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
It frequently happens that we have to deal, simultaneously, with
conditions of chemical and of physical equilibrium, obtaining in the
same system. For instance, a gas like carbon dioxide, in contact
with its saturated solution in water, is in equilibrium with the
dissolved carbon dioxide, and this, in turn, is in equilibrium with
its hydrate, carbonic acid. A substance may be distributed between
two solvents and show a different molecular weight in the two (see
p. 18); it may exist, in the one, primarily in polymeric form, and
only to a slight extent in the simple form, the two forms being
in equilibrium (chemical equilibrium). In the other solvent, it
may exist only in its simple molecular form, and this will be in
equilibrium with the same simple molecular form in the first solvent
(physical equilibrium). In matters dealing with the solubility
of electrolytes in water, and, therefore, in questions of their
‹precipitation› or ‹solution›, such simultaneous conditions of
chemical and physical equilibrium are constantly occurring. Since
qualitative analysis deals to a very considerable extent with just
such precipitates of salts, acids and bases, these cases are of
particular importance to us.
«Earlier Derivation of the Solubility-Product Principle.»—A very
simple relation was derived by Nernst[291] for the combined
conditions of chemical and of physical equilibrium, where difficultly
soluble electrolytes (precipitates) were concerned. We shall develop
the relation first for a simple salt, such as silver acetate.
When water is added to solid silver acetate, the salt will dissolve.
If an excess of the acetate is used, equilibrium will result between
the solid salt and its solution, when the solution is saturated at
the temperature used. As the salt dissolves, it is more or less
ionized, and in the saturated solution we have a [p140] condition of
chemical equilibrium between the salt and its ions:
CH_{3}COOAg ⇄ CH_{3}COO^{−} + Ag^{+}. (1)
If the law of chemical equilibrium is applied to this reversible
action, we have (p. 98)
[CH_{3}COO^{−}] × [Ag^{+}] / [CH_{3}COOAg] = K_{Ionization}. I
The nonionized silver acetate is present in two phases, in the solid
phase and also in solution:
CH_{3}COOAg ↓ ⇄ CH_{3}COOAg. (2)
Applying the law of physical equilibrium to this system, we have
further (p. 121)
[CH_{3}COOAg] / [CH_{3}COOAg]_{solid} = K. II
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