The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
As a hydrate, orthophosphoric acid should be expressed, after the fashion
of other hydrates, as containing three water residues (hydroxyl groups),
_i.e._ as PO(OH)_{3}. This method of expression indicates that the type
PX_{5}, seen in PH_{4}I, is here preserved, with the substitution of
X_{2} by oxygen and X_{3} by three hydroxyl groups. The same type appears
in POCl_{3}, PCl_{5}, PF_{5}, &c. And if we recognise phosphoric acid as
PO(OH)_{3}, we should expect to find three anhydrides corresponding with
it: (1) [PO(OH)_{2}]_{2}O, in which two of the three hydroxyls are
preserved; this is pyrophosphoric acid, H_{4}P_{2}O_{7}. (2) PO(OH)O,
where only one hydroxyl is preserved. This is metaphosphoric acid. (3)
(PO)_{2}O_{3} or P_{2}O_{5}, that is, perfect phosphoric anhydride.
Therefore, _pyro- and metaphosphoric acids are imperfect anhydrides_ (or
anhydro-acids) _of orthophosphoric acid_.[19]
[19] In this sense the ortho-acid itself might be regarded as an
anhydro-acid, counting P(HO)_{5} as the perfect hydrate, if PH_{5}
existed; but as in general the normal hydrates correspond with the
existing hydrogen compounds with the addition of up to 4 atoms of
oxygen, therefore PH_{3}O_{4} is the normal acid, just as
SH_{2}O_{4} and ClHO_{4}; while NHO_{3}, CH_{2}O_{3} are
meta-acids, or higher normal acids (NH_{3}O_{4} and CH_{4}O_{4})
with the loss of a molecule of water.
In order to see the relation between the ortho-, pyro-, and
metaphosphoric acids, the first thing to remark in them is that
the anhydride P_{2}O_{5} is combined with 3, 2, and 1 molecules of
water. In the absence of data for the molecular weight of ortho-
and pyrophosphoric acids it is necessary to mention that all
existing data for metaphosphoric acid indicate (Note 21) that its
molecule is much more complex and contains at least
H_{3}P_{3}O_{9} or H_{6}P_{6}O_{18}. The explanation of the
problems which here present themselves can, it seems to me, be
only looked for after a detailed study of the phenomena of the
polymerisations of mineral substances, and of those complex acids,
such as phosphomolybdic, which we shall hereafter describe
(Chapter XXI.) A similar instance is exhibited in the solubility
of hydrate of silica (produced by the action of silicon fluoride
on water) in fused metaphosphoric acid, with the formation, on
cooling, of an octahedral compound (sp. gr., 3·1) containing
SiO_{2},P_{2}O_{5}. A certain indication (but no proof) that
ordinary orthophosphoric acid is polymerised is given by
Staudenmaier (1893), who obtained a salt, K_{5}H_{4}P_{3}O_{12},
by the action of a solution of KH_{2}PO_{4} upon K_{2}CO_{3}; and
a compound, KH_{3}P_{2}O_{8}, corresponding to the doubled
molecule of H_{3}PO_{4}, by the action of KH_{2}PO_{4} upon
H_{3}PO_{4} itself.
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