Temperature effects on the spatial distribution of electrolyte mixtures at the aqueous liquid-vapor interface

Becky L. Eggimann, J. Ilja Siepmann

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The microscopic picture of ions at the aqueous liquid-vapor interface continues to be an important and active area of research. Both experiments and simulations have shown that certain ions, such as Br- and I-, prefer to adsorb at the interface, but there is not yet a consensus as to the relative importance of various ion-specific properties that influence surface solvation. In a previous study, we systematically explored the effect of ion size on determining whether or not a monovalent ion would adsorb at the surface, and found that, for electrolyte mixtures represented by non-polarizable models, the larger/smaller anions are enriched/depleted at the interface. Here, we extend that study to include temperature effects enabling a van't Hoff analysis of the enthalpic and entropic contributions. We perform configurational-bias Monte Carlo simulations in the Gibbs ensemble to investigate the partitioning of mixtures of differently sized ions at the aqueous liquid-vapor interface from 284.09 K to 347.22 K at a pressure of 1 atm. Ions are represented using our own previously developed models that vary only in size (i.e., the Lennard-Jones σ parameter changes, while all other parameters are held constant across ion types). System properties studied include surface tension, interfacial width, ion surface excess, number density profiles, z-dependent transfer free energy, enthalpy, entropy, and anion-cation coordination numbers.

Original languageEnglish (US)
Pages (from-to)10792-10801
Number of pages10
JournalPhysical Chemistry Chemical Physics
Issue number19
StatePublished - May 21 2020

Bibliographical note

Funding Information:
Financial support from the National Science Foundation (CBET-1159837 and RUI-1159731) and the Industrial Partnership for Research in Interfacial & Materials Engineering at the University of Minnesota is gratefully acknowledged. Part of the computer resources were provided by the Minnesota Supercomputing Institute.

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PubMed: MeSH publication types

  • Journal Article


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