Intrinsic viscosities [η], sedimentation coefficients s, radii of gyration Rg and second virial coefficients A2, refractive index increments and apparent specific volumes were determined in aqueous solution in theta solvents and over a wide range of concentrations ms of a supporting electrolyte KCl, for five samples of potassium polystyrene sulfonate prepared by sulfonation of narrow molecular weight distribution polystyrenes. Coil expansion coefficients α as well as the Flory coefficient Φ relating [η] to coil dimensions were evaluated. Following a theory of Alexandrowicz, α2 was found to be a linear function of M1/4 m−1/3S; Φ appears to decrease with increase in α. The low values of Φ, characteristic for polyelectrolyte solutions, are consistent with the value determined for the Mandelkern‐Flory parameter β = Φ1/3 P−1.

The conductance of aqueous polyelectrolyte solutions was determined at 25°C in the frequency range 400 Hz-100 kHz ; both capacitance and conductance were determined between 0 6 and 30 MHz. Various salts of polystyrenaulphonic acid, polyvinylsulphonic acid and polyacrylic acid with univalent counterions (H+, Li+, Na+, K+, Cs+, (CH&N+, (nC4H&Nf), were investigated. Whereas in the low frequency range the dielectric properties depend on macromolecular size, the dielectric dispersion in the megacycle range is independent of degree of polymerization and is ascribed to the relaxation of the ionic atmosphere surrounding the macroion. The systems investigated are characterized by a spectrum of relaxation times. Above a certain value of the charge density the dispersion becomes independent of the degree of ionization of ionogenic groups on the chains. The average relaxation times decrease with increasing concentration but increase with increasing radius of the hydrated counterions.