The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
The question presents itself as to whether phosphorus in a state of
vapour is the ordinary or some other variety? Hittorf (1865)
collected many data for the solution of this problem, which leave
no doubt that (as experimental figures show) the density of the
vapour of phosphorus is always the same, although the vapour
tension of the different varieties and their mixtures is very
variable. This shows that the different varieties of phosphorus
only occur in a liquid and solid state, as indeed is implied in the
idea of polymerisation. Strictly speaking, the vapour of phosphorus
is a particular state of this substance, and the molecular formula
P_{4} refers only to it, and not to any other definite state of
phosphorus. But Raoult's solution method showed that in a benzene
solution the fall of the freezing point indicates for ordinary
phosphorus a molecule P_{4}, judging by the determinations of
Paterno and Nasini (1888), Hirtz (1890), and Beckmann (1891), who
obtained for sulphur by the same method a molecular weight = S_{6},
in conformity with the vapour density. Further research in this
direction will perhaps show the possibility of finding the
molecular weight of red phosphorus, if a means be discovered for
dissolving it without converting it into the yellow variety.
I think it will not be out of place here to draw the reader's
attention to the fact that red phosphorus, which we must recognise
as polymeric with the yellow, stands nearer to nitrogen, whose
molecule is N_{2}, in its small inclination towards chemical
reactions, although judging by its small vapour tension it must be
more complex than ordinary (yellow and white) phosphorus.
The vapour of phosphorus is colourless; its density remains constant
between 300° and 1000° (Dumas, 1833; Mitscherlich, Deville, and Troost,
1859, and others). The density with respect to air has been determined as
from 4·3 to 4·5. Hence, referred to hydrogen, it is 4·4 × 14·4 = 63,
corresponding with a molecular weight 124, _i.e._ the molecule of
phosphorus in a state of vapour contains P_{4}. The reader will remember
that the molecule of nitrogen contains N_{2}, of sulphur S_{6} or S_{2},
and of oxygen O_{2} or O_{3}.
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