Abstract
AbstractInterionic interaction in dilute solutions of polyelectrolytes (the polymer‐concentration effect) has been discussed using an ionic distribution formula which Wicke and Eigen had proposed, introducing volume exclusion effects of the ions. Thermodynamic quantities, e.g., the activity coefficients, osmotic coefficient, and electric mobility are found to have a tendency to decrease with polymer concentration and to increase after passing through a minimum. A formulation of the “activity coefficient of macroions” has been obtained and is known to give a reasonable expression for the rate of change of the activity coefficient with the polymer concentration. The heat of dilution of polyelectrolyte solutions is shown to be positive in dilute solutions. Moreover, the treatment is extended to the titration behavior, and an interpretation is given for the characteristic run of viscosity‐concentration curves.
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