4} =
150 thousand calories. For the sake of comparison we will take the
combination of chlorine with phosphorus, also according to Thomsen,
per 2 atoms of phosphorus, P_{2} + 3Cl_{2} = 151, P_{2} + 5Cl_{2} =
210 thousand calories. In their reaction on an excess of water
(with the formation of a solution), 2PCl_{3} = 130, 2PCl_{5} = 247,
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