Developing intermolecular-potential models for use with the SAFT-VRMie equation of state
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Published version
Accepted version
Author(s)
Dufal, S
Lafitte, T
Galindo, A
Jackson, G
Haslam, AJ
Type
Journal Article
Abstract
A major advance in the statistical associating fluid theory (SAFT) for potentials of variable range (SAFT-VR) has recently been made with the incorporation of the Mie (generalized Lennard–Jones [LJ]) interaction between the segments comprising the molecules in the fluid (Lafitte et al. J. Chem. Phys. 2013;139:154504). The Mie potential offers greater versatility in allowing one to describe the softness/hardness of the repulsive interactions and the range of the attractions, which govern fine details of the fluid-phase equilibria and thermodynamic derivative properties of the system. In our current work, the SAFT-VR Mie equation of state is employed to develop models for a number of prototypical fluids, including some of direct relevance to the oil and gas industry: methane, carbon dioxide and other light gases, alkanes, alkyl benzenes, and perfluorinated compounds. A complication with the use of more-generic force fields such as the Mie potential is the additional number of parameters that have to be considered to specify the interactions between the model molecules, leading to a degree of degeneracy in the parameter space. A formal methodology to isolate intermolecular-potential models and assess the adequacy of the description of the thermodynamic properties in terms of the complex parameter space is developed. Fluid-phase equilibrium properties (the vapor pressure and saturated-liquid density) are chosen as the target properties in the refinement of the force fields; the predictive capability for other properties such as the enthalpy of vaporization, single-phase density, speed of sound, isobaric heat capacity, and Joule–Thomson coefficient, is appraised. It is found that an overall improvement of the representations of the thermophysical properties of the fluids is obtained using the more-generic Mie form of interaction; in all but the simplest of fluids, one finds that the LJ interaction is not the most appropriate.
Date Issued
2015-06-02
Date Acceptance
2015-03-27
Citation
AIChE Journal, 2015, 61 (9), pp.2891-2912
ISSN
0001-1541
Publisher
Wiley
Start Page
2891
End Page
2912
Journal / Book Title
AIChE Journal
Volume
61
Issue
9
Copyright Statement
© 2015 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
License URL
Subjects
equation of state
SAFT
phase equilibrium
complex fluids
second-derivative properties
parameter estimation
Publication Status
Published