The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
It is evident from the theory of the formation of amides and
nitriles (Chapter IX.) that very many compounds of this kind can
correspond with the acids of phosphorus; but as yet only a few are
known. The easy transitions of the ortho-, meta-, and
pyrophosphoric acids, by means of the hydrogen of ammonia, into
the lower acids, and conversely, tend to complicate the study of
this very large class of compounds, and it is rarely that the
nature of a product thus obtained can be judged from its
composition; and this all the more that instances of isomerism and
polymerism, of mixture between water of crystallisation and of
constitution, &c., are here possible. Many data are yet needed to
enable us to form a true judgment as to the composition and
structure of such compounds. As the best proof of this we will
describe the very interesting and most fully investigated compound
of this class, PNCl_{2}, called _chlorophosphamide_, or nitrogen
chlorophosphorite. It is formed in small quantities when the
vapour of phosphoric chloride is passed over ignited sal-ammoniac.
Besson (1892) heated the compound PCl_{5}8NH_{3} (which is easily
and directly formed from PCl_{5} and NH_{3}) under a pressure of
about 50 mm. (of mercury) to 200°, and obtained brilliant crystals
of PNCl_{2}, which melted at 106° (in the residue after the
distillation of sal-ammoniacal phospham). The chlorine in it is
very stable--quite different from that in phosphoric chloride.
Indeed, the resultant substance is not only insoluble in water
(though soluble in alcohol and ether), but it is not even
moistened by it, and distils over, together with steam, without
being decomposed. In a free state it easily crystallises in
colourless prisms, fuses at 114°, boils at 250° (Gladstone,
Wichelhaus), and when fused with potash gives potassium chloride
and the amidonitrile of phosphoric acid. Judging from its formula
and the simplicity of its composition and reactions, it might be
thought that the molecular weight of this substance would be
expressed by the formula PCl_{2}N, that it corresponds with PON
and with PCl_{5} (like POCl_3), with the substitution of Cl_3 by
N, just as in POCl_3 two atoms of chlorine are replaced by oxygen;
but all these surmises are incorrect, because its vapour density
(referred to hydrogen--Gladstone, Wichelhaus) = 182--that is, the
molecular formula must be three times greater, P_{3}N_{3}Cl_{6}.
The polymerisation (tripling) is here of exactly the same kind as
with the nitriles.
Public-domain text, read in full here on John Shaqi.
Reviews
Reviews
No reviews yet
Be the first to share your thoughts on this work.
Elsewhere in the archive
Join the Discussion
Join the discussion
Sign in to leave a comment or review.
Sign InorCreate an account