Towards a modellisation of the solvation energy in multi-component solvents. The interesting case of a charged solute imbedded in a polymer-containing electrolyte solution

In this paper we propose a mean-field theory to calculate the solvation free energy of a charged solute imbedded in a complex multi-component solvent. We considered a solvent made up of a mixture of small (electrolyte solution) and large (polymer) components. The presence of macromolecules ensures reduced mixing entropy among the different solvent components, an effect due to polymer connectivity. The reduced entropy favours strong preferential distribution of a particular solvent even in the presence of weak preferential solute–solvent interactions. In addition, two energy terms must be considered: (a) the interaction between the solute electrostatic potential and the electrolyte solution and (b) the formation of a polymer–solute interface. Because of the different dielectric permittivity of the solvent components, the electrolyte and polymer distribution functions are strongly coupled: ions, indeed, are more solvated in regions of higher local dielectric permittivity arising from the inhomogeneous mixing of solvent and polymer. We combined together the different energy terms in the framework of the de Gennes free energy functional for polymer solutions along with a generalised Poisson–Boltzmann equation developed for inhomogeneous dielectric media. Moreover, the preferential electrolyte solvation in regions of greater polarity was considered by an extension of the Born equation. Setting the polymer dielectric permittivity smaller than the solvent one and making null the specific polymer–solute interactions, we calculated enhanced electrolyte concentration and reduced polymer concentration near the solute surface on raising the solute surface charge density. The theory shows also the breakdown of the widely used separation between electrostatic and surface tension-dependent contributions to solvation energy when non-ideal mixed solvents are considered. In fact, according to the model, the surface tension of such mixed solvents strongly depends on the solute surface charge density: at high potentials the interfacial tension may increase rather than decrease on raising the polymer volume fraction. The theoretical results have been compared with experimental data on polymer+electrolyte solution surface tension and with solubility data of colloidal particles. The comparison evidences the complex behaviour of multi-component solvents going well beyond the trivial weighted average of the dielectric permittivity and surface tension of the isolated chemical components. Deviations from the simple behaviour predicted by an average picture of multi-component solvents could be understood by developing more sophisticated, but still simple, approaches like that proposed in this paper.Contribution to the Jacopo Tomasi Honorary Issue. This paper is dedicated to Jacopo Tomasi. I learned much of the difficult art of transforming complex problems into simple models after reading his early works on solvation energy.