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The influence of concentration on the molecular surface structure of simple and mixed aqueous electrolytes

Author

  • Niklas Ottosson
  • Jan Heyda
  • Erik Wernersson
  • Wandared Pokapanich
  • Svante Svensson
  • Bernd Winter
  • Gunnar Öhrwall
  • Pavel Jungwirth
  • Olle Bjorneholm

Summary, in English

We investigate various mechanisms contributing to the surface ion distributions in simple and mixed aqueous alkali-halide solutions depending on the total salt concentration, using a combination of photoelectron spectroscopy and molecular dynamics simulations. In simple solutions, the surface enhancement of large polarizable anions is reduced with increasing concentration. In the case of a NaBr/NaCl mixed aqueous solution, with bromide as the minority component, the situation is more complex. While the total anion/cation charge separation is similarly reduced with increasing salt content, this alone does not uniquely determine the ion distribution due to the co-existence of two different anions, Br- and Cl-. We show that bromide is selectively surface enhanced at higher concentrations, despite the fact that the total anion surface enhancement is reduced. This phenomenon, which can be viewed as "salting out'' of bromide by NaCl might have consequences for our understanding of the surface structure of mixed aqueous solutions subjected to concentration increase due to dehydration, such as seawater-born aerosols.

Department/s

Publishing year

2010

Language

English

Pages

10693-10700

Publication/Series

Physical Chemistry Chemical Physics

Volume

12

Issue

36

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Natural Sciences
  • Physical Sciences

Status

Published

ISBN/ISSN/Other

  • ISSN: 1463-9084