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Extensive H-atom abstraction from benzoate by OH-radicals at the air–water interface

Enami, Shinichi and Hoffmann, Michael R. and Colussi, Agustín J. (2016) Extensive H-atom abstraction from benzoate by OH-radicals at the air–water interface. Physical Chemistry Chemical Physics, 18 (46). pp. 31505-31512. ISSN 1463-9076. http://resolver.caltech.edu/CaltechAUTHORS:20161109-095244985

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Abstract

Much is known about OH-radical chemistry in the gas-phase and bulk water. Important atmospheric and biological processes, however, involve little investigated OH-radical reactions at aqueous interfaces with hydrophobic media. Here, we report the online mass-specific identification of the products and intermediates generated on the surface of aqueous (H_2O, D_2O) benzoate-h5 and -d5 microjets by ∼8 ns ˙OH(g) pulses in air at 1 atm. Isotopic labeling lets us unambiguously identify the phenylperoxyl radicals that ensue H-abstraction from the aromatic ring and establish a lower bound (>26%) to this process as it takes place in the interfacial water nanolayers probed by our experiments. The significant extent of H-abstraction vs. its negligible contribution both in the gas-phase and bulk water underscores the unique properties of the air–water interface as a reaction medium. The enhancement of H-atom abstraction in interfacial water is ascribed, in part, to the relative destabilization of a more polar transition state for OH-radical addition vs. H-abstraction due to incomplete hydration at the low water densities prevalent therein.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/C6CP06652F DOIArticle
http://pubs.rsc.org/en/content/articlehtml/2016/cp/c6cp06652fPublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0002-0432-6564
Colussi, Agustín J.0000-0002-3400-4101
Additional Information:© 2016 the Owner Societies. Received 28th September 2016 , Accepted 1st November 2016. First published on the web 2nd November 2016. S. E. is grateful to the Hakubi Project of Kyoto University, the Iwatani Naoji Foundation's Research Grant and JSPS KAKENHI grant number 15H05328. M. R. H. and A. J. C. acknowledge support from the National Science Foundation (U.S.A.) Grant AC-1238977.
Funders:
Funding AgencyGrant Number
Iwatani Naoji FoundationUNSPECIFIED
Japan Society for the Promotion of Science (JSPS)15H05328
NSFAGS-1238977
Record Number:CaltechAUTHORS:20161109-095244985
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20161109-095244985
Official Citation:Extensive H-atom abstraction from benzoate by OH-radicals at the air–water interface Shinichi Enami, Michael R. Hoffmann and Agustín J. Colussi Phys. Chem. Chem. Phys., 2016,18, 31505-31512 DOI: 10.1039/C6CP06652F
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:71873
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:09 Nov 2016 18:21
Last Modified:23 Nov 2016 18:25

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