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
Chemists have always been interested in the problem of the exact
degree of stability of ammonium hydroxide, and, more particularly,
in the problem whether ammonia gives solutions in water showing
very much weaker basic strength[329] than equivalent solutions of
potassium and sodium hydroxides, primarily ‹because only a small
proportion of the ammonia is combined with water to form the real
base, ammonium hydroxide› (which would be present then in much
more dilute solution than the alkali metal hydroxides are in the
solutions with which the comparison is made), or chiefly ‹because
ammonium hydroxide is much less readily ionizable› than potassium or
sodium hydroxide.
For the reversible action NH_{3} + HOH ⇄ NH_{4}OH we would have, at
a constant temperature, according to the law of chemical equilibrium,
[NH_{3}] × [HOH] / [NH_{4}OH] = ‹k›.
For a dilute solution at a given temperature the concentration of
the water may be considered a constant, and therefore
[NH_{3}] / [NH_{4}OH] = ‹k› / [HOH] = ‹k›_{NH_{3}}. (I)
For the ionization of ammonium hydroxide,
NH_{4}OH ⇄ NH_{4}^{+} + HO^{−}, we would have in turn,
[NH_{4}^{+}] × [HO^{−}] / [NH_{4}OH] = ‹k›_{base}. (II)
This constant represents ‹the real ionization constant of ammonium
hydroxide as a base›, and its approximate value has only recently
been determined by Moore[330] and found to be about 5E−5. The
ratio [NH_{3}] / [NH_{4}OH] was found to be approximately 2 at
20°. According to this result, ammonium hydroxide is really a
much weaker, less readily ionized base than potassium or sodium
hydroxide. The ‹efficiency of ammonium hydroxide as a base› depends
[p161] on both conditions of equilibrium; the first equation
states what proportion of ammonium hydroxide can exist, as such,
in solution, if a given amount of ammonia is dissolved in a given
amount of water, and the second equation shows the proportion of the
hydroxide, which is ionized. The equations may be combined[331] into
one expression,
[NH_{4}^{+}] × [HO^{−}] / ([NH_{4}OH] + [NH_{3}]) = K. (III)
That is, ‹the ratio of› [NH_{4}^{+}] × [HO^{−}] ‹to the total
concentration of nonionized ammonium hydroxide and ammonia, is
a constant›. This constant has the value 0.000,018 at 18° (as
given in the table, p. 106) and, as said, comprises in a single
expression a statement measuring the ‹efficiency›, as a base, of a
solution of ammonium hydroxide and ammonia in aqueous solutions.
The concentration of the hydroxide-ion, on which the efficiency as
a base depends, can be ascertained directly from the expression,
provided we know the total concentration of the ammonia and ammonium
hydroxide and the concentration and degree of ionization of any
ammonium salt, which may be present with the base (see p. 161).
These data are easily obtained by direct measurement.
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