Exploring the interactions in binary mixtures of polyelectrolytes: Influence of mixture composition, concentration, and temperature on counterion condensation

The counterion condensation in the binary mixtures of like-charged polyelectrolytes with two different molecular weights, where both are negatively charged, has been studied by conductance measurement in aqueous medium. Sodium polystyrenesulfonate with two different chain lengths have been selected as model polyelectrolyte and the investigation has been carried out in the absence of any added salt. The specific conductance-polyelectrolyte concentration data were analyzed in the light of the scaling argument for the conformation of polyion chains in solutions to quantify the fractions of free counterions. Effects of polyelectrolyte concentration, molecular weights of the components of the mixture, and solution temperature on the condensation of counterions have been investigated to explore polyion-counterion interaction, and inter- and intra-chain interactions in these polyelectrolyte mixtures. This investigation revealed that the extent of counterion condensation is significantly influenced by the mixture composition, the polyelectrolyte concentration and the temperature. Evaluation of the polyion transference numbers provided important information as to the direction of the motion of the counterions under the action of the applied electric field.