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Understanding chemical reactivity has been the permanent concern of
chemists from time immemorial. If we were able to understand it and
express it quantitatively there would practically remain no
unsolved mystery, and reactions would be fully predictable, with
their products and rates and even side reactions. The beautiful
developments of thermodynamics through the 19th century supplied us
with the knowledge of the way a reactions progresses, and the
statistical view initiated by Gibbs has progressively led to an
unders tanding closer to the microscopic phenomena. But is was
always evident to all that these advances still left our
understanding of chemical reactivity far behind our empirical
knowledge of the chemical reaction in its practically infinite
variety. The advances of recent years in quantum chemistry and
statistical mechanics, enhanced by the present availability of
powerful and fast compu ters, are very fast changing this picture,
and bringing us really close to a microscopic understanding of
chemical equilibria, reaction rates, etc.... This is the reason why
our Society encouraged a few years ago the initiative of Professor
Savo Bratos who, with a group of French colleagues, prepared an
impressive study on "Reactivite chimique en phase liquide," a
prospective report which was jointly published by the Societe Fran"
The presence of freely moving charges gives peculiar properties to
electrolyte solutions, such as electric conductance, charge
transfer, and junction potentials in electrochemical systems. These
charges play a dominant role in transport processes, by contrast
with classical equilibrium thermodynamics which considers the
electrically neutral electrolyte compounds. The present status of
transport theory does not permit a first prin ciples analys1s of
all transport phenomena with a detailed model of the relevant
interactions. Host of the models are still unsufficient for real
systems of reasonable complexity. The Liouville equation may be
adapted with some Brownian approximations to problems of interact
ing solute particles in a continuum (solvent>; however, keeping
the Liouville level beyond the limiting laws is an unsolvable task.
Some progress was made at the Pokker-Planck level; however, despite
a promising start, this theory in its actual form is still unsatis
factory for complex systems involving many ions and chemical reac
tions. A better approach is provided by the so-called Smoluchowski
level in which average velocities are used, but there the hydrodyna
mic interactions produce some difficulties. The chemist or chemical
engineer, or anyone working with complex electrolyte solutions in
applied research wants a general representa tion of the transport
phenomena which does not reduce the natural complexity of the
multicomponent systems. Reduction of the natural complexity
generally is connected with substantial changes of the systems."
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