Thermodynamic study of aqueous solutions of polyelectrolytes of low and medium charge density without added salt by direct measurement of osmotic pressure

A special block osmometer has been constructed and applied to a systematic study of poly (vinyl alcohol and vinyl sulphate ester) (PVS) sodium salts in dilute and moderately concentrated salt free aqueous solutions. In order to avoid surely ionic contamination all parts of the equipment that can contact with the polyelectrolyte solutions were made of different kinds of plastics and glass. The pressure range spans from (50 to 1.3 · 10⁵) Pa. The measuring system was found to be appropriate for determination of the molar mass of water soluble polymers, too. Above a certain analytical density of dissociable groups (ADDG) an ion size dependent transition was observed on the reduced osmotic pressure vs. concentration curves. The analysis of the osmotic pressure data has clearly revealed that the dependence of the degree of dissociation on ADDG calculated at zero polyelectrolyte concentration contradicts to ‘ion condensation’ theory. With increasing polyelectrolyte concentration the degree of dissociation decreased rather steeply but at very low concentrations sharp maximums appeared due either to the change in conformation of these charged macromolecules, or formation of dynamic clusters induced by salting out of neutral parts of the macromolecules by the ionized groups. The applicability of the scaling concept as well as the many possible ways of characterization of non-ideality of polyelectrolyte solutions will be discussed in detail.