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
[544] The potential of a solution of the iron salts is given by
ε = 0.058 log(10^{17} × [Fe^{3+}] / [Fe^{2+}]). In a solution of
a ferric salt, if [Fe^{2+}] = 0, the potential would obviously be
∞, which could not present a condition of equilibrium. Equilibrium
is established in such a solution, as will be shown further on
in the text, by the liberation of chlorine and the formation of
ferro-salt, according to 2 Fe^{3+} + 2 Cl^{−} ⇄ 2 Fe^{2+} + Cl_{2},
until the potential, resulting from the tendency of chlorine to
form chloride-ion, just balances the tendency of the ferric-ion
to form ferro-ion. But when a ferric chloride solution is used
as the source of supply of positive electricity, as in the
experiment described in the text, ‹both› the ferric-ion and the
chlorine tend to charge the platinum electrode with positive
electricity and to revert to a condition of equilibrium in
reference to their individual constants. The relations are much
like those between a cupric salt solution and a copper plate: if
[Cu^{2+}] > K_{Cu^{2+}}, equilibrium will be established, as we
have seen, by the positive charging of the plate in sufficient
degree to oppose the tendency of the cupric-ion to discharge (see
p. 259). But when the solution and plate are used as the source of
supply for an electric current (p. 264), both the positive charge
on the plate, and the tendency of the cupric-ion to discharge and
acquire the concentration [Cu^{2+}] = K_{Cu^{2+}}, will supply
the positive current. In calculations we ignore the positive
charge already deposited on the plate and deal only with the
concentration of Cu^{2+}. The chlorine, liberated in a solution of
ferric chloride, plays practically the same rôle as does the copper
plate in a cupric salt solution, and it can be ignored in the
discussion of the combination described in the text. In a ferrous
salt solution, in a similar manner, some ferric-ion must always be
formed by liberation of hydrogen (see p. 282), until equilibrium
is reached according to 2 Fe^{2+} + 2 H^{+} ⇄ 2 Fe^{3+} + H_{2}.
Hydrogen plays here the same rôle as chlorine does in the ferric
chloride solution.
[545] The condition for equilibrium is [Fe^{2+}] : [Fe^{3+}] =
10^{17}, in a solution considered for itself.
[546] This ratio need not be 10^{17}, since we have two solutions
combined with each other and the total potential will be expressed
by:
ε = ε_{1} − ε_{2} = 0.058 (log(10^{17} × [Fe^{3+}]_{1} /
[Fe^{2+}]_{1}) − log(10^{17} × [Fe^{3+}]_{2} / [Fe^{2+}]_{2}))
= 0.058 log([Fe^{3+}]_{1} × [Fe^{2+}]_{2} /
([Fe^{2+}]_{1} × [Fe^{3+}]_{2})).
Equilibrium is reached when the total potential is 0. Then
[Fe^{3+}]_{1} × [Fe^{2+}]_{2} / ([Fe^{2+}]_{1} × [Fe^{3+}]_{2}) = 1
and [Fe^{2+}]_{1} / [Fe^{3+}]_{1} = [Fe^{2+}]_{2} / [Fe^{3+}]_{2}.
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