Colligative properties of polyelectrolyte solutions. V. Activity coefficients of counter‐ and by‐ions

Simultaneous measurements of the activity coefficients of counter‐ and by‐ions in polyelectrolyte solutions were carried out. Sodium polyvinyl alcohol sulfate was used as the sample of polyelectrolyte and sodium chloride as the extraneous salt. The activity coefficient of sodium counter‐ion was determined by using a sodium amalgam electrode and that of chloride ion was determined by a sliver‐silver chloride elctrode. It was found that the activity coefficient of both counter‐ and by‐ions has little relationship with the volume of polymer coil, and that the additivity of counter‐ion activity found for hydrogen ion by Mock and Marshall holds also for sodium ion. It was also found that there is good agreement between the experimental results and the theory of Katchalsky and Lifson if we use their same theory for calculating the volume of polymer coil, although the volume is too large to be considered reasonable.