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Issue 46, 2016
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Extensive H-atom abstraction from benzoate by OH-radicals at the air–water interface

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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.

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

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Supplementary files

Article information


Submitted
28 Sep 2016
Accepted
01 Nov 2016
First published
02 Nov 2016

This article is Open Access

Phys. Chem. Chem. Phys., 2016,18, 31505-31512
Article type
Paper

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

S. Enami, M. R. Hoffmann and A. J. Colussi, Phys. Chem. Chem. Phys., 2016, 18, 31505
DOI: 10.1039/C6CP06652F

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