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
of ionized acid›, and since the ions are the carriers of the current,
the ‹conductivity› of the solution should be ‹increased› because of
this change in the ‹composition› of the electrolyte. Experiment shows
that such is the case.
EXP. 20 c.c. of water is added to the 20 c.c. of 4-molar acid in the
cell, and the mixture is stirred. The current is decidedly increased
(from 0.17 to 0.22 ampere in the experiment under discussion).
If 40, 80, 160 and 320 c.c. of water are added in succession
to the contents of the cell, the conductivity is ‹increased by
every addition of water›. But, while each addition dilutes the
acid to one-half the previous concentration, the ‹increase grows
proportionally smaller and smaller with increasing dilution›. In
the following table, "Ratios I" are the ratios of the observed
conductivities ‹to the original conductivity›, "Ratios II" the ratio
of each observed conductivity to the ‹preceding one›.
‹Concentration› ‹Observed› Ratios I. Ratios II.
‹of Acid.› ‹Conductivity.›[A]
4-molar 0.17 1 1.
2-molar 0.22 1.30 1.30
1-molar 0.26 1.53 1.18
0.5-molar 0.30 1.76 1.15
0.25-molar 0.31 1.83 1.04
0.125-molar 0.32 1.88[B] 1.03
TABLE NOTES:
A. This is an artificial scale (see text) of conductivities,
and does not represent reciprocal ohms, the standard units of
conductivity.
B. In the exact data on the conductivities of 4-molar and
1/8-molar HCl (Kohlrausch and Holborn, ‹Leitvermögen der
Elektrolyte› (1898) p. 160), the ratio 348 / 181.5, or 1.92,
is found, in place of 1.88 as observed.
We should expect, further, that the increase in conductivity, being
dependent on the increased dissociation of a finite quantity of
electrolyte, should tend towards a ‹limit›, a maximum conductivity
being reached when (practically) all the acid is ionized. As a
matter of experience, the conductivity of a given quantity of an
acid or other ionogen does tend toward a ‹limit›. In the experiment
just made, the conductivity of the acid increases very rapidly at
first, as the 4-molar acid is diluted by water; but the increase
in conductivity with the succeeding dilutions grows ‹smaller› and
‹smaller› and the conductivity is plainly approaching [p050] a limit
(see the ratios I and II in the table). For hydrochloric acid at 18°,
the limit for one mole[81] (36.5 grams HCl) at infinite dilution, as
deduced from the curve of conductivities at finite dilutions, is 384
reciprocal ohms.[82]
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