Abstract
The Flory theory of solution thermodynamics is used to predict exess volumes for systems containing a series of n-alkanes mixed with liquids of higher P* parameter and internal pressure, i.e., cyclopentane, cyclohexane, carbon tetrachloride, benzene and dioxane as well as of lower P*, i.e., decamethyltetrasiloxane. Trends of VE, e.g. changes of sign with alkane carbon number are well predicted and indicate the importance of the P* contribution in VE. Mixtures of hexane isomers with liquids of much higher P* typically have large excess enthalpies through zero as an S-shaped curve against composition which is negative on the side of the high P* component. This behaviour is interpreted as arising from increasingly large negative P* contributions in VE.
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Costas, M., Patterson, D. Volumes of mixing and theP * effect: Part II. Mixtures of alkanes with liquids of different internal pressures. J Solution Chem 11, 807–821 (1982). https://doi.org/10.1007/BF00650520
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DOI: https://doi.org/10.1007/BF00650520