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
We will turn now to the consideration of evidence bearing on the
theory of ionization, found in the data on osmotic pressure.
The apparent molecular weight of hydrogen chloride is found to
be smaller than 36.5, when determined in aqueous solution (p.
37), and it is found to approach the limit 18.25 as a more and
more dilute acid is used.[114] The value found represents the
average molecular weight of all the molecules in any solution,
the osmotic pressure, freezing-point or boiling-point of which
has been taken. It is evident that, if there is dissociation
of hydrogen chloride into hydrogen and chloride ions, the
average values found for the molecular weight must be lower
than 36.5, ‹must be variable›, and must ‹approach› the ‹limit›
18.25, as the dissociation into the smaller molecules becomes
more and more complete. Such a result is, therefore, what we
would anticipate on the basis of the theory of ionization. For
a salt like potassium chloride KCl, a similar tendency toward
a minimum, average molecular weight of (K^{+} + Cl^{−}) / 2 or
(39.1 + 35.5) / 2 = 37.3 would be anticipated, and, as a matter of
fact, molecular weight determinations with potassium chloride in
aqueous solution give results agreeing with such a tendency.[115]
For a salt like calcium chloride, on the other hand, we would
expect that its ionization into ‹three› ions, according to the
equation CaCl_{2} ⇄ Ca^{2+} + 2 Cl^{−}, would give a minimum,
not of one-half the formula weight, but of one-third, viz.,
(Ca^{2+} + 2 Cl^{−}) / 3 or (40 + 71) / 3 = 37, when the molecular
weight determination is carried out in aqueous solution. As a matter
of fact, with salts of this type, the determinations, by osmotic
pressure methods, indicate a dissociation into ‹three› smaller
components, as required by the theory. It may be added that, for
[p068] a salt, sodium mellitate, Na_{6}(C_{12}O_{12}), the salt of
a hexabasic acid, Taylor found average molecular weights tending
to a minimum of ‹one-seventh› of the formula weight, as we should
expect from the ionization of the salt into seven smaller molecules,
(C_{12}O_{12})Na_{6} ⇄ 6 Na^{+} + (C_{12}O_{12})^{6−}.
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