Exploring multicomponent phase equilibria by Monte Carlo simulations: Toward a description of gas-liquid chromatography

Martin, MG; Siepmann, JI; Schure, MR

HERO ID

4866874

Reference Type

Journal Article

Year

2000

HERO ID 4866874
In Press No
Year 2000
Title Exploring multicomponent phase equilibria by Monte Carlo simulations: Toward a description of gas-liquid chromatography
Authors Martin, MG; Siepmann, JI; Schure, MR
Journal ACS Symposium Series
Volume 748
Page Numbers 82-95
Abstract The calculation of retention times, retention indices, and partition constants is a long sought-after goal for theoretical studies in gas chromatography. Although advances in computational chemistry have improved our understanding of molecular interactions, little attention has been focused on chromatography, let alone calculations of retention properties. Configurational-bias Monte Carlo simulations in the Gibbs ensemble have been used to calculate single and multi-component phase diagrams for a variety of hydrocarbon systems. Transferable force fields for linear and branched alkanes have been derived from these simulations. Using calculations for helium/n-heptane/n-pentane systems, it is demonstrated that this approach yields very precise partition constants and free energies of transfer. Thereafter, the partitioning of linear and branched alkane solutes (with five to eight carbon atoms) between a squalane liquid phase and a helium vapor phase is investigated. The Kovats retention indices of the solutes are calculated directly from the partition constants.
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