Solvation entropy

Having defined the process of solvation, we proceed to introduce the corresponding thermodynamic quantities. We shall henceforth talk about solvation entropy, solvation energy, solvation volume, and so on, meaning the change in the corresponding thermodynamic quantity associated with the solvation process as defined above. 

Lynden-Bell R M and Rasaiah J C 1997 From hydrophobic to hydrophilic behavior a simulation study of solvation entropy and free energy of simple solutes J. Chem. Phys. 107 1981... 

Although the right-hand sides of Eqs. (8.27) and (8.28) are the same, the former applies to the mixture (subscript mix), while the latter applies to the mixing process (subscript m). The fact that these are identical emphasizes that in Eq. (8.27) we have calculated only that part of the total entropy of the mixture which arises from the mixing process itself. This is called the configurational entropy and is our only concern in mixing problems. The possibility that this mixing may involve other entropy effects—such as an entropy of solvation-is postponed until Sec. 8.12. 

The quantity in parentheses on the right-hand side is reminiscent of the expression AH - T AS, with the quantity 1/2R a contribution from the configurational entropy of the Flory-Huggins theory. Since our objective is to incorporate a solvation entropy into the discussion, we add the latter -in units of R for convenience-to 1/2R ... 

Whether AH for a projected reaction is based on bond-energy data, tabulated thermochemical data, or MO computations, there remain some fundamental problems which prevent reaching a final conclusion about a reaction s feasibility. In the first place, most reactions of interest occur in solution, and the enthalpy, entropy, and fiee energy associated with any reaction depend strongly on the solvent medium. There is only a limited amount of tabulated thermochemical data that are directly suitable for treatment of reactions in organic solvents. Thermodynamic data usually pertain to the pure compound. MO calculations usually refer to the isolated (gas phase) molecule. Estimates of solvation effects must be made in order to apply either experimental or computational data to reactions occurring in solution. 

Similar observations hold for solubility. Predominandy ionic halides tend to dissolve in polar, coordinating solvents of high dielectric constant, the precise solubility being dictated by the balance between lattice energies and solvation energies of the ions, on the one hand, and on entropy changes involved in dissolution of the crystal lattice, solvation of the ions and modification of the solvent structure, on the other [AG(cryst->-saturated soln) = 0 = A/7 -TA5]. For a given cation (e.g. K, Ca +) solubility in water typically follows the sequence... 

However, solubility, depending as it does on the rather small difference between solvation energy and lattice energy (both large quantities which themselves increase as cation size decreases) and on entropy effects, cannot be simply related to cation radius. No consistent trends are apparent in aqueous, or for that matter nonaqueous, solutions but an empirical distinction can often be made between the lighter cerium lanthanides and the heavier yttrium lanthanides. Thus oxalates, double sulfates and double nitrates of the former are rather less soluble and basic nitrates more soluble than those of the latter. The differences are by no means sharp, but classical separation procedures depended on them. 

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