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

Literature Information

Publication Date 2016-11-02
DOI 10.1039/C6CP06652F
Impact Factor 3.676
Authors

Shinichi Enami, Michael R. Hoffmann, Agustín J. Colussi


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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 (H2O, D2O) 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.

Related Literature

GSC Tokyo Statement

2003-09-18 News

DOI: 10.1039/B304889F

Front cover

Cover

DOI: 10.1039/B0RP90001J

Contents pages

Other

DOI: 10.1039/JA99611BX011

Chemicals in the environment

2003-07-16 Editorial

DOI: 10.1039/B307692J

Front cover

Cover

DOI: 10.1039/B1RP90001C

Front cover

Other

DOI: 10.1039/JA99611FX005

Glossary of abbreviations

Other

DOI: 10.1039/JA995100310R

Editorial

Paper

DOI: 10.1039/B003524F

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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