Polyelectrolyte solutions + multivalent salts = phase separation

Summary A queous solutions of highly charged flexible polyelectrolytes phase separate in the presence of multivalent counterions. We present a theoretical model which explains this behavior in terms of electrostatic bridging between monomers via the condensed counterions. The ?Polymer Reference Interaction Site Model? with the Debye-Hückel closure (equivalent to the ?Random Phase Approximation?) is sufficient to understand the crucial role of the valency of the counterions, to predict a demixion above a given valency and a redissolution of the precipitate in excess of added salt. The model successfully reproduces the different experimental phase diagrams of polystyrene sulfonate suspensions with different added electrolytes. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.