Abstract
The results of transference number measurements in solutions of sodium and magnesium poly(styrenesulphonates) are presented, for a range of concentrations and at several temperatures. By combination with conductometric measurements, the fraction of apparently free counterions is determined, and compared with theoretical predictions. The extent of ion binding is relatively insensitive to the temperature and, for sodium poly(styrenesulphonate) solutions, is in very good agreement with the predictions of the cylindrical cell model for polyelectrolyte solutions. The theory is less satisfactory for solutions with divalent magenesium counterions, unless corrections beyond the mean-field/ Poisson-Boltzmann approximation are introduced. A higher degree of binding of magnesium ions at lower temperature indicates the existence of noncoulombic ion-polyion forces. Conductivity and transference measurements provide information about the hydrodynamic friction coefficients of the polyion, the temperature dependence of which is predicted roughly by the Walden relation. No evidence for significant conformational changes is obtained.
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