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
In the first place, if the formation of ions occurs primarily
during the exchange of atoms in ‹collisions of molecules›, then,
as Whetham[85] has shown, the specific conductivity (of 1 cm.^3)
of an electrolyte, like hydrochloric acid, must increase with the
concentration and must increase, approximately, as a function of
the ‹third› power of the concentration. The more concentrated the
solution, the more frequent the collisions between the dissolved
molecules must be. As a matter of fact, as shown in the following
table, the conductivity [p053] increases a ‹little less› than
proportionally to the ‹first› power of the concentration—‹which is
in conflict with the assumption made in the hypothesis of Clausius›,
but in perfect agreement with the hypothesis of Arrhenius. The
small ‹decrease› with increasing concentration, in the simple ratio
between conductivity and concentration, is due to the decreasing
degree of ionization in the more concentrated solutions, as demanded
by the hypothesis of Arrhenius.
The table gives, in the first column, the specific conductivities
of hydrochloric acid at 18°, and, in the second column, the
concentrations; these concentrations are expressed in moles or
gram-equivalents per cubic centimeter; the last column gives the
ratio of conductivity to concentration.
Conductivity Conductivity
of 1 c.c. Concentration ─────────────
Concentration.
0.00370 0.00001 370
0.00734 0.00002 367
0.01092 0.00005 364
0.01800 0.00005 360
0.03510 0.00010 351
Furthermore, facts admitted by Clausius to be inexplicable by his
own assumptions receive, in the theory of Arrhenius, at least a
quantitative formulation borne out by a mass of corroborative
evidence. The difference in conductivity between pure water and
sulphuric acid is such a fact, mentioned by Clausius. Determinations
of the ionization of sulphuric acid and of water, by the
conductivity methods which are based on the theory of Arrhenius,
show that, while sulphuric acid is very considerably ionized (see
p. 104), water is scarcely ionized at all. The ionization of
water (see p. 104) has been determined quantitatively by at least
four independent methods of examination,[86] and, minimal as the
ionization is, the results agree so well with each other that van 't
Hoff[87] was led to write: "If one is not previously convinced of
the correctness of the theory of electrolytic dissociation, hardly
any result won by means of it is so convincing, as the agreement
between the conclusions reached in completely different ways as to
the degree of dissociation of water itself. After such an agreement,
it is hardly conceivable that the basis on which all these results
rest should further be altered."
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