Abstract
AbstractA semi‐empirical interaction function previously used in the quantitative description of critical miscibility data for the system cyclohexane/polystyrene is reconsidered in terms of molecular parameters. The empirical part of the function has approximately the same magnitude as correction terms which, owing to the dependence of the average randomness of orientation of molecules and polymer segments on the composition of the liquid, have to be applied to the combinatory entropy of mixing. Such a treatment largely ignores excess volume effects. These have been quantitatively dealt with by Flory et al., who had to bring in an empirical entropy correction whose order of magnitude may prove to be compatible with the orientational entropy contributions mentioned above. A full treatment in terms of molecular parameters seems within reach, but this will have to take the variation of the segment density distribution with concentration into account.
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