Document Type
Article
Original Publication Date
2015
Journal/Book/Conference Title
Journal of Chemical Physics
Volume
142
First Page
124705
DOI of Original Publication
http://doi.org/10.1063/1.4914461
Date of Submission
May 2022
Abstract
Using a newly developed grand canonical Monte Carlo approach based on fractional exchanges of dissolved ions and water molecules, we studied equilibrium partitioning of both components between laterally extended apolar confinements and surrounding electrolyte solution. Accurate calculations of the Hamiltonian and tensorial pressure components at anisotropic conditions in the pore required the development of a novel algorithm for a self-consistent correction of nonelectrostatic cut-off effects. At pore widths above the kinetic threshold to capillary evaporation, the molality of the salt inside the confinement grows in parallel with that of the bulk phase, but presents a nonuniform width-dependence, being depleted at some and elevated at other separations. The presence of the salt enhances the layered structure in the slit and lengthens the range of inter-wall pressure exerted by the metastable liquid. Solvation pressure becomes increasingly repulsive with growing salt molality in the surrounding bath. Depending on the sign of the excess molality in the pore, the wetting free energy of pore walls is either increased or decreased by the presence of the salt. Because of simultaneous rise in the solution surface tension, which increases the free-energy cost of vapor nucleation, the rise in the apparent hydrophobicity of the walls has not been shown to enhance the volatility of the metastable liquidinthepores.
Rights
© AIP Publishing LLC
Is Part Of
VCU Chemistry Publications
Comments
This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in J. Chem. Phys. 142, 124705 (2015) and may be found at http://doi.org/10.1063/1.4914461.