Pure and Applied Chemistry

Abstract: A short review of recent theoretical and experimental advances in studies of polyelectrolyte solutions is presented. The focus is on ion-specific effects as revealed in measurements of osmotic pressure and enthalpy of dilution. We review the experimental results for two different polyelectrolyte systems: (i) salts of polyanetholesulfonic acid, and (ii) aliphatic ionenes (polycations) in aqueous solution with various counterions. A theoretical approach based on the extension of Wertheim's integral equation theory [J. Stat. Phys. 35, 19 (1984)] is used to analyze the experimental data. Preliminary results, based on the all-atom simulation of model 3,3 ionene oligomers, are discussed in the light of polyelectrolyte hydration.