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Received May 21, 2010
Accepted June 16, 2010
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Expanded ensemble Monte Carlo simulations for the chemical potentials of supercritical carbon dioxide and hydrocarbon solutes
Department of Chemical Engineering, University of Seoul, Siripdae-gil 13, Dongdaemun-gu, Seoul 130-743, Korea
changjaee@uos.ac.kr
Korean Journal of Chemical Engineering, February 2011, 28(2), 597-601(5), 10.1007/s11814-010-0359-4
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Abstract
We carry out expanded ensemble Monte Carlo simulations in order to calculate the chemical potentials of carbon dioxide as solvent and those of hydrocarbons as solutes at supercritical conditions. Recently developed adaptive method is employed to find weight factors during the simulation, which is crucial to achieving high accuracy for free energy calculation. The present simulation method enables us to obtain chemical potentials of large solute molecules dissolved in compressed phase from a single run of simulation. Simulation results for the excess chemical potentials of pure carbon dioxide at 300, 325 and 350 K are compared with experimental data and values predicted by the Peng-Robinson equation of state. A good agreement is found for high pressures up to 500 bar. The chemical potentials of hydrocarbon solutes dissolved in carbon dioxide at infinite dilution are predicted by simulation. Less than eight intermediate subensembles are required to gradually insert (or delete) hydrocarbon solute molecules from methane to noctane into dense CO2 phase of approximately 1.0 g cm^(-3).
References
Frenkel D, Smit B, Understanding Molecular Simulations 2nd Ed., Academic, San Diego (2002)
Widom B, J. Chem. Phys., 39, 2808 (1963)
Zwanzig RW, J. Chem. Phys., 22, 1420 (1954)
Kirkwood JG, J. Chem. Phys., 3, 300 (1935)
Bennett CH, J. Comput. Phys., 22, 245 (1976)
Lyubartsev AP, Martsinovski AA, Shevkunov SV, Vorontsov-Vel’yaminov PN, J. Chem. Phys., 96, 1776 (1992)
Lyubartsev AP, Laaksonen A, Vorontsov-Velyaminov PN, Mol. Phys., 82, 455 (1994)
Lyubartsev AP, Laaksonen A, Vorontsov-Velyaminov PN, Mol. Simul., 18, 455 (1996)
Lyubartsev AP, Jacobsson SP, Sundholm G, Laaksonen A, J. Phys. Chem. B, 105(32), 7775 (2001)
Errington JR, Boulougouris GC, Economou IG, Panagiotopoulos AZ, Theodorou DN, J. Phys. Chem. B, 102(44), 8865 (1998)
Boulougouris GC, Errington JR, Economou IG, Panagiotopoulos AZ, Theodorou DN, J. Phys. Chem. B, 104(20), 4958 (2000)
Khare AA, Rutledge GC, J. Chem. Phys., 110(6), 3063 (1999)
Khare AA, Rutledge GC, J. Phys. Chem. B, 104(15), 3639 (2000)
Aberg KM, Lyubartsev AP, Jacobsson SP, Laaksonen A, J. Chem. Phys., 120(8), 3770 (2004)
Chang J, Sandler SI, J. Chem. Phys., 118(18), 8390 (2003)
Chang J, Lenhoff AM, Sandler SI, J. Chem. Phys., 120(6), 3003 (2004)
Chang J, Lenhoff AM, Sandler SI, J. Phys. Chem. B, 109(41), 19507 (2005)
Chang J, Sandler SI, J. Chem. Phys., 125, 054705 (2006)
Chang J, J. Chem. Phys., 131, 074103 (2009)
Harris JG, Yung KH, J. Phys. Chem., 99(31), 12021 (1995)
Vorholz J, Harismiadis VI, Rumpf B, Panagiotopoulos AZ, Maurer G, Fluid Phase Equilib., 170(2), 203 (2000)
Martin MG, Siepmann JI, J. Phys. Chem. B, 102(14), 2569 (1998)
Wick CD, Martin MG, Siepmann JI, J. Phys. Chem. B, 104(33), 8008 (2000)
Chen B, Potoff JJ, Siepmann JI, J. Phys. Chem. B, 105(15), 3093 (2001)
Lemmon EW, McLinden MO, Friend DG, “Thermophysical Properties of Fluid Systems” in NIST Chemistry WebBook, NIST Standard Reference Database Number 69, Eds. Linstrom PJ and Mallard WG, National Institute of Standards and Technology, Gaithersburg MD, 20899, http://webbook.nist.gov (retrieved April 10, 2010).
Peng DY, Robinson DB, Ind. Eng. Chem. Fundam., 15, 59 (1976)
Sandler SI, Chemical, Biochemical and Engineering Thermodynamics 4th Ed., John Wiley & Sons (2006)
Widom B, J. Chem. Phys., 39, 2808 (1963)
Zwanzig RW, J. Chem. Phys., 22, 1420 (1954)
Kirkwood JG, J. Chem. Phys., 3, 300 (1935)
Bennett CH, J. Comput. Phys., 22, 245 (1976)
Lyubartsev AP, Martsinovski AA, Shevkunov SV, Vorontsov-Vel’yaminov PN, J. Chem. Phys., 96, 1776 (1992)
Lyubartsev AP, Laaksonen A, Vorontsov-Velyaminov PN, Mol. Phys., 82, 455 (1994)
Lyubartsev AP, Laaksonen A, Vorontsov-Velyaminov PN, Mol. Simul., 18, 455 (1996)
Lyubartsev AP, Jacobsson SP, Sundholm G, Laaksonen A, J. Phys. Chem. B, 105(32), 7775 (2001)
Errington JR, Boulougouris GC, Economou IG, Panagiotopoulos AZ, Theodorou DN, J. Phys. Chem. B, 102(44), 8865 (1998)
Boulougouris GC, Errington JR, Economou IG, Panagiotopoulos AZ, Theodorou DN, J. Phys. Chem. B, 104(20), 4958 (2000)
Khare AA, Rutledge GC, J. Chem. Phys., 110(6), 3063 (1999)
Khare AA, Rutledge GC, J. Phys. Chem. B, 104(15), 3639 (2000)
Aberg KM, Lyubartsev AP, Jacobsson SP, Laaksonen A, J. Chem. Phys., 120(8), 3770 (2004)
Chang J, Sandler SI, J. Chem. Phys., 118(18), 8390 (2003)
Chang J, Lenhoff AM, Sandler SI, J. Chem. Phys., 120(6), 3003 (2004)
Chang J, Lenhoff AM, Sandler SI, J. Phys. Chem. B, 109(41), 19507 (2005)
Chang J, Sandler SI, J. Chem. Phys., 125, 054705 (2006)
Chang J, J. Chem. Phys., 131, 074103 (2009)
Harris JG, Yung KH, J. Phys. Chem., 99(31), 12021 (1995)
Vorholz J, Harismiadis VI, Rumpf B, Panagiotopoulos AZ, Maurer G, Fluid Phase Equilib., 170(2), 203 (2000)
Martin MG, Siepmann JI, J. Phys. Chem. B, 102(14), 2569 (1998)
Wick CD, Martin MG, Siepmann JI, J. Phys. Chem. B, 104(33), 8008 (2000)
Chen B, Potoff JJ, Siepmann JI, J. Phys. Chem. B, 105(15), 3093 (2001)
Lemmon EW, McLinden MO, Friend DG, “Thermophysical Properties of Fluid Systems” in NIST Chemistry WebBook, NIST Standard Reference Database Number 69, Eds. Linstrom PJ and Mallard WG, National Institute of Standards and Technology, Gaithersburg MD, 20899, http://webbook.nist.gov (retrieved April 10, 2010).
Peng DY, Robinson DB, Ind. Eng. Chem. Fundam., 15, 59 (1976)
Sandler SI, Chemical, Biochemical and Engineering Thermodynamics 4th Ed., John Wiley & Sons (2006)
