Thermodynamic study of polymer–solvent systems by reversed‐flow gas chromatography

Abstract

Abstract Reversed‐flow gas chromatography, a new method for studying heterogeneous catalysis, diffusion, adsorption, evaporation, and other related phenomena, is now applied to the determination of activity of the solvent in a polymer–solvent system in the whole range of polymer concentration, as well as for the calculation of excess partial molar thermodynamic functions of mixing. The systems used were polystyrene in cyclohexane, polyvinylacetate in cyclohexanone and polyvinylpyrrolidone in methanol. In the first system, which was studied in detail, weight fraction activity coefficients ( a 1 / w 1 ) at several temperatures (333.8–348.1 K) and various polymer concentrations (0.020–0.131 g/g) were determined. From the latter parameters weight fraction activity coefficients at infinite dilution ( a 1 / w 1 ) ∞ were computed. Flory–Huggins interaction parameters x and solubility parameters δ 2 were also determined. Finally, the thermodynamic parameters found by the present method are compared with those determined by other techniques or calculated theoretically.