title: Chemical Potentials, Activity Coefficients, and Solubility in Aqueous NaCl Solutions: Prediction by Polarizable Force Fields.
abstract: We describe a computationally efficient molecular simulation methodology for calculating the concentration dependence of the chemical potentials of both solute and solvent in aqueous electrolyte solutions, based on simulations of the salt chemical potential alone. We use our approach to study the predictions for aqueous NaCl solutions at ambient conditions of these properties by the recently developed polarizable force fields (FFs) AH/BK3 of Kiss and Baranyai (J. Chem. Phys. 2013, 138, 204507) and AH/SWM4-DP of Lamoureux and Roux (J. Phys. Chem. B 2006, 110, 3308 - 3322) and by the nonpolarizable JC FF of Joung and Cheatham tailored to SPC/E water (J. Phys. Chem. B 2008, 112, 9020 - 9041). We also consider their predictions of the concentration dependence of the electrolyte activity coefficient, the crystalline solid chemical potential, the electrolyte solubility, and the solution specific volume. We first highlight the disagreement in the literature concerning calculations of solubility by means of molecular simulation in the case of the JC FF and provide strong evidence of the correctness of our methodology based on recent independently obtained results for this important test case. We then compare the predictions of the three FFs with each other and with experiment and draw conclusions concerning their relative merits, with particular emphasis on the salt chemical potential and activity coefficient vs concentration curves and their derivatives. The latter curves have only previously been available from Kirkwood-Buff integrals, which require approximate numerical integrations over system pair correlation functions at each concentration. Unlike the case of the other FFs, the AH/BK3 curves are nearly parallel to the corresponding experimental curves at moderate and higher concentrations. This leads to an excellent prediction of the water chemical potential via the Gibbs-Duhem equation and enables the activity coefficient curve to be brought into excellent agreement with experiment by incorporating an appropriate value of the standard state chemical potential in the Henry Law convention.
authors.affiliation: Faculty of Science, J. E. Purkinje University , 400 96 Ústí nad Labem, Czech Republic.
authors.forename: Filip
authors.initials: F
authors.lastname: Moučka
authors.affiliation: Faculty of Science, J. E. Purkinje University , 400 96 Ústí nad Labem, Czech Republic.|Institute of Chemical Process Fundamentals, Academy of Sciences , 165 02 Prague 6, Czech Republic.
authors.forename: Ivo
authors.initials: I
authors.lastname: Nezbeda
authors.affiliation: Department of Mathematics and Statistics, University of Guelph , Guelph, Ontario N1G 2W1, Canada.|Faculty of Science, University of Ontario Institute of Technology , Oshawa, Ontario L1H 7K4, Canada.
authors.forename: William R
authors.initials: WR
authors.lastname: Smith
mesh_terms: D004573:Electrolytes / Q000737:chemistry; D012965:Sodium Chloride / Q000737:chemistry*; D012995:Solubility; D014867:Water / Q000737:chemistry*
chemical_list: D004573:Electrolytes; D014867:Water; D012965:Sodium Chloride