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Pure Appl. Chem., 2008, Vol. 80, No. 6, pp. 1253-1266

Polyelectrolyte hydration: Theory and experiment

Vojko Vlachy

Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, SI-1000 Ljubljana, Slovenia

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.