All the preceding account of the subject is, then, independent of any
view we may take of the nature of electrolytes, and stands on the basis
of direct experiment. Nevertheless, the facts considered point to a very
definite conclusion. The specific velocity of an ion is independent of
the nature of the opposite ion present, and this suggests that the ions
themselves, while travelling through the liquid, are dissociated from
each other. Further evidence, pointing in the same direction, is
furnished by the fact that since the conductivity is proportional to the
concentration at great dilution, the equivalent-conductivity, and
therefore the ionic velocity, is independent of it. The importance of
this relation will be seen by considering the alternative to the
dissociation hypothesis. If the ions are not permanently free from each
other their mobility as parts of the dissolved molecules must be secured
by continual interchanges. The velocity with which they work their way
through the liquid must then increase as such molecular rearrangements
become more frequent, and will therefore depend on the number of solute
molecules, i.e. on the concentration. On this supposition the observed
constancy of velocity would be impossible. We shall therefore adopt as a
wording hypothesis the theory, confirmed by other phenomena (see
ELECTROLYSIS), that an electrolyte consists of dissociated ions.
It will be noticed that neither the evidence in favour of the
dissociation theory which is here considered, nor that described in the
article ELECTROLYSIS, requires more than the effective dissociation of
the ions from each other. They may well be connected in some way with
solvent molecules, and there are several indications that an ion
consists of an electrified part of the molecule of the dissolved salt
with an attendant atmosphere of solvent round it. The conductivity of a
salt solution depends on two factors--(1) the fraction of the salt
ionized; (2) the velocity with which the ions, when free from each
other, move under the electric forces.[12] When a solution is heated,
both these factors may change. The coefficient of ionization usually,
though not always, decreases; the specific ionic velocities increase.
Now the rate of increase with temperature of these ionic velocities is
very nearly identical with the rate of decrease of the viscosity of the
liquid. If the curves obtained by observations at ordinary temperatures
be carried on they indicate a zero of fluidity and a zero of ionic
velocity about the same point, 38.5° C. below the freezing point of
water (Kohlrausch, _Sitz. preuss. Akad. Wiss._, 1901, 42, p. 1026). Such
relations suggest that the frictional resistance to the motion of an ion
is due to the ordinary viscosity of the liquid, and that the ion is
analogous to a body of some size urged through a viscous medium rather
than to a particle of molecular dimensions finding its way through a
crowd of molecules of similar magnitude.
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