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
AgCl ⇄ AgCl ↓
It is clear, from a comparison of this series of equations with
equations (1), that they represent the same reversible reactions in
a somewhat different order. ‹Since equilibrium conditions for any
reversible reaction› (‹e.g.› for A + B ⇄ C + D) ‹are independent
of the order in which the components› (‹e.g.› A, B, C, D) ‹are
brought into the system› (p. 94), the difference of order, indicated
by equations (1) and (2), cannot affect the final condition of
equilibrium in the system under discussion. For instance, since we
again have silver chloride in contact with its saturated solution,
we again must have [Ag^{+}] × [Cl^{−}] = K_{AgCl}, and ‹the
experimental confirmation› of this relation (and similarly of the
relation [Ag^{+}] × [NH_{3}]^2 / [Ag(NH_{3})_{2}^{+}] = K) ‹agrees
as well with this second path of the action as with the first›.
Conversely, since the path, by which the equilibrium is reached,
does not affect the condition of equilibrium, it is perfectly
legitimate to draw conclusions from equilibrium constants, ‹without
assuming to know anything at all about the path by which the
condition is reached›.[475]
For analytical work, the vital point is the ‹ultimate condition of
equilibrium, which determines whether a precipitate may exist and be
formed in a given system or not›. The instability constants of the
complex ions and the solubility-product constants of precipitates
are the constant factors involved in the ultimate conditions for
equilibrium, and they do not depend on the path by which equilibrium
is reached. Consequently, we find that the application of [p237]
the theory of complex ions to analytical problems of precipitation
has been in no wise invalidated by the problems presented by Haber.
The theory forms now, as before, in fact, the best quantitative
basis for the expression of the experimental results. The stability
constants, and the concentrations of the components used, determine
the limiting concentrations in which a given metal ion is capable of
continued existence, and determine, therefore, the question whether
an ionogen, of a given solubility, is capable of existence as a
solid phase in a given system.
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