Thermodynamic Interactions In Dilute Polymer Solutions: The Virial Coefficients

Abstract

The statistical thermodynamics of dilute polymer solutions is reviewed from the point of view of the continuum theory based on molecular distribution functions. The comparatively rigorous perturbation treatment of the second and third virial coefficients, and various approximate theories derived from it to give closed-form expressions useful for good-solvent systems, are outlined. Indications from theory and representative experimental data are discussed for linear chains, branched chains, and binary solutes comprising polymers alike chemically but different in molecular weight and/or branched structure. It is suggested that apparently anomalous thermodynamic and conformational behaviour observed with branched chains reveals a basic inadequacy in the so called ‘two-parameter’ class of statistical theories. © 1972, Walter de Gruyter. All rights reserved.