Contributions of the polyion and counterions to the internal and free energies of polyelectrolyte solutions

摘要

From the solution of the Poissonndash;Boltzmann equation for the cell model of a polyelectrolyte solution, the contributions of the polyion and counterion to the electrostatic internal and free energies, and to the heat of dilution, are calculated. Computations are made not only for polyelectrolyte solutions containing one kind of counterions species, but also for mixtures of counterions differing in charge and size. The results are presented as functions of the polymer concentration, its degree of ionization, and valencies and mole fractions of the counterions.