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 Economou, J. Ilja Siepmann

Research output: Contribution to journalArticle

62 Citations (Scopus)

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
Pages (from-to)11234-11246
Number of pages13
JournalJournal of Physical Chemistry B
Volume116
Issue number36
DOIs
Publication statusPublished - 13 Sep 2012
Externally publishedYes

Fingerprint

Cyclic Ethers
Alkanes
Ethers
Phase equilibria
Paraffins
alkanes
ethers
Atoms
Molecules
Cyclohexane
cyclohexane
field theory (physics)
atoms
Vapor Pressure
Cyclopentanes
molecules
Density of liquids
rings
Boiling point
Ethanol

ASJC Scopus subject areas

  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Transferable potentials for phase equilibria-united atom description of five- and six-membered cyclic alkanes and ethers. / Keasler, Samuel J.; Charan, Sophia M.; Wick, Collin D.; Economou, Ioannis; Siepmann, J. Ilja.

In: Journal of Physical Chemistry B, Vol. 116, No. 36, 13.09.2012, p. 11234-11246.

Research output: Contribution to journalArticle

Keasler, Samuel J. ; Charan, Sophia M. ; Wick, Collin D. ; Economou, Ioannis ; Siepmann, J. Ilja. / Transferable potentials for phase equilibria-united atom description of five- and six-membered cyclic alkanes and ethers. In: Journal of Physical Chemistry B. 2012 ; Vol. 116, No. 36. pp. 11234-11246.
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