The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
_Orthophosphoric acid_[13] is obtained by oxidising phosphorus with
nitric acid until the phosphorus entirely passes into solution and the
lower oxides of nitrogen cease to be evolved. The reaction takes place
best with dilute nitric acid, and when aided by heat. The resultant
solution is evaporated to a syrup. If a weighed quantity of phosphorus
(dried in a current of dry carbonic anhydride) be taken, a crystalline
mass of the acid can be obtained by evaporating the solution until it
consists only of the quantity[14] of phosphoric acid corresponding with
the amount of phosphorus taken (from 31 parts of P, 98 parts of
solution). The acid fuses at +39°; specific gravity of the liquid 1·88.
Phosphorus pentachloride, PCl_{5}, and oxychloride, POCl_{3} (see further
on), give orthophosphoric acid and hydrochloric acid with water. The two
other varieties of phosphoric acid, with which we shall presently become
acquainted, give the same ortho-acid when under the influence of acids,
with particular ease when boiled and more slowly in the cold. By itself
orthophosphoric acid (either in solution or when dry) does not pass into
the other varieties; it does not oxidise, and therefore presents the
limiting and stable form. When heated to 300°, it loses water and passes
into pyrophosphoric acid, 2H_{3}PO_{4} = H_{2}O + H_{4}P_{2}O_{7}, whilst
at a red heat it loses twice as much water and is converted into
metaphosphoric acid, H_{3}PO_{4} = H_{2}O + HPO_{3}. In aqueous solution
orthophosphoric acid differs clearly from pyro- or metaphosphoric acids,
because the solutions of these latter acids give different reactions:
thus orthophosphoric acid does not precipitate albumin, does not give a
precipitate with barium chloride, and forms a yellow precipitate of
silver orthophosphate, Ag_{3}PO_{4}, with silver nitrate (in the presence
of alkalis, but not otherwise); whilst a solution of pyrophosphoric acid,
H_{4}P_{2}O_{7}, although it does not precipitate albumin or barium
chloride, gives a white precipitate of silver pyrophosphate,
Ag_{4}P_{2}O_{7}, with silver nitrate; and a solution of metaphosphoric
acid, HPO_{3}, precipitates both albumin and barium chloride, and gives a
white precipitate of silver metaphosphate, AgPO_{3}, with silver nitrate.
These points of distinction were studied by Graham, and are exceedingly
instructive. They show that the solution of a substance does not
determine the maximum of chemical combination with water, that solutions
may contain various degrees of combination with water, and that there is
a clear difference between the water serving for solution and that
entering into chemical combination. Graham's experiments also showed that
the water whose removal or combination determines the conversion of
ortho- into meta- and pyrophosphoric acids differs distinctly from water
of crystallisation, for he obtained the salts of ortho-, meta-, and
pyrophosphoric acids with water of crystallisation, and they differed in
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