Derivation of the thermodynamics of polymer solutions through use of the free volume concept. B. Heat of mixing

Prediction of thermodynamic properties of polymer solutions using the UNIFAC group-contribution method

A theory is proposed for the entropy of mixing of polymer and solvent. The theory is an extension of Hildebrand's derivation of the Flory-Huggins combinatorial entropy of mixing by use of free-volume concepts. The noncombinatorial (or equation of state) entropy of mixing originates, according to the proposed theory in the different free volume fractions which characterize ordinary simple solvents and high polymers. Two parameters are introduced: a parameter ρ, which is the ratio of the free volume fractions in the polymer and in the solvent, and a parameter c, which describes the external degrees of freedom of the polymer segments and is equivalent to Prigogine's parameter c. The noncombinatorial entropy of mixing, as derived from the present theory is equivalent (but not identical) to that derived from the newer theory of Flory et al. Concomitantly, the agreement with experiment of the calculated interaction parameter × for the athermal system polyisobutylene-cyclohexane is about the same as that obtained from the theory of Flory et al.

Derivation of the thermodynamics of polymer solutions through use of the free volume concept. B. Heat of mixing

Citations

Prediction of thermodynamic properties of polymer solutions using the UNIFAC group-contribution method

Entropy of mixing of polymer and solvent as derived from the free-volume concept

Enthalpy of mixing for polymer solutions based on Gibbs excess function limit of hard spheres mixtures

The enthalpy of mixing a polymer with a solvent as derived from the free volume concept

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