Synopsis
While many authors have proposed thermodynamic equations for liquid mixtures containing surface fractions besides volume fractions, also the most sophisticated treatment of Guggenheim is not applicable to solutions of folded macromolecules with intramolecular contacts. In this paper a complete and consistent treatment is proposed, based upon Guggenheim’ equations on one hand and on a model of molecules with intramolecular contacts proposed by the author in 1950 on the other hand. The treatment results in equations for the free energy and the heat of mixing as functions of ψ, the volume fraction of the polymer. It turns out, that the free energy of mixing depends on two parameters, both representing surface ratio’s, γ and γm. The latter measures the surface of the macromolecule when it is free of intramolecular contacts, while γ is the real surface ratio and depends on ϕ.
Suggestions for the experimental determination of these parameters are given. The generally employed erroneous definition of “athermal solutions” is replaced by two correct definitions of athermal and random solutions respectively.
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© 1986 Elsevier Applied Science Publishers Ltd
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Staverman, A.J. (1986). Statistics of Surface Contact Distributions. In: Kleintjens, L.A., Lemstra, P.J. (eds) Integration of Fundamental Polymer Science and Technology. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4185-4_2
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DOI: https://doi.org/10.1007/978-94-009-4185-4_2
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-8359-1
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