The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
According to Tamman's researches, vitreous metaphosphoric acid
contains a mixture consisting chiefly of two varieties, differing
in the solubility and degree of stability of their salts. The
least stable corresponds to Fleitmann's hexa-acid, and gives three
isomeric salts. Tamman came to the conclusion that there exist
polymers also in the form of penta-, ortho-, and
deca-metaphosphoric acids. Without going into details upon this
subject, I do not think it superfluous to point out that the
undoubted capability of metaphosphoric acid to polymerise should
be connected with its faculty of combining with water, whilst the
degree of polymerisation and the number of polymeric forms cannot
yet be considered as sufficiently explained.
In order to see the relation between phosphoric acid and the lower acids
of phosphorus, it is simplest to imagine the substitution of hydroxyl in
H_{3}PO_{4} or PO(OH)_{3} by hydrogen. Then from orthophosphoric acid,
PO(OH)_{3}, we shall obtain phosphorous acid, POH(OH)_{2}, and
hypophosphorous acid, POH(OH); and, furthermore, phosphorous acid should
be bibasic if orthophosphoric acid was tribasic, and hypophosphorous acid
should be monobasic. This conclusion[21 bis] is, in fact, true, and hence
all the acids of phosphorus may be referred to one common type, PX_{5},
whose representatives are PH_{4}I and PCl_{5}, POCl_{3}, PCl_{2}F_{3},
&c.
[21 bis] The bibasity of H_{3}PO_{3}, established by Würtz, has been
proved by many direct experiments (see, for instance, Note 22),
among which we may mention that Amat (1892) took a mixture of the
aqueous solutions of Na_{2}HPO_{3} and NaHO and added absolute
alcohol to it. Two layers were formed; the upper, alcoholic,
contained all the excess of NaHO, whilst the lower only contained
the salt Na_{2}HPO_{3}, which was therefore unable to react with
the excess of NaHO. Amat also obtained NaH_{2}PO_{3} by saturating
H_{3}PO_{3} with soda until he obtained a neutral reaction with
methyl-orange. The replacement of one atom of H by sodium here, as
in phosphoric acid (Note 16), gives more heat than the replacement
of the second atom. For the third atom there is no formation of a
salt, and therefore no evolution of heat. The monometallic
salts--for example, NaH_{2}PO_{3}--or the ammonia salts, when
heated to 160°, give, as Amat had previously shown, a salt of
bibasic pyrophosphorous acid, Na_{2}H_{2}P_{2}O_{5}.
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