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
Now, solid ‹salts› have higher dielectric constants than has[206]
solid water, and the dielectric constant of a compound is usually
much higher in the liquid than in the solid form.[207] It is
possible, therefore, that the presence of salts in the solution
increases the dielectric or, at any rate, the ionizing power of
the solvent and there are many facts which would be explained by
such a behavior. Unfortunately for any decision of the question,
determinations of the dielectric constants of salt solutions
have given contradictory results; the more recent, and possibly
more reliable results of Drude[208] indicate that salt solutions
show approximately the same dielectric behavior as water itself.
Smale, in Nernst's laboratory, on the other hand, obtained results
indicating that salt solutions have decidedly higher dielectric
constants than pure water.[209] A final decision in the matter would
be of great importance.[210] But, as explained before (p. 64),
there are other properties of a solvent which seem to be intimately
related to its ionizing power and which may be modified by the
presence of salts, ‹i.e.› of strong electrolytes. The value obtained
for the proportion [Me^{+}] × [X^{−}] / [MeX] grows rapidly
with increasing concentration, ‹indicating a disproportionately
large ionization in the more concentrated solutions›—which is
what one would expect, if ‹electrolytes or their ions in some way
increased› the ionizing power of the medium. In agreement with such
a conclusion, Arrhenius found[211] that ‹the ionization of weak
acids›, like acetic acid, is increased by the presence of ‹foreign
neutral› salts, such as sodium chloride. This means, of course, that
the strength of acetic acid, as an acid, is increased likewise.
EXP. 0.5 c.c. of 0.1 molar acetic acid is added to 100 c.c. of a
dilute solution of methyl orange in each of three test glasses.
When some solid sodium chloride (3 grams, and then 3 grams
more—altogether 0.1 mole) is added to the one solution, a plain
increase in the intensity of the acid tint is observed.[212] The
addition of cane sugar to a second solution has no such effect.
The addition of sodium chloride to a fourth portion of the methyl
orange, to which no acetic acid has been added, shows that its
color remains unchanged: the effect on the indicator in the first
case, then, is the result of the action of the salt on the acetic
acid.[213] [p111]
The so-called "salt-effect" on the ionization of ammonium hydroxide
may be illustrated in a similar way.
EXP. 0.5 cc of 0.1 molar ammonium hydroxide is added to each of
two portions (100 c.c.) of a dilute solution of phenolphthaleïn.
When some sodium chloride solution is then added to one of
the two portions, the basicity of the solution is distinctly
increased. The addition of sodium chloride to a third portion of
the phenolphthaleïn solution shows that its own reaction to the
indicator is neutral.
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