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Correlation Analysis in Chemistry of Solutions (Hardcover)
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Correlation Analysis in Chemistry of Solutions (Hardcover)
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The behavior of substances in solutions may not be adequately
characterized by the effect of any single physicochemical parameter
of solvents, nor are numerous semi-empirical scales of the solvent
effect (their 'polarity') suitable for their limited selections
only. In recent decades, it has been found that the variation of
reaction rate constants in solutions or that spectral parameters of
dissolved substances are determined by the total effect of
different solvation processes. This monograph presents numerous
examples of such an approach and characterizes various empirical
and semi-empirical scales of solvent properties. It is shown that
additional consideration of some structural parameters of solvents,
namely, their cohesive energy and the molar volume, may provide for
spreading this approach on homolytical and catalytic reaction.
It is also shown that for the solvolysis reaction, one of the
excessive reagents may represent either a reagent or a solvent,
which requires additional consideration of its structural
characteristics in the Hammeth equation.
The application of the principle of free energy linearity also
allowed adequate generalization of data on the effect of solvents
on different physicochemical processes, such as dissolution of
gases and solids in various solvents, swelling of polymers and
solid fossil fuels, coal extraction, adsorption, absorption,
diffusion, and chromatography. Special attention is paid to
substance distribution between two immiscible phases. Properties of
both an extractive phase and an active extractant dissolved in
inert diluter are taken into account. The majority of these
processes indicate the efficiency of solvent self-association
factorthat defines the energy consumption for formation of a void
for an alien molecule injection.
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