The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
In order to see the relation between phosphoric acid and
hypophosphoric acid which does not contain the elements of
phosphorous acid (because it does not reduce either gold or
mercury from their solutions), but which nevertheless is capable
of being oxidised (for example, by potassium permanganate) into
phosphoric acid, it is simplest to apply the law of substitution.
This clearly indicates the relation between oxalic acid,
(COOH)_{2}, and carbonic acid, OH(COOH). The relation between the
above acids is exactly the same if we express phosphoric acid as
OH(POO_{2}H_{2}), because in this case P_{2}H_{4}O_{6}, or
(POO_{2}H_{2})_{3}, will correspond with it just as oxalic does
with carbonic acid. A similar relationship exists between
hyposulphuric or dithionic acid, (SO_{2}OH)_{2}, and sulphuric
acid, OH(SO_{2}OH), as we shall find in the following chapter.
Dithionic acid corresponds with the anhydride S_{2}O_{5},
intermediate between SO_{2} and SO_{3}; oxalic acid with
C_{2}O_{3}, intermediate between CO and CO_{2}; hypophosphoric
acid corresponds with the anhydride P_{2}O_{4}, intermediate
between P_{2}O_{3} and P_{2}O_{5}, and the analogue of N_{2}O_{4}.
Judging by the general law of the formation of acids (Chapter XV.), the
series of phosphorus compounds should include the following _ortho-acids_
and their corresponding anhydrides, answering to phosphuretted hydrogen,
H_{3}P:--
H_{3}PO_{4}, phosphoric acid, and P_{2}O_{5}, anhydride,
H_{3}PO_{3}, phosphorous acid, and P_{2}O_{3}, anhydride,
H_{3}PO_{2}, hypophosphorous acid, and P_{2}O, anhydride.[12]
The last of these (the analogue of N_{2}O) is almost unknown. Phosphoric
anhydride (P_{2}O_{5}) with a small quantity of water does not at first
give orthophosphoric acid, PH_{3}O_{4}, but a compound P_{2}O_{5},H_{2}O,
or PHO_{3}, whose composition corresponds with that of nitric acid; this
is _metaphosphoric acid_. Even with an excess of water, combining with
phosphoric anhydride, this metaphosphoric acid, and not the ortho-,
passes at first into solution. Metaphosphoric acid in solution only
passes into orthophosphoric acid when the solution is heated or after a
lapse of time.
[12] Besides the hydrates enumerated, a compound, PH_{3}O, should
correspond with PH_{3}. This hydrate, which is analogous to
hydroxylamine, is not known in a free state, but it is known as
triethylphosphine oxide, P(C_{2}H_{5})_{3}O, which is obtained by
the oxidation of triethylphosphine, P(C_{2}H_{5})_{3}. It must be
observed that there may also be lower oxides of phosphorus
corresponding with PH_{3}, like N_{2}O and NO, and there are even
indications of the formation of such compounds, but the data
concerning them cannot be considered as firmly established.
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