Core-level photoelectron spectroscopy measurements have been performed of aqueous solutions of NaCl codissolved with . Each species has a distinct Cl electron binding energy, which can be exploited for depth-profiling experiments to study the competition between and anions for residing in the outermost layers of the solution/vapor interface. Strongest propensity for the surface is observed for (perchlorate), followed by (chlorate), (chlorite), (chloride), and (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.
Large variations in the propensity of aqueous oxychlorine anions for the solution/vapor interface
Niklas Ottosson, Robert Vácha, Emad F. Aziz, Wandared Pokapanich, Wolfgang Eberhardt, Svante Svensson, Gunnar Öhrwall, Pavel Jungwirth, Olle Björneholm, Bernd Winter; Large variations in the propensity of aqueous oxychlorine anions for the solution/vapor interface. J. Chem. Phys. 28 September 2009; 131 (12): 124706. https://doi.org/10.1063/1.3236805
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