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Anions dramatically enhance proton transfer through aqueous interfaces

Mishra, Himanshu and Enami, Shinichi and Nielsen, Robert J. and Hoffmann, Michael R. and Goddard, William A., III and Colussi, Agustín J. (2012) Anions dramatically enhance proton transfer through aqueous interfaces. Proceedings of the National Academy of Sciences of the United States of America, 109 (26). pp. 10228-10232. ISSN 0027-8424. PMCID PMC3387034.

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Proton transfer (PT) through and across aqueous interfaces is a fundamental process in chemistry and biology. Notwithstanding its importance, it is not generally realized that interfacial PT is quite different from conventional PT in bulk water. Here we show that, in contrast with the behavior of strong nitric acid in aqueous solution, gas-phase HNO_3 does not readily dissociate upon collision with the surface of water unless a few ions (>1 per 10^6 H2O) are present. By applying online electrospray ionization mass spectrometry we monitor in situ the surface of aqueous jets exposed to HNO3_(3(g)) beams and found that NO_3 − production increases dramatically on >30-μM inert electrolyte solutions. We also performed quantum mechanical calculations confirming that HNO3 dissociation on the surface of small water clusters is hindered by a sizable barrier, which is drastically lowered in the presence of an anion. Anions electrostatically assist in drawing the proton away from NO_3 −, which lingers outside the cluster because its incorporation is hampered by the energetic cost of opening a cavity therein. Present results provide both direct experimental evidence and mechanistic insights on the counterintuitive slowness of PT at water- hydrophobe boundaries and its remarkable sensitivity to electrostatic effects.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle
Hoffmann, Michael R.0000-0002-0432-6564
Goddard, William A., III0000-0003-0097-5716
Colussi, Agustín J.0000-0002-3400-4101
Additional Information:© 2012 National Academy of Sciences. Edited by Richard J. Saykally, University of California, Berkeley, CA, and approved May 1, 2012 (received for review January 17, 2012). S.E. thanks the Japan Society for the Promotion of Sciences Postdoctoral Fellowship for Research Abroad. Research supported by National Science Foundation Grant AGS-964842 (to M.R.H.). H.M. and S.E. contributed equally to this work. Author contributions: A.J.C. designed research; H.M., S.E., and R.J.N. performed research; M.R.H. contributed new reagents/analytic tools; H.M., S.E., R.J.N., M.R.H. and W.A.G. edited paper; M.R.H. provided financial support; H.M., S.E., R.J.N., W.A.G., and A.J.C. analyzed data; and A.J.C. wrote the paper. The authors declare no conflict of interest. This article is a PNAS Direct Submission. This article contains supporting information online at
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)UNSPECIFIED
Subject Keywords:air–water interface; catalysis; nitric acid dissociation
PubMed Central ID:PMC3387034
Record Number:CaltechAUTHORS:20120525-111436467
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Official Citation:Himanshu Mishra, Shinichi Enami, Robert J. Nielsen, Michael R. Hoffmann, William A. Goddard III, and Agustín J. Colussi Anions dramatically enhance proton transfer through aqueous interfaces PNAS 2012 109 (26) 10228-10232; published ahead of print June 11, 2012, doi:10.1073/pnas.1200949109
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:31654
Deposited By: Kristin Buxton
Deposited On:25 May 2012 18:27
Last Modified:14 Dec 2015 19:09

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