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
Whereas water, as an acid and as a base, is so exceedingly weak,
that it can form but traces of its own salts, sodium hydroxide and
hydrochloric acid, when acting on sodium chloride and competing for
the base with such a strong acid as hydrochloric acid and for the
acid with such a strong base as sodium hydroxide (see p. 179), the
result, evidently, is quite different when water competes for a base
with so weak an acid as hydrocyanic acid. In this case, we note that
a considerable quantity of (ionized) potassium hydroxide, the salt of
water in its rôle of an acid, is formed as a result of the action of
water on potassium cyanide. [p182]
The theory of ionization, with the aid of the law of chemical
equilibrium, gives us the means for ‹accurately defining the
relative concentrations of the products, in the final condition of
equilibrium›.[368] For the weak acid, hydrocyanic acid, we have the
condition of equilibrium
[H^{+}] × [CN^{−}] / [HCN] = K_{HCN} = 7E−10.
The symbols [H^{+}], [CN^{−}] and [HCN] denote the final
concentrations for the condition of equilibrium, indicated in the
equations on p. 180; in such a mixture [H^{+}] is ‹not equal to›
[CN^{−}], as it is in pure solutions of hydrocyanic acid in water.
[CN^{−}], representing the total concentration of the cyanide-ion,
is very much larger than [H^{+}], since the salt, potassium cyanide,
produces the cyanide-ion in large concentrations.
For water, we have [H^{+}] × [HO^{−}] = K_{HOH} = 1.2E−14, at 25°.
Here, again, the symbols represent the final, total concentrations
of the ions in the mixture and [HO^{−}] is much larger than [H^{+}],
since hydroxide-ion is formed in large quantities, as described
above.
Combining the two equations, we have:
[CN^{−}] / ([HCN] × [HO^{−}]) = K_{HCN} / K_{HOH} = K_{Hydrolysis}.
The cyanide-ion, whose concentration is expressed by [CN^{−}],
is formed practically altogether by the ionization of potassium
cyanide, which is an easily ionizable and almost entirely ionized
salt; the hydroxide-ion, whose concentration is expressed by
[HO^{−}], is formed by the ionization of potassium hydroxide,
which is an easily ionizable base, ionized to practically the same
degree as is the potassium cyanide in the solution. If we represent
the ‹total› concentration of the potassium cyanide, ionized and
nonionized, at the point of equilibrium, by [KCN] and its degree
of ionization by α_{1}, and if we represent, similarly, the total
concentration of potassium hydroxide by [KOH] and its degree of
ionization by α_{2}, the equilibrium equation may be written:
α_{1}[KCN] / ([HCN] × α_{2}[KOH]) = K_{HCN} / K_{HOH} = K_{Hydrolysis}.
Since the degrees of ionization of the two strong electrolytes are
practically the same, we have further simply
[KCN] / ([HCN] × [KOH]) = K_{HCN} / K_{HOH} = K_{Hydrolysis}.
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