Precision measurements of osmotic pressure in concentrated polymer solutions—II

Precision measurements of osmotic pressure have been carried out with several polymers (polystyrene, polymethylmethacrylate and polyvinyl acetate) in organic solvents. The concentration dependence of the osmotic pressure over a wide range of concentrations (up to 0·2 g/cm³) was established and the osmotic virial coefficients were evaluated. From the temperature dependence of the osmotic pressure, the partial molar heats and entropies of mixing were also determined. In the system polystyrene-cyclohexane, measurements were carried out near the θ-temperature; variation of the virial coefficients with temperature and molecular weight was studied. It was found that the conventionally defined θ-temperature is molecular weight dependent. At the θ-temperature, the third virial coefficient is positive and tends to a nonzero limit when the molecular weight tends to infinity.