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
presumably, would the dissociating power of such a molecule be. The
dissociation may be effected, possibly, by the ‹action of these
intensified charges› upon ‹charges already existing›[108] within the
molecule of the dissolved ionogen.
In liquid ammonia we might well have, for instance, the action
^{+}NH_{3}-NH_{3}^{−} + HCl ⇄ ^{+}(NH_{3}-NH_{3})H + Cl^{−}, or
^{+}NH_{3}-NH_{3}^{−} + H^{+}Cl^{−} ⇄ ^{+}(NH_{3}-NH_{3})H + Cl^{−}.
Now, in liquid ammonia, the salts NH_{4}Cl, NH_{4}NO_{3} [or, more
probably, (NH_{3})_{‹x›}HCl, (NH_{3})_{‹x›},HNO_{3}] have the
functions of the aqueous acids[109]; that is, the ‹hydrogen-ion›
of the acids is found ‹combined with the solvent› ammonia. The ion
^{+}(NH_{3}-NH_{3})H, and similar ions in liquid ammonia, would
correspond then to what is considered the hydrogen-ion in aqueous
solutions[110] (formed according to HCl ⇄ H^{+} + Cl^{−}, as
ordinarily written), and the ‹polarized charges on molecules› like
^{+}NH_{3}-NH_{3}^{−} appear thus as ‹possible active agents› in
this dissociation of the hydrogen chloride molecules. [p066]
Now, it is a significant fact that all the best ionizing solvents
are compounds whose simple ‹molecules are unsaturated› exactly like
those of ammonia; this is true for water H_{2}O, the unsaturated
character of whose oxygen atom is now universally recognized. It
is now a familiar fact that liquid water is not represented by the
formula H_{2}O but consists of more complex molecules (H_{2}O)_{n}.
According to the most recent investigations,[111] while steam is
H_{2}O, or monohydrol, ice is trihydrol (H_{2}O)_{3}, and liquid
water, at ordinary temperatures, a mixture consisting chiefly of
dihydrol (H_{2}O)_{2}, some trihydrol, and very little monohydrol.
The proportion of the last appears to increase with a rise of
temperature; the proportion of trihydrol seems to increase with a
fall in temperature. One can easily see how such aggregates would
result from the saturation of the free charges on oxygen, by further
molecules of water. One can also see that such an association of
water molecules could leave a positive and a negative charge on the
associated molecules, which would be ‹polarized› and more effective
than the simple molecule would be.
That the molecule of hydrogen cyanide contains a similarly
unsaturated atom was demonstrated by Nef.[112] He proved that the
behavior of hydrocyanic acid agrees with the structure expressed
by the formula HN=C=, which we may well write HN=C^{±}. In sulphur
dioxide, another good ionizing solvent, we have, similarly,
unsaturated sulphur, the sulphur atom being here quadrivalent,
whereas its maximum valence is six.
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