Abstract
The theory of excess enthalpy (HE) and enthalpic component of the interaction parameter (χh), dealt with in previous papers of this series, is extended to allow for the effects of intramolecular contacts in chain molecule solutes. The number of these contacts, as a function of the number of mers in the chain molecules and their concentration in the solution, is estimated from enumerations over a class of self-avoiding walks (paths) in a lattice-graph. Applied to solutions of polymethylenes in benzene, for which the equilibrium constant parameter (K) has been previously estimated to be unity, we find intramolecular contacts to have little effect on the excess enthalpy at 25°C even for long chains. The enthalpic part of the interaction function is predicted to depend strongly on the extent of intramolecular contacting. Extensions of the theory to solutions for which K≠1 are briefly considered.
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Huggins, M., Kennedy, J. Thermodynamic Properties of Liquids Including Solutions. XV. Intramolecular Contacts and Their Effects on Excess Enthalpies of Solutions of Chain Molecules, Especially Benzene Solutions of Normal Alkanes and Polymethylenes. Polym J 11, 315–322 (1979). https://doi.org/10.1295/polymj.11.315
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DOI: https://doi.org/10.1295/polymj.11.315