The extrapolation of phase equilibrium curves of mixtures in the isobaric-isothermal Gibbs ensemble

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

A powerful extrapolation scheme is proposed to determine the vapour-liquid and liquid-liquid equilibrium curves of mixtures by performing a single isothermal isobaric Gibbs ensemble Monte Carlo (GEMC) simulation. The coexistence curves for the mole fraction and the density are extrapolated as functions of the temperature and the pressure by second-order Taylor series. The coefficients of the Taylor series, which are the temperature and pressure derivatives of these quantities along the coexistence curves, can be calculated from the data produced by a single GEMC simulation on the basis of fluctuation formulas. We show that the application of a Padé approximant considerably widens the temperature and pressure range where the extrapolation is accurate. Using Lennard-Jones mixtures as test systems, we show that the technique is able to produce quite accurate equilibrium curves at fixed temperature in the function of the pressure and vice versa. The procedure yields good results not only for vapour-liquid but also for liquid-liquid coexistence curves. The calculation of the vapour pressure curves at a fixed composition of the liquid side is straightforward with the method.

Original languageEnglish
Pages (from-to)3429-3441
Number of pages13
JournalMolecular Physics
Volume100
Issue number21
DOIs
Publication statusPublished - Nov 10 2002

Fingerprint

Extrapolation
Phase equilibria
extrapolation
Pressure
Temperature
Liquids
curves
liquids
Taylor series
Vapor Pressure
Vapors
vapors
temperature
Vapor pressure
vapor pressure
simulation
Derivatives
coefficients
Chemical analysis

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

The extrapolation of phase equilibrium curves of mixtures in the isobaric-isothermal Gibbs ensemble. / Kristóf, T.; Liszi, J.; Boda, D.

In: Molecular Physics, Vol. 100, No. 21, 10.11.2002, p. 3429-3441.

Research output: Contribution to journalArticle

@article{128139a201ae48d8890f091ccab38b78,
title = "The extrapolation of phase equilibrium curves of mixtures in the isobaric-isothermal Gibbs ensemble",
abstract = "A powerful extrapolation scheme is proposed to determine the vapour-liquid and liquid-liquid equilibrium curves of mixtures by performing a single isothermal isobaric Gibbs ensemble Monte Carlo (GEMC) simulation. The coexistence curves for the mole fraction and the density are extrapolated as functions of the temperature and the pressure by second-order Taylor series. The coefficients of the Taylor series, which are the temperature and pressure derivatives of these quantities along the coexistence curves, can be calculated from the data produced by a single GEMC simulation on the basis of fluctuation formulas. We show that the application of a Pad{\'e} approximant considerably widens the temperature and pressure range where the extrapolation is accurate. Using Lennard-Jones mixtures as test systems, we show that the technique is able to produce quite accurate equilibrium curves at fixed temperature in the function of the pressure and vice versa. The procedure yields good results not only for vapour-liquid but also for liquid-liquid coexistence curves. The calculation of the vapour pressure curves at a fixed composition of the liquid side is straightforward with the method.",
author = "T. Krist{\'o}f and J. Liszi and D. Boda",
year = "2002",
month = "11",
day = "10",
doi = "10.1080/00268970210158641",
language = "English",
volume = "100",
pages = "3429--3441",
journal = "Molecular Physics",
issn = "0026-8976",
publisher = "Taylor and Francis Ltd.",
number = "21",

}

TY - JOUR

T1 - The extrapolation of phase equilibrium curves of mixtures in the isobaric-isothermal Gibbs ensemble

AU - Kristóf, T.

AU - Liszi, J.

AU - Boda, D.

PY - 2002/11/10

Y1 - 2002/11/10

N2 - A powerful extrapolation scheme is proposed to determine the vapour-liquid and liquid-liquid equilibrium curves of mixtures by performing a single isothermal isobaric Gibbs ensemble Monte Carlo (GEMC) simulation. The coexistence curves for the mole fraction and the density are extrapolated as functions of the temperature and the pressure by second-order Taylor series. The coefficients of the Taylor series, which are the temperature and pressure derivatives of these quantities along the coexistence curves, can be calculated from the data produced by a single GEMC simulation on the basis of fluctuation formulas. We show that the application of a Padé approximant considerably widens the temperature and pressure range where the extrapolation is accurate. Using Lennard-Jones mixtures as test systems, we show that the technique is able to produce quite accurate equilibrium curves at fixed temperature in the function of the pressure and vice versa. The procedure yields good results not only for vapour-liquid but also for liquid-liquid coexistence curves. The calculation of the vapour pressure curves at a fixed composition of the liquid side is straightforward with the method.

AB - A powerful extrapolation scheme is proposed to determine the vapour-liquid and liquid-liquid equilibrium curves of mixtures by performing a single isothermal isobaric Gibbs ensemble Monte Carlo (GEMC) simulation. The coexistence curves for the mole fraction and the density are extrapolated as functions of the temperature and the pressure by second-order Taylor series. The coefficients of the Taylor series, which are the temperature and pressure derivatives of these quantities along the coexistence curves, can be calculated from the data produced by a single GEMC simulation on the basis of fluctuation formulas. We show that the application of a Padé approximant considerably widens the temperature and pressure range where the extrapolation is accurate. Using Lennard-Jones mixtures as test systems, we show that the technique is able to produce quite accurate equilibrium curves at fixed temperature in the function of the pressure and vice versa. The procedure yields good results not only for vapour-liquid but also for liquid-liquid coexistence curves. The calculation of the vapour pressure curves at a fixed composition of the liquid side is straightforward with the method.

UR - http://www.scopus.com/inward/record.url?scp=0037058491&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037058491&partnerID=8YFLogxK

U2 - 10.1080/00268970210158641

DO - 10.1080/00268970210158641

M3 - Article

AN - SCOPUS:0037058491

VL - 100

SP - 3429

EP - 3441

JO - Molecular Physics

JF - Molecular Physics

SN - 0026-8976

IS - 21

ER -