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
If the conductivity of a given weight of hydrogen chloride, for
instance, is measured under comparable conditions, it should be
found to be greater, the more completely the acid is ionized. Now,
in aqueous solutions, hydrogen chloride ionizes under the influence
of the ‹solvent water› (pp. 41, 61), and the theory would lead us
to anticipate that the greater the proportion of water used, the
more extensively will it ionize the acid. Consequently, the addition
of water to a given weight of acid should increase the latter's
efficiency as a conductor. This conclusion has been fully verified by
exact methods of measurement and may be readily demonstrated by the
following series of experiments:
EXP.[78] An electrolytic cell, having the shape of a
parallelopipedon and a capacity of about one liter, is fitted with
electrodes of copper, which reach from the bottom to the top of
the cell and are connected with a storage cell and an ammeter. The
cell is first filled with distilled water: no perceptible current
passes through the water and the latter is therefore practically a
nonconductor. The cell is then emptied by means of a siphon and 20
c.c. of 4-molar hydrochloric acid is brought into it. The ammeter
shows that a definite current passes through the solution (0.17
ampere in an experiment[79] with a cell 4.6 cm. wide and 11.5 cm.
long, with copper electrodes 4.6 cm. broad and 21 cm. high). (See
Fig. 9, p. 48.) [p048]
[Illustration: FIG. 9.]
The conductivity of a solution, like that of a metal conductor, is
the reciprocal of its resistance. Since, according to Ohm's law,[80]
the current for a ‹given potential› is inversely proportional to
the resistance, the current is also directly proportional to the
conductivity. The resistances of the metal connections and of
the ammeter in the experiment are very small compared with the
resistance of the solution, and they may be considered negligible
for our purpose. Thus, ‹the current indicated by the ammeter is a
closely approximate measure of the conductivity of the solution›.
Now, if a volume of water (20 c.c.) equal to the volume of acid,
were to be added to the latter, the cross section through which the
current flows from plate to plate would be ‹doubled›, and, since the
conductivity of a liquid conductor, like that of a metal, increases
proportionally to the cross section, the current should be doubled by
the change in this one factor. On the other hand, the concentration
of the conducting acid is now ‹one-half› of the original
concentration, and this should in turn reduce the conductivity of the
solution to one-half. Consequently, if there were no further change
in the electrolyte, the original conductivity should be maintained
when the acid is thus diluted. But, according to the theory of
ionization, as has just been shown, the addition of [p049] water to
a given weight of hydrochloric acid ‹should increase the proportion
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