Equation of state and force fields for Feynman-Hibbs-corrected Mie fluids. II. Application to mixtures of helium, neon, hydrogen, and deuterium.
File(s)
Accepted version
Author(s)
Aasen, Ailo
Hammer, Morten
Müller, Erich A
Wilhelmsen, Øivind
Type
Journal Article
Abstract
We extend the statistical associating fluid theory of quantum corrected Mie potentials (SAFT-VRQ Mie), previously developed for pure fluids [Aasen et al., J. Chem. Phys. 151, 064508 (2019)], to fluid mixtures. In this model, particles interact via Mie potentials with Feynman-Hibbs quantum corrections of first order (Mie-FH1) or second order (Mie-FH2). This is done using a third-order Barker-Henderson expansion of the Helmholtz energy from a non-additive hard-sphere reference system. We survey existing experimental measurements and ab initio calculations of thermodynamic properties of mixtures of neon, helium, deuterium, and hydrogen and use them to optimize the Mie-FH1 and Mie-FH2 force fields for binary interactions. Simulations employing the optimized force fields are shown to follow the experimental results closely over the entire phase envelopes. SAFT-VRQ Mie reproduces results from simulations employing these force fields, with the exception of near-critical states for mixtures containing helium. This breakdown is explained in terms of the extremely low dispersive energy of helium and the challenges inherent in current implementations of the Barker-Henderson expansion for mixtures. The interaction parameters of two cubic equations of state (Soave-Redlich-Kwong and Peng-Robinson) are also fitted to experiments and used as performance benchmarks. There are large gaps in the ranges and properties that have been experimentally measured for these systems, making the force fields presented especially useful.
Date Issued
2020-02-21
Date Acceptance
2020-01-01
Citation
Journal of Chemical Physics, 2020, 152 (7), pp.074507-1-074507-18
ISSN
0021-9606
Publisher
AIP Publishing
Start Page
074507-1
End Page
074507-18
Journal / Book Title
Journal of Chemical Physics
Volume
152
Issue
7
Copyright Statement
© 2020 Author(s).
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/32087642
Grant Number
EP/E016340/1
EP/J014958/1
EP/R013152/1
Subjects
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Chemical Physics
Publication Status
Published
Coverage Spatial
United States
Date Publish Online
2020-02-19