Electrical and mass transport in salt-free polyelectrolyte solutions

Abstract

On the basis of non-equilibrium thermodynamic principles, a description of electrical and mass transport in salt-free polyelectrolyte solutions is given. An attempt to create a unified theory is presented by expressing transport parameters in terms of macroscopic frictional coefficients. The significance of these coefficients and how they may be determined experimentally is explained. The correlation between relaxation effects in electrophoresis, transference and self-diffusion mobilities is established. The usefulness of the formulation is substantiated with the evaluation of friction coefficients and transport parameters for some stiff polyelectrolyte models. The essential features of these models according to the state of ionization and polyion conformation are discussed. A parallel with experimental data is made.