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The free-volume theory for solvent self-diffusion coefficients in polymer−solvent systems is modified to include a more general analysis of the effects of solvent size. The predictions of the theory are compared with self-diffusion data for a diverse set of solvents and four polymers, polystyrene, poly(vinyl acetate), poly(methyl methacrylate), and poly( p -methylstyrene). The new prediction of size effects is based on the consideration of the asymmetry of solvent molecules.
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Vrentas et al. (1996) studied this question.
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