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
In accordance with the convention as to signs, adopted in this
book, the ratio of concentrations (C / K), used in the logarithm
of Nernst's formula, is the ‹reciprocal› of the ratio usually
given. The change has been made in order that the algebraic signs
of the values obtained from the application of the formula should
be the same as those observed in the experimental arrangements, as
demanded by the convention.
[532] When two electrodes are combined to form an electric cell
or couple, the potential difference of the couple is always
the (algebraic) ‹difference› of the two individual electrode
potentials, and hence these are ‹subtracted› from each other
(algebraically). The electrode of the first term of the difference
(the minuend) is named first in the subscript of the potential
of the couple; then the sign of the difference represents the
character of the charge on that electrode, in agreement with the
convention (see footnote 2, p. 261). In illustration: two copper
electrodes may be taken, each of which, considered by itself,
carries a positive charge, because the concentrations of the
cupric-ion in the solutions bathing them are both greater than
K; when they are combined, each of the two electrodes will tend
to send a positive current, in ‹opposite› directions, into the
metal connecting them. But the potential of the electrode with the
heavier charge (the one dipping into the solution containing the
greater concentration of cupric-ion) will overcome the potential
of the other electrode, and the current will flow, through the
connecting metal, with a potential that represents the difference
between the two values. If the electrode of the more concentrated
solution is named first in the subscript of the potential of the
couple, its individual electrode-potential appears as the first
term of the difference (the minuend) and is reduced by the value
of the electrode-potential of the second electrode; as this is
numerically smaller than the value of the minuend, the difference
will be positive, showing that the electrode in the stronger
solution, named first in the subscript of the potential difference
of the couple, carries a positive charge. Further, if the second
electrode dips into a solution, in which the concentration of the
cupric-ion is smaller than K, the logarithmic expression for its
electrode-potential will be found to give a negative value; and
the (algebraic) subtraction of this negative quantity from the
electrode-potential of the first electrode will give a larger
potential difference, for the couple, than that possessed by the
first electrode alone—all of which agrees with the experimental
results, when such combinations are made.
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