The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
In the two molecules of the
monobasic hypophosphorous acid taken, there are only two atoms of
hydrogen replaceable by metals, whilst in the molecule of the
resultant phosphoric acid there are three. Perhaps relations of
this nature determine the relative stability of the dimetallic
salts of orthophosphoric acid.
The monobasic _hypophosphorous acid_, PH_{3}O_{2}, gives salts
PH_{2}O_{2}Na, (PH_{2}O_{2})_{2}Ba, &c.; the two remaining atoms of
hydrogen (which exist in the same form as in phosphine, PH_{3}) are not
replaceable by metals, and this determines the property of these salts of
evolving phosphuretted hydrogen when heated (especially with alkalis). In
acting on substances liable to reduction it is this hydrogen which acts,
and, for example, _reduces_ gold and mercury from the solutions of their
salts, or converts cupric into cuprous salts. In all these instances the
hypophosphorous acid is converted into phosphoric acid. Under the action
of zinc and sulphuric acid it gives phosphine, PH_{3}. Nevertheless,
neither hypophosphorous acid nor its dry salts absorb oxygen from the
air. The salts of hypophosphorous acid are more soluble than those of the
preceding acids of phosphorus. Thus the sodium salt PNaH_{2}O_{2} does
not give a precipitate with barium chloride, and the salts of calcium,
barium, and many other metals are soluble.[23] The hypophosphites are
prepared by boiling an alkali with phosphorus so long as phosphuretted
hydrogen is evolved. The acid itself is obtained from barium
hypophosphite (prepared in the same manner by boiling phosphorus in
baryta water), by decomposing its solution with sulphuric acid. By
concentration of the solution of hypophosphorous acid (it must not be
heated above 130°, at which temperature it decomposes) a syrup is formed
which is able to crystallise. In the solid state hypophosphorous acid
fuses at +17°, and has the properties of a clearly defined acid.
[23] Calcium hypophosphite is used in medicine. According to Cavazzi, a
mixture of sodium hypophosphite, NaH_{2}PO_{2}, and sodium nitrate
explodes violently.
The types PX_{3} and PX_{5}, which are evident for the hydrogen and
oxygen compounds of phosphorus, are most clearly seen in its halogen
compounds,[24] to the consideration of which we will proceed, fixing our
attention more especially on the chlorine compounds, as being the most
important from the historical, theoretical, and practical point of view.
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