Multicomponent Polyelectrolyte Solutions. Part II. Excluded Volume Study of Polyvinylsulfonate Alkali Halide Systems

Abstract

Excluded volume theory of nonionic high‐polymer solutions has been extended to mixed polyelectrolyte‐added simple electrolyte systems. A systematic study has been undertaken of fractionated polyvinylsulfonate alkali halide systems. ``Ideal'' Θ temperatures, determined from phase separation experiments and from the vanishing of the second virial coefficient in light‐scattering experiments, agree closely with each other. At the Θ temperature the intrinsic viscosity, for all systems investigated, is closely proportional to the square root of the degree of polymerization. Unperturbed dimensions (at the Θ temperature) in various systems are discussed. The entropy parameters ψ1 * for various systems, derived from the temperature dependence of intrinsic viscosity and from phase separation, agree satisfactorily with each other. The value of ψ1 * as a function of added electrolyte type and concentration is discussed. The relation between the intrinsic viscosity—sedimentation constant and intrinsic viscosity—second virial coefficient has been examined, for selected systems, as a function of the degree of polymerization.