Interfacial behavior of perchlorate versus chloride ions in aqueous solutions

The Journal of Physical Chemistry. B
Marcel D BaerSutapa Ghosal

Abstract

In recent years, theoretical as well as experimental studies have presented a novel view of the aqueous interface, wherein hard and/or multiply charged ions are excluded from the interface but large polarizable anions show interfacial enhancement relative to the bulk. The observed trend in the propensity of anions to adsorb at the air/water interface appears to follow an inverse order of the Hofmeister series for anions. This study focuses on experimental and theoretical examination of the partitioning behavior of perchlorate (ClO(4)(-)) and chloride (Cl(-)) ions at the air/water interface. We have used ambient pressure X-ray photoelectron spectroscopy to directly probe the interfacial concentrations of ClO(4)(-) and Cl(-) ions in sodium perchlorate and sodium chloride solutions, respectively. In the case of ClO(4)(-) ion, experimental observations are compared with molecular dynamics simulations utilizing both first principles based interaction potentials as well as polarizable classical force fields. Both the experimental and the theoretical results show enhancement of ClO(4)(-) ion at the interface, compared with the absence of such enhancement in the case of the Cl(-) ion. Our observations are in agreement with the expected...Continue Reading

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Citations

Aug 27, 2011·Langmuir : the ACS Journal of Surfaces and Colloids·Christine BrowneFranz Grieser
Jul 5, 2013·Physical Chemistry Chemical Physics : PCCP·Ling GePatricia Hunt
Mar 29, 2013·The Journal of Chemical Physics·Abraham C SternDouglas J Tobias
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Jun 26, 2013·Faraday Discussions·Marcel D Baer, Christopher J Mundy
May 6, 2021·Proceedings of the National Academy of Sciences of the United States of America·Chang Yun Son, Zhen-Gang Wang
Jun 7, 2012·The Journal of Physical Chemistry Letters·Marcel D BaerChristopher J Mundy
Dec 19, 2013·The Journal of Physical Chemistry Letters·Wei HuaHeather C Allen

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