The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.Stieglitz, Julius
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The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.
Stieglitz, Julius
Chemistry, Analytic -- Qualitative
If it can be shown that the flow of electricity, resulting from
such unequal diffusibility of ions, is a function not only of the
difference in the total concentration of the electrolyte in the
two solutions brought into contact with each other, but is also a
function of the relative degrees of ionization of the electrolyte
in the two solutions, as defined by the theory of Arrhenius, then
this method of experimentation may be used as a further test of
the validity of this theory as against that of Clausius. It is
obvious that if such currents are the results of the diffusion of
‹ions› from higher to lower concentrations, then the essential
concentrations do not embrace all of the electrolyte, but only the
ionized part. W. K. Lewis[97] has rather recently shown that the
degrees of dissociation of electrolytes may be measured by the use
of concentration cells, and that the results agree well with the
determinations of the degree of dissociation from conductivity
measurements (p. 50). From calculations, based on Jahn's accurate
measurements of the electromotive forces of concentration cells,
A. A. Noyes[98] finds that "when the conductivity ratio is assumed
to represent the degree of ionization of the salt, the calculated
values of the electromotive force of concentration cells exceed the
measured ones by only about one per cent, in the case of potassium
and sodium chloride between the concentrations of 1 / 600 and 1 / 20
molar."
«The Rôle of the Solvent in Ionization.»—A question that has
profoundly interested chemists, particularly during the last few
years, has been that of the rôle which the solvent plays in the
[p062] dissociation of electrolytes into ions. The most important
ionizing solvent is water and, of the common solvents which cause
ionization, it is the most powerful in this particular. Alcohols have
also ionizing power; methyl or wood alcohol, which stands nearest
to water, has a higher ionizing power than ordinary ethyl alcohol.
The exact work[99] of Franklin and Kraus, on the conductivity of
solutions of salts in liquid ammonia, showed that the same general
relations obtain for such solutions as for solutions in water, the
differences being differences of degree rather than of kind. Salts
are found to be less ionized in liquid ammonia than in equivalent
aqueous solutions, but their conductivities are higher, the result of
smaller friction in ammonia. Liquid hydrogen cyanide is also a very
good ionizing medium.
Solvents which cause ionization only to a minimal extent are benzene
(C_{6}H_{6}), carbon bisulphide, ether, chloroform, petroleum ether
(gasoline) and similar solvents. Hydrogen chloride dissolved in
benzene has an extremely small conductivity, indicating only a trace
of ionization.[100]
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