Relaxation and electrophoretic effects in polyelectrolyte solutions. I. Salt‐free solutions

Relations between relaxation and electrophoretic effects in salt‐free polyelectrolyte solutions are studied in terms of nonequilibrium thermodynamics and of binary friction coefficients. The significance and the method of determining these coefficients are explained. Consideration of experimental results and of long‐ and short‐range interactions suggests that the concept of “ion condensation” is needed to provide a consistent desciption of transport processes for linear flexible polyelectrolytes. Empirical relations previously used are shown to have only limited validity.

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