Electrostatic contributions to thermodynamic functions of systems containing polyions and mixtures of counterions differing in charge and size

Abstract

By the combination of the analytical and numerical solutions of the Poisson–Boltzmann equation for the cell model of a polyelectrolyte solution with mixtures of counterions differing in size and charge, the electrostatic internal and free energies, degree of binding of counterions, osmotic coefficient and distribution of counterions around the polyion are calculated. These properties are presented as functions of charges, radii and mole fractions of counterions, and the possibility of their application for interpretation of the scarce experimental data is discussed.