Modelling of the thermodynamic and solvation properties of electrolyte solutions with the statistical associating fluid theory for potentials of variable range
File(s)Schreckenberg et al.pdf (1.36 MB)
Accepted version
Author(s)
Type
Journal Article
Abstract
An improved formulation of the extension of the statistical associating fluid theory for potentials of variable range to electrolytes (SAFT-VRE) is presented, incorporating a representation for the dielectric constant of the solution that takes into account the temperature, density and composition of the solvent. The proposed approach provides an excellent correlation of the dielectric-constant data available for a number of solvents including water, representative alcohols and carbon dioxide, and it is shown that the methodology can be used to treat mixed-solvent electrolyte solutions. Models for strong electrolytes of the metal-halide family are considered here. The salts are treated as fully dissociated and ion-specific interaction parameters are presented. Vapour pressure, density, and mean ionic activity coefficient data are used to determine the ion–ion and solvent–ion parameters, and mixed-salt electrolyte solutions (brines) are then treated predictively. We find that the resulting intermolecular potential models follow physical trends in terms of energies and ion sizes with a close relationship observed with well-established ionic diameters. A good description is obtained for the densities, mean ionic activity coefficients, and vapour pressures of the electrolyte solutions studied. The theory is also seen to provide excellent predictions of the osmotic coefficient and of the depression of the freezing temperature, and provides a qualitative estimate of the solvation free energy. The vapour pressure of aqueous brines is predicted accurately, as is the density of these solutions, although not at the highest pressures considered. Calculations for the vapour–liquid and liquid–liquid equilibria of salts in water+methanol and water+n-butan-1-ol are presented. In addition, it is shown that the salting-out of carbon dioxide in sodium chloride solutions is captured well using a predictive model.
Date Issued
2014-09-01
Date Acceptance
2014-03-20
Citation
Molecular Physics: An International Journal at the Interface Between Chemistry and Physics, 2014, 112 (17), pp.2339-2364
ISSN
0026-8976
Publisher
Taylor and Francis
Start Page
2339
End Page
2364
Journal / Book Title
Molecular Physics: An International Journal at the Interface Between Chemistry and Physics
Volume
112
Issue
17
Copyright Statement
© 2014 Taylor & Francis. ‘This is an Author's Original Manuscript of an article whose final and definitive form, the Version of Record, has been published in the Molecular Physics :an International Journal at the Interface Between Chemistry and Physics, 2014. copyright Taylor & Francis., available online at: http://www.tandfonline.com/10.1080/00268976.2014.910316
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Pfizer Incorporated
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/J014958/1
8500208599 / 1400
EP/E016340/1
EP/J003840/1
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
SAFT-VR
equation of state
phase behaviour
water
electrolyte
alcohols
solvation energy
EQUATION-OF-STATE
DIOXIDE PLUS WATER
DIRECTIONAL ATTRACTIVE FORCES
VAPOR-LIQUID-EQUILIBRIA
MEAN SPHERICAL APPROXIMATION
FREEZING-POINT DEPRESSION
PRESSURE PHASE-EQUILIBRIA
AQUEOUS SALT-SOLUTIONS
SAFT-VR APPROACH
M F MEASUREMENTS
Chemical Physics
0202 Atomic, Molecular, Nuclear, Particle and Plasma Physics
0306 Physical Chemistry (incl. Structural)
0307 Theoretical and Computational Chemistry
Publication Status
Published
Date Publish Online
2014-09-01