On the Self-Diffusion of Ions in a Polyelectrolyte Solution

The self-diffusion of ions in a polyelectrolyte solution is investigated both with respect to the average time an ion is associated with a particular polyelectrolyte molecule and with respect to the effect of the electrostatic field of the macro-ions on the macroscopic self-diffusion constant. The results on the macroscopic self-diffusion constant are shown to be generally compatible with experiments on self-diffusion of counterions in polyelectrolyte solutions. On the other hand, the study of the time of association of a counterion with a particular macro-ion yields results which cannot be reconciled with the common interpretation of transference experiments on the same solutions.