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
When the cyanide is dissolved in water, we must obtain, for the same
reasons as were developed in the discussion of the hydrolysis of
sodium chloride, a ‹little› nonionized potassium hydroxide, from the
union of potassium ions with hydroxide ions, formed by the water.
Potassium hydroxide being a strong, easily ionizable base, there
will be only a ‹slight tendency› towards this union. Hydrocyanic
acid, on the other hand, is an exceedingly weak acid. The value
of its ionization constant K_{HCN} = [H^{+}] × [CN^{−}] / [HCN]
is only 7E−10, as compared with a similar ratio approximating 1
for potassium hydroxide ([K^{+}] × [HO^{−}] / [KOH] = 1; see the
tables, p. 104 and p. 106 and see pp. 106–7). The hydrogen-ion,
formed from the water, must therefore combine with cyanide-ion, ‹to
form nonionized hydrocyanic acid›, much more completely than the
hydroxide-ion combines with potassium-ion. With the disappearance
of the ions of water, in this case notably of its hydrogen ions,
more water must ionize to satisfy the ionization constant [p181]
for water (p. 176), and the formation of hydrocyanic acid will
continue, towards the satisfying of its own constant. It is important
to note that, for the reasons given, the hydrogen-ion of water ‹is
used up to a far greater extent› than is the hydroxide-ion; ‹the
latter therefore accumulates›, and this accumulation results in the
formation of smaller and smaller concentrations of the hydrogen-ion,
by the water. Since [H^{+}] × [HO^{−}] = 1.2E−14 (at 25°; p.
104), as [HO^{−}] grows larger, [H^{+}] must grow ‹proportionally
smaller›. The ‹suppression of the hydrogen-ion by the accumulation
of the hydroxide ion› will, ultimately, make [H^{+}] so small,
that the equilibrium ratio [H^{+}] × [CN^{−}] / [HCN] will equal
the equilibrium constant. Since the union of the hydrogen-ion with
the cyanide-ion, to form little ionized hydrocyanic acid, is the
main moving cause for the changes, the latter will then come to a
standstill and equilibrium will be established. The net result of
the action of water on potassium cyanide may be said to consist in
the formation of practically nonionized hydrocyanic acid and the
liberation of (chiefly) ionized potassium hydroxide, ‹until all the
equilibrium constants› of the system are satisfied. We note that
potassium cyanide solution must react strongly alkaline (‹exp.›) and
that a free acid (‹e.g.› HCN) may well exist in the presence of a
free base (‹e.g.› KOH), provided the acid is present in a nonionized,
and therefore chemically inactive, condition (inactive as an ‹acid›).
Ignoring the (practically) unimportant formation of small quantities
of nonionized potassium hydroxide, we may summarize the action in a
single equation, which shows the main action:
CN^{−} + HOH ⇄ HCN + HO^{−}.
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