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Title: The Importance of Polarisability in the Modeling of Solubility: Quantifying the Effect of Charged Co-Solutes on the Solubility of Small Non-Polar Solutes

Abstract

In a recent work (Dyer et al., J. Chem. Phys. 129 (2008), 024508), we demonstrated that by accounting for the polarisability of small non-polar solutes, in an explicit manner, it is possible to approach quantitative agreement with experimental values of the excess chemical potential of the molecules in pure water. Here, we continue this line of research by considering the effects of ionic co-solutes (i.e. salts) on the solubility of an explicitly polarisable model suitable for a variety of small non-polar solutes. In doing so, we calculate the excess chemical potential that is related to the solubility of the solute in the solution, and investigate how the solubility of hydrophobic solutes varies with ion concentration, i.e. salting-out/salting-in effects, as measured by the Setchenow parameter. In particular, we consider the solubility of Ne, Ar, Kr, Xe and CH4 in aqueous NaCl solutions for the TIP3P, TIP4P-Ew and TIP4P/2005 models of water. Using these models, we discover that the addition of explicit polarisability to the solute models decreases the excess chemical potential, but fails to obtain quantitative agreement with experimental values. In addition, we determine that explicit polarisation has minimal effect on the Setchenow parameter and, in turn, minimal effect on salting-out.more » Instead, we show that the over-prediction of the excess chemical potential is due to an inaccurate ion–solute interaction potential. Further to this, we demonstrate that, by accounting for polarisability explicitly, it is possible to obtain pair interaction potentials from ab initio calculations that perform as well as, or better than the models commonly used to study these systems.« less

Authors:
; ;
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1065381
DOE Contract Number:  
ERKCC61
Resource Type:
Journal Article
Journal Name:
Molecular Simulations
Additional Journal Information:
Journal Volume: 37; Journal Issue: 4; Related Information: FIRST partners with Oak Ridge National Laboratory (lead); Argonne National Laboratory; Drexel University; Georgia State University; Northwestern University; Pennsylvania State University; Suffolk University; Vanderbilt University; University of Virginia; Journal ID: ISSN 0892--7022
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous), solar (fuels), energy storage (including batteries and capacitors), hydrogen and fuel cells, electrodes - solar, mechanical behavior, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Docherty, H., Dyer, P., and Cummings, Peter T. The Importance of Polarisability in the Modeling of Solubility: Quantifying the Effect of Charged Co-Solutes on the Solubility of Small Non-Polar Solutes. United States: N. p., Web. doi:10.1080/08927022.2011.553225.
Docherty, H., Dyer, P., & Cummings, Peter T. The Importance of Polarisability in the Modeling of Solubility: Quantifying the Effect of Charged Co-Solutes on the Solubility of Small Non-Polar Solutes. United States. https://doi.org/10.1080/08927022.2011.553225
Docherty, H., Dyer, P., and Cummings, Peter T. . "The Importance of Polarisability in the Modeling of Solubility: Quantifying the Effect of Charged Co-Solutes on the Solubility of Small Non-Polar Solutes". United States. https://doi.org/10.1080/08927022.2011.553225.
@article{osti_1065381,
title = {The Importance of Polarisability in the Modeling of Solubility: Quantifying the Effect of Charged Co-Solutes on the Solubility of Small Non-Polar Solutes},
author = {Docherty, H. and Dyer, P. and Cummings, Peter T.},
abstractNote = {In a recent work (Dyer et al., J. Chem. Phys. 129 (2008), 024508), we demonstrated that by accounting for the polarisability of small non-polar solutes, in an explicit manner, it is possible to approach quantitative agreement with experimental values of the excess chemical potential of the molecules in pure water. Here, we continue this line of research by considering the effects of ionic co-solutes (i.e. salts) on the solubility of an explicitly polarisable model suitable for a variety of small non-polar solutes. In doing so, we calculate the excess chemical potential that is related to the solubility of the solute in the solution, and investigate how the solubility of hydrophobic solutes varies with ion concentration, i.e. salting-out/salting-in effects, as measured by the Setchenow parameter. In particular, we consider the solubility of Ne, Ar, Kr, Xe and CH4 in aqueous NaCl solutions for the TIP3P, TIP4P-Ew and TIP4P/2005 models of water. Using these models, we discover that the addition of explicit polarisability to the solute models decreases the excess chemical potential, but fails to obtain quantitative agreement with experimental values. In addition, we determine that explicit polarisation has minimal effect on the Setchenow parameter and, in turn, minimal effect on salting-out. Instead, we show that the over-prediction of the excess chemical potential is due to an inaccurate ion–solute interaction potential. Further to this, we demonstrate that, by accounting for polarisability explicitly, it is possible to obtain pair interaction potentials from ab initio calculations that perform as well as, or better than the models commonly used to study these systems.},
doi = {10.1080/08927022.2011.553225},
url = {https://www.osti.gov/biblio/1065381}, journal = {Molecular Simulations},
issn = {0892--7022},
number = 4,
volume = 37,
place = {United States},
year = {},
month = {}
}