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
The sulphides of the metal ions of the zinc group are readily
precipitated by ammonium or sodium sulphide, but hydrogen sulphide,
in the presence of a small excess of a strong acid, such as
hydrochloric acid, does not precipitate any of these sulphides (or
any of the sulphides of the aluminium, the alkaline earth and the
alkali groups). Under the same conditions ‹the sulphides of the metal
ions of the silver group›, Ag^{+}, Hg^{+}, Pb^{2+}, of ‹the copper
group›, Hg^{2+}, Pb^{2+}, Bi^{3+}, Cu^{2+}, Cd^{2+}, and also of ‹the
arsenic group›, As^{3+}, As^{5+}, Sb^{3+}, Sb^{5+}, Sn^{2+}, Sn^{4+},
Pt^{2+}, Pt^{4+}, Au^{+}, and Au^{3+}, are precipitated. Advantage
is taken of these relations in the following way, in systematic
analysis: after the separation of the silver group, by precipitation
of the difficultly soluble chlorides, hydrogen sulphide, in the
presence of an excess of acid, is used to precipitate the sulphides
of the ions of the copper and the arsenic groups, the two groups
being precipitated together. Hydrogen sulphide, under these
conditions, does not precipitate any sulphides of the zinc group or
those of any of the remaining groups. Hydrogen sulphide is used, in
this way, as one of the most valuable reagents in analytical work,
enabling the analyst to separate whole groups of metal ions from
other groups. There is also no other agent, equally important, which
is more likely to be used in a wrong way and to lead to error.
«The Ionization of Hydrogen Sulphide.»—Before taking up the theory
of the separation of these groups by precipitation with hydrogen
sulphide in the presence of a strong acid, a discussion of some
of the characteristics of the reagent will be in place. Hydrogen
sulphide, like carbonic acid and other dibasic acids, ionizes in
two stages; it produces first hydrogen-ion and hydrosulphide-ion,
HS^{−}, and this ion in turn dissociates, producing hydrogen-ion and
sulphide-ion, S^{2−}. [p200]
For the first dissociation, HSH ⇄ H^{+} + HS^{−}, we have
[H^{+}] × [HS^{−}] / [H_{2}S] = K_{1} (I)
The value of the constant[395] for this primary ionization of
hydrogen sulphide is 0.91E−7. It is apparent that hydrogen sulphide,
even in the primary ionization, is a very weak acid and produces
a very small concentration of hydrosulphide-ion. In a solution,
saturated at 25°, the total concentration of hydrogen sulphide is
approximately 0.1 molar, and the concentration of hydrosulphide-ion,
therefore, in the absence of any foreign acid, at most[396] 0.95E−4.
The concentration of the dissolved, nonionized hydrogen sulphide,
[H_{2}S], is practically a constant, if solutions saturated with
hydrogen sulphide under a given pressure, say under atmospheric
pressure, are considered. For such solutions, then, we may put more
simply[396]
[H^{+}] × [HS^{−}] = ‹k› = (0.95E−4)^2 = 0.9E−8. (II)
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