Diffusion in polymer—solvent systems. I. Reexamination of the free‐volume theory

Abstract The free‐volume theory describing diffusion in polymer–solvent systems is reexamined. Calculation of the specific free volume for such systems is discussed, and equations are presented for the determination of the self‐diffusion coefficients of the polymer and the solvent. Conditions under which the mutual diffusion coefficient can be deduced solely from free‐volume considerations are clarified, and a more general version of the free‐volume diffusion theory proposed by Fujita is presented. The further restrictions needed for the theory of Fujita are discussed, and it is concluded that these additional restrictions are responsible for failures of the Fujita theory.