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
In a similar way, the conductivity of every solution of an
electrolyte may be shown to represent the sum of the mobilities
of the ions carrying the current (‹principle of Kohlrausch›). The
limit of the conductivity of one equivalent of an electrolyte is
the sum of the mobilities of the ions composing the electrolyte.
The frictional forces being constant for infinitely dilute
solutions, at a given temperature, an ion will always show
the same mobility, irrespective of the nature of the ion of
opposite charge, with which it forms the electrolyte. We may
then put Λ_{∞} = (‹l›^{+}_{∞} + ‹l›^{−}_{∞}), if ‹l›^{+}_{∞} and
‹l›^{−}_{∞} are used to designate the limits of the mobilities
of gram-equivalents of the positive and negative ions forming
the electrolyte. The following table[90] gives the limits of the
mobilities for gram equivalents of some of the most important ions
at 18°.
‹Limits of Mobilities of Common Ions at› 18°.
K: 65.3 ½ Ca: 53.0 I: 66.7
Na: 44.4 H: 318.0 NO_{3}: 60.8
(NH_{4}): 64.2 OH: 174.0 C_{2}H_{3}O_{2}: 33.7
Ag: 55.7 Cl: 65.9 ½ SO_{4}: 69.7
For quite dilute solutions, in which the friction may be assumed to
be approximately constant, the conductivity will depend, not only
on the mobilities of the ions, which may be taken to be the same as
for solutions of extreme dilution, but also ‹on the proportion of
electrolyte that is ionized›, ‹i.e.› on the degree of ionization,
α. Then Λ_{‹v›} = α (‹l›^{+}_{∞} + ‹l›^{−}_{∞}), which is an
elaboration of the original equation given on page 50.
Now, Kohlrausch discovered the principle of the summation of the
mobilities of ions a number of years before the theory of Arrhenius
was advanced, and the proportion in which the ion is present in a
given solution being unknown, the effect of what is here known as
the degree of ionization was included empirically in the value of
the mobility. It is not surprising, then, that an ion was found
to have approximately the same mobility ‹only› in solutions of
the same concentration ‹of strictly analogous and closely related
salts›, which, according to present methods of investigation, are
‹now› found to have approximately the same degree of ionization. For
instance, the mobility of the gram-equivalent of the chloride-ion
was found to be approximately the same, 47.3 and 50.5 respectively,
in molar solutions of sodium and potassium chloride at 18°, no
account being taken of the degrees of ionization. However, the
degrees of ionization of the two salts are approximately the same,
66.9% and 74.9% respectively, and might be ignored in a comparison
of the conductivities, without affecting the result of the
comparison in any marked way. [p057]
Public-domain text, read in full here on John Shaqi.
Reviews
Reviews
No reviews yet
Be the first to share your thoughts on this work.
Elsewhere in the archive
Join the Discussion
Join the discussion
Sign in to leave a comment or review.
Sign InorCreate an account