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Increased Propensity of I-aq(-) for the Water Surface in Non-neutral Solutions: Implications for the Interfacial Behavior of H3Oaq+ and OHaq-

Ottosson, N.; Cwiklik, L.; Soderstrom, J.; Bjorneholm, O.; Öhrwall, Gunnar LU and Jungwirth, P. (2011) In The Journal of Physical Chemistry Letters 2(9). p.972-976
Abstract
By a combination of surface-sensitive photoelectron spectroscopy and molecular dynamics simulations, we characterize the surface propensity of the iodide anion in aqueous solutions at acidic, neutral, and basic conditions (pH = 1, 6.8 and 13). In both experiments and simulations, an increased surface concentration of I- is found in non-neutral solutions. We interpret these findings in terms of I- surface coadsorption with hydronium at low pH and "salting out" of iodide by hydroxide from the bulk solution to the surface at high pH. The present study is thus in accord with the picture of a weak surface adsorption of hydronium and surface depletion of hydroxide, being in sharp contradiction with the interpretation of electrophoretic and... (More)
By a combination of surface-sensitive photoelectron spectroscopy and molecular dynamics simulations, we characterize the surface propensity of the iodide anion in aqueous solutions at acidic, neutral, and basic conditions (pH = 1, 6.8 and 13). In both experiments and simulations, an increased surface concentration of I- is found in non-neutral solutions. We interpret these findings in terms of I- surface coadsorption with hydronium at low pH and "salting out" of iodide by hydroxide from the bulk solution to the surface at high pH. The present study is thus in accord with the picture of a weak surface adsorption of hydronium and surface depletion of hydroxide, being in sharp contradiction with the interpretation of electrophoretic and titration measurements in terms of strong surface enrichment of OH-. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Letters
volume
2
issue
9
pages
972 - 976
publisher
The American Chemical Society
external identifiers
  • wos:000290372900009
  • scopus:79955909583
ISSN
1948-7185
DOI
10.1021/jz2003233
language
English
LU publication?
yes
id
6e5ce4fa-9830-40ae-920f-a98d0359843c (old id 1987808)
date added to LUP
2011-06-29 08:58:41
date last changed
2017-01-01 05:54:01
@article{6e5ce4fa-9830-40ae-920f-a98d0359843c,
  abstract     = {By a combination of surface-sensitive photoelectron spectroscopy and molecular dynamics simulations, we characterize the surface propensity of the iodide anion in aqueous solutions at acidic, neutral, and basic conditions (pH = 1, 6.8 and 13). In both experiments and simulations, an increased surface concentration of I- is found in non-neutral solutions. We interpret these findings in terms of I- surface coadsorption with hydronium at low pH and "salting out" of iodide by hydroxide from the bulk solution to the surface at high pH. The present study is thus in accord with the picture of a weak surface adsorption of hydronium and surface depletion of hydroxide, being in sharp contradiction with the interpretation of electrophoretic and titration measurements in terms of strong surface enrichment of OH-.},
  author       = {Ottosson, N. and Cwiklik, L. and Soderstrom, J. and Bjorneholm, O. and Öhrwall, Gunnar and Jungwirth, P.},
  issn         = {1948-7185},
  language     = {eng},
  number       = {9},
  pages        = {972--976},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Letters},
  title        = {Increased Propensity of I-aq(-) for the Water Surface in Non-neutral Solutions: Implications for the Interfacial Behavior of H3Oaq+ and OHaq-},
  url          = {http://dx.doi.org/10.1021/jz2003233},
  volume       = {2},
  year         = {2011},
}