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
We see, then, that copper would be directly in equilibrium with
solutions of cupric salts only if they contain this exceedingly
minute concentration of cupric ions. When such is the case, the
ionization of the metal and the formation of the metal, by the
deposit of discharging ions, may be considered to proceed ‹with the
same velocity› (p. 94).
But, if the metal is dipped into a solution of greater concentration
of cupric ions than that represented by the constant, say into a
solution of 0.1 molar copper sulphate, the velocity of deposition
of the metal would be proportionally increased (p. 92), while the
velocity of ionization and solution of the metal would remain
unchanged. We would consequently have the ions discharging and
forming metal more rapidly than they are formed. A condition of
change, not of equilibrium, exists. If we [p260] consider the
changes that must occur, we see that the ions, discharging on the
metal, would ‹charge› it with ‹positive electricity›, and the
positive charge would, in turn, repel from the metal the positive
cupric ions remaining in the solution. Equilibrium would be expected
to result when the charge on the plate becomes heavy enough to repel
from the film, immediately surrounding it, all the cupric ions
excepting those representing a concentration of 8E−22, as required
by the value of the equilibrium constant. The positive charge on the
plate would attract and hold negative sulphate ions, freed by the
discharge of cupric ions, in a kind of "double layer," the surface of
the metal holding positive charges and the film of liquid in contact
with it holding an excess of negative ions. An ‹electric potential›
would thus be established between the positive metal and the negative
solution, bathing it.[527] It is evident that the more concentrated
the solution of cupric ions, the heavier the charge must be that
will be required to repel the cupric ions sufficiently to establish
equilibrium.[528]
If copper is placed in a solution in which the concentration of the
cupric ions is smaller than the constant 8E−22, the velocity of
ionization will be greater than the velocity of the deposition of the
metal. The ions formed, having assumed positive charges, will leave
a negative charge on the metal, and, as a result of the electrical
attraction, a "double layer," surrounding the metal, will again be
formed, the positive ions clinging to the negative metal. Equilibrium
will be reached when the concentration of the cupric ions originally
present, increased by the new ions formed in this "double layer,"
will have reached, in the film bathing the plate, the concentration
demanded by the equilibrium constant. An electrical potential will
be established as before, the metal being negative, the solution, in
this case, positive.
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