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
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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
«Electrolysis.»—When ions touch an electrode, they are discharged,
and with the discharge, are changed chemically, and, according to the
electron theory, also materially. Cupric ions, Cu^{2+} or Cu^{−2 ε},
receiving two electrons at the cathode, are precipitated as metallic
copper. When a current is passed through a solution of hydrochloric
acid, the hydrogen ions, by the pairing of the discharged ions,
yield hydrogen gas consisting of molecules, H_{2}; the chloride ions
are converted at the anode into chlorine Cl_{2}. The formation of
these molecules, X_{2}, may be variously interpreted, as resulting
either from the union of two discharged or neutral atoms, or as
consisting, for instance in the case of hydrogen, in the discharge
of a hydrogen ion H^{+}, at the negative electrode, ‹followed by
the assumption of a negative charge or electron by the neutral
atom›, the new ion H^{−} combining at once with the positive ion
H^{+} to form the molecule H^{+}H^{−}. At the positive pole, by an
analogous recharging of a discharged negative chloride-ion Cl^{−},
we should obtain a positive ion,[76] Cl^{+}, and immediately the
formation of Cl_{2} or Cl^{+}Cl^{−} would follow. Helmholtz advocated
the latter conception of the action at the electrodes, and, more
recently, J. J. Thomson[77] brings forward, as a very important
argument in favor of it, the fact that iodine, which according to
vapor density determinations dissociates into monatomic molecules
at high temperatures (I_{2} ⇄ 2 I), becomes, simultaneously
with this dissociation, also an excellent ‹gaseous conductor
of electricity›, as would be anticipated from a dissociation,
I^{+}I^{−} ⇄ I^{+} + I^{−}. This fact is emphasized here, because
in it we seem to have a case of ‹conductivity› coinciding with
‹gaseous dissociation›, the existence of which is recognized by the
universally accepted laws of gases, and differing in no important
respect from the dissociation assumed for conductors in solution.
«Conductivity and Dilution.»—The passage of a current through an
electrolyte consists, then, in a transfer of electricity by material
particles, the ions. According to the theory of ionization only
[p047] the ionized portion of an electrolyte can carry the current
at any moment, and, consequently, a ‹given weight› of an ionogen
should, under comparable conditions, be the more efficient as a
conductor, the more completely it is dissociated into ions.
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