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.