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
[438] The following solubilities have been determined at 25°:
[Ag^{+}] × [Cl^{−}] = 2E−10; [Ag^{+}] = 1.4E−5.
[Ag^{+}] × [I^{−}] = 1E−15; [Ag^{+}] = 1E−8.
[Ag^{+}]^2 × [S^{2−}] = 4E−50; [Ag^{+}] = 4.3E−17.
[439] 100 c.c. molar ammonia dissolves at 25° only 0.6 milligram of
silver iodide (Bodländer, ‹loc. cit.›, p. 606).
[440] Fresenius, ‹Qualitative Analysis›, p. 378.
[441] In regard to Cu(NH_{3})_{4}^{2+} see Locke and Forssall,
‹Am. Chem. J.›, «31», 268, 297 (1904), and Dawson, ‹J. Chem. Soc.›
(London), «89», 1674 (1906).
[442] Euler, ‹Ber. d. chem. Ges.›, «36», 3403 (1903).
[443] See footnote, p. 212.
[444] See pp. 165, 210 and 213.
[445] The acid HAg(CN)_{2}, corresponding to the salt, is
crystallizable and is a strong acid. It is largely decomposed, by
water, into silver cyanide and hydrocyanic acid.
[446] See the experiments described on pp. 45 and 89.
[447] In solutions containing an excess of potassium cyanide
greater than 0.05 molar, the salt K_{2}[Ag(CN)_{3}] is formed.
The dissociation or instability constant for the complex ion
Ag(CN)_{3}^{2−} is 1E−22.
[448] ‹Z. anorg. Chem.›, «39», 222 (1904).
[449] The solubility-product constant for silver chloride at
25° is 2E−10. If the concentration of chloride-ion be made
1.0 by the addition of potassium chloride to a 0.05 molar
solution of KAg(CN)_{2}, then the concentration of silver-ion,
necessary for the precipitation of the chloride, would be
K_{S.P.} / [Cl^{−}] = 2E−10 gram-ion. Neglecting the fact
that the complex salt is not completely ionized and putting
[Ag(CN)_{2}^{−}] = 0.05, and calling ‹x› the concentration of the
cyanide-ion just necessary to prevent the precipitation of the
chloride, we have:
[Ag^{+}] × [CN^{−}]^2 / [Ag(CN)_{2}^{−}] =
2E−10 × ‹x›^2 / 0.05 = 10^{−21}.
We find ‹x› = 5E−7 mole, or approximately 0.03 milligram potassium
cyanide (cyanide-ion) per liter. This minute quantity of free
cyanide, if not originally present in the solution used, would be
formed by the liberation of potassium cyanide from the complex
(according to KAg(CN)_{2} + KCl → AgCl + 2 KCN) as soon as 2.5E−7
mole, or 0.036 milligram, of silver chloride per liter have been
formed, a quantity too small to be perceptible.
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