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
We may consider, with Haber, a liter of a 0.05 molar solution of
K_{2}Ag(CN)_{3}, containing an excess[466] of 0.95 mole potassium
cyanide. In such a solution, the concentration of silver-ion
is reduced to 8E−24 gram-ion per liter. Now, according to the
best determinations of the ultimate dimensions of molecules,
about 10^{24} molecules are estimated to be contained in a mole
(gram-molecule), and 10^{24} ions, therefore, in a gram-ion (‹e.g.›
in 108 grams of silver-ion there would be 10^{24} individual silver
ions). Then a liter of the solution we are considering would
contain, at any moment, only eight individual silver ions, which are
different ones from moment to moment, since the reversible reactions
Ag^{+} + 3 CN^{−} ⇄ Ag(CN)_{3}^{2−}, are going on continually. Thus
100 c.c. of the solution would not contain even one silver ion all
the time, but the requirements of the equilibrium conditions could
be met[467] by silver ions "flashing up and disappearing" in such
a way, that the required average concentration in unit time is
maintained. There is nothing irrational in such a conception.
One may ask, however, what must be the velocities, with which the
complex is formed from the components, and is resolved into them,
in order to satisfy an instability constant[466] 10^{−22} and still
enable us to obtain a practically instantaneous precipitation, say
of silver sulphide, the action being analyzed on the basis of the
ordinary conception that only the silver-ion itself, and not the
complex ion, is directly active in the formation of the silver
sulphide. A condition of equilibrium, in a reversible action,
implies that the velocities of the two continuous, opposed reactions
are equal (p. 94). For the action Ag^{+} + 3 CN^{−} → Ag(CN)_{3}^{2−}
the ‹velocity› of ‹formation› of the ‹complex› is proportional to
a characteristic constant, K_{Formation}, to the concentration,
[Ag^{+}], of the silver-ion, and to the third power (see p. 94) of
the concentration, [CN^{−}], of the cyanide-ion. The ‹velocity›
of the ‹opposed reaction› of ‹decomposition› of the complex is
proportional to another characteristic constant, K_{Decomposition},
and to the concentration, [Ag(CN)_{3}^{2−}], of the complex ion.
For the condition of equilibrium, the velocities of the opposed
reactions are equal, and we derive the relation:
[Ag^{+}] × [CN^{−}]^3 / [Ag(CN)_{3}^{2−}] =
K_{Decomposition} / K_{Formation} = 1 / 10^{22}.
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