History of Chemistry, Volume 2 (of 2): From 1850 to 1910Thorpe, T. E. (Thomas Edward)
History
History of Chemistry, Volume 2 (of 2): From 1850 to 1910
Thorpe, T. E. (Thomas Edward)
Chemistry -- History
Kekulé was of opinion that the valency, or affinity-value, of an
element was a definite and invariable quantity—a fundamental property
of the atom as immutable as its atomic weight. Many facts appear to
show that such is not the case. Thus phosphorus and nitrogen are
sometimes trivalent and at other times pentavalent; tin, in certain
of its compounds, is divalent; in others, tetravalent. Sulphur may
be a dyad, a tetrad, or a hexad. It will be seen that the valency of
these particular elements varies by two units: this was at one time
held to be a natural law, and the various elements were divided by
Frankland into the two main groups of (1) _perissads_, or elements of
odd atomic value, and (2) _artiads_, or elements of even atomic value.
Experience has demonstrated that a rigid classification on this basis
is not possible. Many instances are known of elements not only varying
in valency by two units, but even by one unit. Thus nitrogen, which
is usually a perissad, is apparently an artiad in nitric oxide and in
gaseous nitrogen peroxide. Roscoe has shown that uranium and tungsten,
originally regarded as artiads, form pentachlorides.
To what the difference in the affinity-value of an element is due, and
why different elements should manifest different values, is at present
unknown. Valency, like other properties, appears to be a periodic
function of atomic weight; from the behaviour of such analogous
compounds as phosphorus pentafluoride, phosphorus pentachloride,
phosphorus pentabromide, it seems, too, to be related to the weights
of the atoms in combination. Further, it would appear that the mutual
affinities of substances vary with temperature—_i.e._, with the energy
imparted to their molecules; numerous instances appear to indicate
that the atom-fixing power of an element decreases when it is strongly
heated—that is, when the internal energy imparted to its combinations
exceeds a certain limiting value. Van ’t Hoff has attempted a
mechanical explanation of valency depending on the shape of the atoms,
as affected by variation in their vibratory motions resulting from
differences of temperature. Helmholtz suggested that the different
charges of electricity associated with the atoms may determine their
affinity-values—that, for example, a monad carries a single charge, a
dyad two, a triad three charges. Many considerations go to show that
the affinity-value of an element is not capable of definite numerical
expression in the sense which the doctrine of valency as generally
understood implies, and that the variations are not of the _per saltum_
character assumed by saying that the affinity-value is sometimes 1,
sometimes 2, at other times 3, and so on. When we have apparently
satisfied the accepted atomic value of an element by allocating to it
what we regard as the necessary complement of atoms of other bodies, it
is frequently evident that the capacity for combination of the whole
molecule is not satisfied.
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