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Large variations in the propensity of aqueous oxychlorine anions for the solution/vapor interface

  • Niklas Ottosson
  • Robert Vacha
  • Emad F. Aziz
  • Wandared Pokapanich
  • Wolfgang Eberhardt
  • Svante Svensson
  • Gunnar Öhrwall
  • Pavel Jungwirth
  • Olle Bjorneholm
  • Bernd Winter
Publiceringsår: 2009
Språk: Engelska
Publikation/Tidskrift/Serie: Journal of Chemical Physics
Volym: 131
Nummer: 12
Dokumenttyp: Artikel i tidskrift
Förlag: American Institute of Physics


Core-level photoelectron spectroscopy measurements have been performed of aqueous solutions of NaCl codissolved with NaClOn (n=1-4). Each species has a distinct Cl 2p electron binding energy, which can be exploited for depth-profiling experiments to study the competition between Cl-and ClOn- anions for residing in the outermost layers of the solution/vapor interface. Strongest propensity for the surface is observed for n=4 (perchlorate), followed by n=3 (chlorate), n=2 (chlorite), n=0 (chloride), and n=1 (hypochlorite). Molecular dynamics simulations rationalize the greatest surface propensity of the most oxidized anions in terms of their larger size and polarizability. The anomalous behavior of hypochlorite, being less surface-active than chloride, although it is both larger and more polarizable, is suggested to arise from the charge asymmetry over the anion, increasing its efficiency for bulk solvation. (C) 2009 American Institute of Physics. [doi:10.1063/1.3236805]


  • Physical Sciences
  • Natural Sciences


  • ISSN: 0021-9606

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