Specific Solvation Effects on Reaction Rates

(5-99) was checked in detail in a large number of studies, but an extensive treatment of primary and secondary salt effects on reaction rates is beyond the scope of this Section. The reader is referred to references [2-5, 11, 12, 19-21, 28], particularly to the excellent comprehensive reviews of Davies [260], Blandamer et al. [828], and Loupy et al. [829]. 

In conclusion, it can be said that the electrostatic theory of solvent effects is a most useful tool for explaining and predicting many reaction patterns in solution. However, in spite of some improvements, it still does not take into account a whole series of other solute/solvent interactions such as the mutual polarization of ions or dipoles, the specific solvation etc., and the fact that the microscopic relative permittivity around the reactants may be different to the macroscopic relative permittivity of the bulk solvent. The deviations between observations and theory, and the fact that the relative permittivity cannot be considered as the only parameter responsible for the changes in reaction rates in solution, has led to the creation of different semiempirical correlation equations, which correlate the kinetic parameters to empirical parameters of solvent polarity (see Chapter 7). 

The intermolecular forces responsible for the association of dissolved ions or molecules with solvent molecules, consist of other forces beside the non-specific directional, indue- 

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Specific Solvation Effects on Reaction Rates 269 5.5.6 Solvent Influence on the Reactivity of Ambident Anions... 

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