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Subsequent reports will be concerned with some
quantitative aspects of subjects treated qual itatively
in this report, and with Equilibria II and Ill,
and, hence, with oxidation-reduc
including mass transfer.
A large percentage
liquid systems can be classified as acid-base analog
reactions or as on-reduction reactions, In
most systems t re of the solvent controls
the acid-base analog reaction, while in oxidationreduction
reactions the solvent usually plays a
minor role. On the other hand, oxidation-reduction
reactions in fused hydroxides are related to acidbase
equilibria in at least three ways, First, acidbase
reactions depend on Equilibrium I and oxidation-reduction
reactions depend on Equilibrium II,
Equilibrium Ill. Second,
ent can stabilize higher
Is through solvolytic reaction.
Third, in some cases the kinetics of the
hydrogen replacement reaction in fused sodium hydroxide
appears to be dependent on acid-base equilibria
in a way analogous to similar replacement
reactions in liquid ammonia, Thus, a study of
acid-base equilibria in fused hydroxides is a necessary
prelude to a more interesting study of the
oxidation-reduction reactions whic
in the corrosion
In order to foc
acid-base analog reactions, only Equilibrium I will
This treatment is valid at lower
in the absence of strong oxidizing
or reducing - agents, -
PERIOD ENDING DECEMBER 70,1954
This “inert” behavior of the cations in ac:id-base
processes stems from tw actors: first, the large
ionic radius and small charge of the cations and,
second, the exceptionally small ionization energy
of the parent atoms.
Solvent-System Concept. In terms of the solvent-
system concept first introduced by Franklin7 for
liquid ammonia and subsequently applied by
Jander8 to a variety of liquids, it is clear that
Eq. 2 fulfills the formal requirements for CI water-
like acid-base equilibrium and, hence, that the
fused alkali-metal hydroxides may be properly
considered as acid-base solvent systems.
The remainder of this report is concerned with
a determination of the types of reaction