Statistical mechanics of irreversible processes in polymer solutions

Abstract

The Kirkwood theory of irreversible processes in polymer solutions has been reformulated so as to include all contributions to the frictional forces exerted on the monomer units. The generalized diffusion equation for the nonequilibrium distribution function derived on this basis contains a new perturbation term, dependent upon the external field of force. The solution of this equation may be expressed by a perturbation expansion analogous to that given previously. The general theory has been applied to the intrinsic viscosity problem. Although the general theory reverts to the previous one, new techniques have been applied which enable the intrinsic viscosity and rigidity to be expressed in terms of the eigenfunctions and eigenvalues of the Oseen interaction tensor and the generalized diffusion operator. Moreover, a second formulation of the viscosity has been devised in which the result appears in terms of appropriate time correlation functions.