Formal Separation of Solvent Effects

Formal Separation of Solvent Effects We consider the transition 

The symbols in (8.8.2) are similar to the symbols in (8.7.5). AUis the energy change for the transition (8.8.1) in vacuum, fV(a vv) is the coupling work of the solute a (either U or F) to the solvent w (which may be pure liquid or any mixture of liquids), and is the thermodynamic standard Gibbs energy change for the specific reaction (8.8.1). In (8.7.5) we also included in Qa the momentum PF of each solute. Here, the momentum PFs of U and F are the same and therefore cancel out in (8.8.2). The solvent-induced contribution to AG° is defined as in (8.7.7) by 

The solvent contribution defined in (8.8.2) can be expressed as a ratio of two average quantities i.e., 

In order to proceed with the analysis of the various contributions to 5G(U F), we use the same division of the solute-solvent interaction as in (8.7.11) or (8.7.12). We shall find both of these useful, depending on how we want to estimate the overall value of 5G and on the availability of relevant experimental data (see section 8.8.2). In the following we shall use the notation of (8.7.22), i.e.. 

The classification of all FGs into three groups is essentially the same as in section 8.7.2. Briefly, a FG belongs to the E group if 

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