The A in SAFT: developing the contribution of association to the Helmholtz free energy within a Wertheim TPT1 treatment of generic Mie fluids
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Author(s)
Type
Journal Article
Abstract
An accurate representation of molecular association is a vital ingredient of advanced equations of state (EOSs), providing a description of thermodynamic properties of complex fluids where hydrogen bonding plays an important role. The combination of the first-order thermodynamic perturbation theory (TPT1) of Wertheim for associating systems with an accurate description of the structural and thermodynamic properties of the monomer fluid forms the basis of the statistical associating fluid theory (SAFT) family of EOSs. The contribution of association to the free energy in SAFT and related EOSs is very sensitive to the nature of intermolecular potential used to describe the monomers and, crucially, to the accuracy of the representation of the thermodynamic and structural properties. Here we develop an accurate description of the association contribution for use within the recently developed SAFT-VR Mie framework for chain molecules formed from segments interacting through a Mie potential [T. Lafitte, A. Apostolakou, C. Avendaño, A, Galindo, C. S. Adjiman, E. A. Müller, and G. Jackson, J. Chem. Phys. 139, 154504 (2013)]. As the Mie interaction represents a soft-core potential model, a method similar to that adopted for the Lennard-Jones potential [E. A. Müller and K. E. Gubbins, Ind. Eng. Chem. Res. 34, 3662 (1995)] is employed to describe the association contribution to the Helmholtz free energy. The radial distribution function (RDF) of the Mie fluid (which is required for the evaluation of the integral at the heart of the association term) is determined for a broad range of thermodynamic conditions (temperatures and densities) using the reference hyper-netted chain (RHNC) integral-equation theory. The numerical data for the association kernel of Mie fluids with different association geometries are then correlated for a range of thermodynamic states to obtain a general expression for the association contribution which can be applied for varying values of the Mie repulsive exponent. The resulting SAFT-VR Mie EOS allows for a much improved description of the vapour-liquid equilibria and single-phase properties of associating fluids such as water, methanol, ammonia, hydrogen sulphide, and their mixtures. A comparison is also made between the theoretical predictions of the degree of association for water and the extent of hydrogen bonding obtained from molecular simulations of the SPC/E and TIP4P/2005 atomistic models.
Date Issued
2015-05-19
Date Acceptance
2015-03-05
Citation
Molecular Physics, 2015, 113 (9-10), pp.948-984
ISSN
1362-3028
Publisher
Taylor & Francis
Start Page
948
End Page
984
Journal / Book Title
Molecular Physics
Volume
113
Issue
9-10
Copyright Statement
© 2015 The Author(s). Published by Taylor & Francis.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Permission is granted subject to the terms of the License under which the work was published. Please check the License conditions for the work which you wish to reuse. Full and appropriate attribution must be given. This permission does not cover any third party copyrighted material which may appear in the work requested.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Permission is granted subject to the terms of the License under which the work was published. Please check the License conditions for the work which you wish to reuse. Full and appropriate attribution must be given. This permission does not cover any third party copyrighted material which may appear in the work requested.
License URL
Sponsor
Qatar Shell Research and Technology Center QSTP LLC
Engineering & Physical Science Research Council (EPSRC)
Pfizer Incorporated
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Qatar Petroleum
Grant Number
490000724
EP/J014958/1
8500208599 / 1400
EP/E016340/1
EP/H500227/1
N/A
Subjects
Science & Technology
Physical Sciences
Physics, Atomic, Molecular & Chemical
Physics
complex associating fluids
integral equation theory
perturbation theory
statistical mechanics
hydrogen bonding
EQUATION-OF-STATE
THERMODYNAMIC PERTURBATION-THEORY
DIRECTIONAL ATTRACTIVE FORCES
HYPERNETTED-CHAIN EQUATION
MONTE-CARLO SIMULATIONS
HYDROGEN-BONDED FLUIDS
LENNARD-JONES FLUID
STATISTICAL-MECHANICAL MODELS
PHASE-EQUILIBRIA CALCULATIONS
PERCUS-YEVICK APPROXIMATION
Publication Status
Published