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
Science
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
When the conductivities of unlike electrolytes are compared, the
‹introduction of the conception of the degree of ionization›
(by Arrhenius,) into Kohlrausch's principle of the independent
conductivities of specific ions, shows most striking results and
‹demonstrates the value of the new conception›. For instance, the
equivalent conductivity of potassium chloride at 18° in 0.075 molar
solution is 113.8 reciprocal ohms and the partial conductivity of
the chloride-ion in the solution is 57.4. But the conductivity of
an equivalent solution of ‹mercuric chloride› at 18° is only 1.51,
which is very much less than the conductivity of the chloride-ion
alone in the potassium chloride solution. Now, mercuric chloride,
according to investigations of its conductivities and of its effect
in depressing the freezing-point of water,[91] is one of a very few
salts that are difficultly ionizable (p. 107); according to the data
mentioned, it is ionized, at most, to the extent of 2.5 per cent in
the solution in question, whereas 87.5 per cent of the potassium
chloride is ionized in such a solution. When the difference in
the degree of ionization is taken into account, the conductivity
which mercuric chloride ‹should show› may be calculated, ‹on
the assumption that the chloride-ion has the same mobility› in
the two solutions, but that there is less of it in the mercuric
solutions. We put Λ_{HgCl_{2}} = α (‹l›_{Hg} + ‹l›_{Cl}) = 0.025
(48 + 65.9) = 2.8. We thus find that the conductivity of the
mercuric chloride should be, approximately, only 2.8 reciprocal
ohms, which is of the same order as that found (1.51).[92]
In the same way, when we compare the conductivity of a strong acid,
like hydrochloric acid, with that of a weak acid, like acetic
acid—the conductivity of 0.1 molar hydrochloric acid is 351, of
0.1 molar acetic acid only 4.6—the principle of the specific,
characteristic mobility of the hydrogen-ion, which is present in
both solutions, has significance only if we take into account
the very different concentrations of the hydrogen-ion in the two
solutions, ‹resulting from the different degrees of ionization of
the two acids›—91% for the hydrochloric and only 1.7% for the acetic
acid. The same relations hold in the comparison of the conductivity
of a solution of a strong base like sodium hydroxide with that of
an equivalent solution of a weak, i.e. much less ionized base like
ammonium hydroxide, or in comparing the conductivity of a ‹weak
acid› or a ‹weak base› with the conductivities of their ‹much more
highly ionized salts›.
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