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
without indicating the number of cyanide groups, CN, in the
complex, and we use the same generic ‹ending› "cyanide" as is used
to designate the simple cyanide ion, ‹e.g.› to designate the ion
formed from potassium cyanide, KCN ⇄ K^{+} + CN^{−}.
[426] The hydroxide-ion appears with the same coefficient, 1, on
both sides of the equilibrium equation and need not be included in
the mathematical statement; it would appear as a factor in both
terms of the ratio given and would cancel out.
[427] Bodländer and Fittig, ‹Z. phys. Chem.›, «39», 602 (1903).
[428] Bonsdorff, ‹Ber. d. chem. Ges.›, «36», 2324 (1903).
[429] It is also frequently called the ‹dissociation constant› of
the complex ion, indicating the tendency of the complex ion to
dissociate into its components.
[430] Two independent experimental methods were used and gave
concordant results—one having as its basis the solubility of silver
salts (chloride, bromide), the other the electrolytic potentials of
silver against ammoniacal silver solutions (see Chap. XV).
[431] ‹Bull. de la Soc. Chim. de Paris›, (3), «13», 386 (1895).
[432] We may consider the salt to be ionized to about the same
extent as ammonium or potassium nitrate in 0.05 molar solutions,
or, approximately, 87%. If we call ‹x› the concentration of
silver-ion, formed by the decomposition of the silver-ammonium-ion,
then 2 ‹x› is the concentration of the free ammonia, and
(0.05 × 0.87 − ‹x›) is the concentration of the complex ion. Since
‹x› is a small number in comparison with 0.0435, we may write, with
sufficient accuracy for our purposes,
[NH_{3}]^2 × [Ag^{+}] / [(NH_{3})_{2}Ag^{+}] =
(2 ‹x›)^2 × ‹x› / 0.0435 = 6.8E−8.
Then, ‹x› = [Ag^{+}] = 0.0009.
[433] Kohlrausch and Holborn, ‹loc. cit.›, p. 202.
[434] The dilution of the silver-ammonium nitrate (10 c.c.
to 11 c.c.) and the decrease in ionization due to the added
salt reduce the concentration of silver-ion from 0.0009 to
0.00085. [Ag(NH_{3})_{2}^{+}] = (0.05 × 10 / 11) × 0.8 = 0.0364
and 4 ‹x›^3 = 6.8E−8 × 0.0364 (see footnote, p. 220). Then
‹x› = [Ag^{+}] = 0.00085.
[435] Thiel (‹cf.› Bodländer and Fittig, ‹loc. cit.›). The
solubility given in the table at the end of the laboratory manual
refers to 18°. The constant for the complex ion was determined at
25°.
[436] The combined concentration of the salts is 0.055
and their degree of ionization may be taken as 87%, the
same as the degree of ionization of 0.05 to 0.06 molar
KNO_{3}. Then [Cl^{−}] = (0.1 × 1 / 11) × 0.87 = 0.008.
[Ag(NH_{3})_{2}^{+}] = (0.05 × 10 / 11) × 0.87 = 0.04 and
‹x› = [Ag^{+}] = 0.00089 (see the method of calculation in the
footnote, p. 220).
[437] The strong solution of ammonia is used in order to avoid
unnecessary dilution, and in the experiment, described below,
the dilution of the liquids by the added ammonia is considered
negligible.
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