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 would thus have a silver-ammonium ion, [(NH_{3})_{2}Ag]^{+},
and its hydroxide, silver-ammonium hydroxide, corresponding to the
[p219] ammonium ion and its hydroxide, ammonium hydroxide. The
properties of ammoniacal solutions of silver oxide are in entire
agreement with this conception. The hydroxide is a stronger base than
barium hydroxide.[428] It forms salts, [(NH_{3})_{2}Ag]X, in which
silver appears as part of a so-called positive "complex ion." The
hydroxide, like ammonium hydroxide, is unstable and is only known
in solution and in the presence of free ammonia, exactly as is the
case for ammonium hydroxide. The mathematical equation expressing the
equilibrium conditions for the complex ion,
[NH_{3}]^2 × [Ag^{+}] / [(NH_{3})_{2}Ag^{+}] = K_{Instability},
gives a ‹definite measure› of the ‹stability› of this complex ion.
It is clear, that the ‹larger› the constant, the more ‹unstable› the
complex ion would be, and so the constant is called the ‹Instability
Constant›[429] of the complex silver-ammonium-ion. Bodländer found
the value of the constant to be 6.8E−8 at 25°.[430]
According to the composition of the complex ion, two molecules of
ammonia should be required for every molecule of silver nitrate,
to produce a solution containing the nitrate of the complex ion:
Ag^{+} + NO_{3}^{−} + 2 NH_{3} ⇄ [(NH_{3})_{2}Ag]^{+} + NO_{3}^{−}.
As a matter of fact, 20 c.c. of a molar solution of ammonium
hydroxide (= 200 c.c. of a 0.1 molar solution) must be added to
100 c.c. of a 0.1 molar solution of silver nitrate, to convert the
silver nitrate into the salt of the complex silver-ammonium-ion.
If the ammonium hydroxide solution is allowed to flow slowly, from
a pipette, into the silver nitrate solution, we find that the last
trace of the precipitated silver hydroxide redissolves just as the
‹last› drop or two of the 20 c.c. is added to the mixture (‹exp.›).
Working more exactly, Reychler[431] found that the addition of
ammonia to a silver nitrate solution, in the proportion of two
molecules of the former to one of the nitrate, does not change the
freezing-point of the solution, and therefore [p220] does not
increase the total number of molecules in the solution. This result
agrees with the conception that two molecules of ammonia combine with
one silver ion to form a complex ion.
«Application in Analysis.»—Turning now to the consideration of
the bearing of these relations on the detection of silver-ion in
analysis, we may conclude, in the first place, from the value of
the constant as given, that only a ‹small proportion› of the total
silver in such ammoniacal solutions is present in the form of
silver-ion; but, in the second place, there is, at least, a ‹portion›
of the silver present in the form of its ion—it is ‹not entirely›
suppressed; and, in the third place, it is clear, from the form of
the equilibrium equation, that any ‹excess› of ‹ammonia› must very
rapidly reduce the ‹concentration of silver-ion› in such solutions.
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