Extreme surface propensity of halide ions in water

Lukasz Piatkowski, Zhen Zhang, Ellen H. G. Backus, Huib J. Bakker and Mischa Bonn ()
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Lukasz Piatkowski: FOM Institute AMOLF
Zhen Zhang: Max Planck Institute for Polymer Research
Ellen H. G. Backus: Max Planck Institute for Polymer Research
Huib J. Bakker: FOM Institute AMOLF
Mischa Bonn: Max Planck Institute for Polymer Research

Nature Communications, 2014, vol. 5, issue 1, 1-7

Abstract: Abstract Water possesses an extremely high polarity, making it a unique solvent for salts. Indeed, aqueous electrolyte solutions are ubiquitous in the atmosphere, biology, energy applications and industrial processes. For many processes, chemical reactions at the water surface are rate determining, and the nature and concentration of the surface-bound electrolytes are of paramount importance, as they determine the water structure and thereby surface reactivity. Here we investigate the dynamics of water molecules at the surface of sodium chloride and sodium iodide solutions, using surface-specific femtosecond vibrational spectroscopy. We quantify the interfacial ion density through the reduced energy transfer rates between water molecules resulting from the lowered effective interfacial density of water molecules, as water is displaced by surface active ions. Our results reveal remarkably high surface propensities for halogenic anions, higher for iodide than for chloride ions, corresponding to surface ion concentrations several times that of the bulk.

Date: 2014
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DOI: 10.1038/ncomms5083

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