Transferable potentials for phase equilibria-united atom description of five- and six-membered cyclic alkanes and ethers

Samuel J. Keasler, Sophia M. Charan, Collin D. Wick, Ioannis G. Economou, J. Ilja Siepmann

Research output: Contribution to journalArticle

69 Scopus citations

Abstract

While the transferable potentials for phase equilibria-united atom (TraPPE-UA) force field has generally been successful at providing parameters that are highly transferable between different molecules, the polarity and polarizability of a given functional group can be significantly perturbed in small cyclic structures, which limits the transferability of parameters obtained for linear molecules. This has motivated us to develop a version of the TraPPE-UA force field specifically for five- and six-membered cyclic alkanes and ethers. The Lennard-Jones parameters for the methylene group obtained from cyclic alkanes are transferred to the ethers for each ring size, and those for the oxygen atom are common to all compounds for a given ring size. However, the partial charges are molecule specific and parametrized using liquid-phase dielectric constants. This model yields accurate saturated liquid densities and vapor pressures, critical temperatures and densities, normal boiling points, heat capacities, and isothermal compressibilities for the following molecules: cyclopentane, tetrahydrofuran, 1,3-dioxolane, cyclohexane, oxane, 1,4-dioxane, 1,3-dioxane, and 1,3,5-trioxane. The azeotropic behavior and separation factor for the binary mixtures of 1,3-dioxolane/cyclohexane and ethanol/1,4-dioxane are qualitively reproduced.

Original languageEnglish (US)
Pages (from-to)11234-11246
Number of pages13
JournalJournal of Physical Chemistry B
Volume116
Issue number36
DOIs
StatePublished - Sep 13 2012

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