Thermodynamics of polystyrene solutions. I. Interaction parameters and polymer order

The Maron theory was used to deduce from mostly osmotic pressure and light-scattering data the interaction parameters as a function of concentration, temperature, and polymer molecular weight for solutions of polystyrene in seven different solvents. These interaction parameters were then utilized to calculate the activity coefficients of the solvent in more concentrated solutions for comparison with experimental values deduced from vapor pressure measurements. When order was absent in the polymers (all cases but two), the agreement between calculated and observed activity coefficients was found to be very good. In the two cases where order was present, the activity coefficients observed in the concentrated solutions were higher than those calculated. These deviations were employed to find the degree of polymer order both in solution and in the original polymers.