Enami, Shinichi and Hoffmann, Michael R. and Colussi, A. J. (2016) Halogen Radical Chemistry at Aqueous Interfaces. Journal of Physical Chemistry A, 120 (31). pp. 6242-6248. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20160815-132203166
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Halogens play key roles in the chemical composition of marine boundary layers, the free troposphere and the stratosphere. Atmospheric halogen chemistry is dominated by reactions between gas-phase and aqueous species on the surfaces of the ocean and marine aerosol. The mechanisms of interfacial halogen radical/halide reactions, however, are not fully understood, partly due to the dearth of techniques for in situ monitoring of the products and intermediates of fast interfacial halogen radical reactions. Here, we report the online electrospray mass spectrometric identification of the species produced on the surface of aqueous Br^– and I^– microjets collided by I•(g) pulses generated from the 266 nm laser photolysis of CH_3I/O_2/N_2 gas mixtures. Mass-specific identification of intermediates and products in D_2O and H_2^(18)O solutions and their dependences on I•(g) fluxes let us outline mechanisms of formation. We found that the uptake of I•(g) on the surface of Br^– and I^– microjets (effective uptake coefficient γ_(eff) ≥ 2 × 10^(–4)) yields IBr•–/I_2•– radical intermediates, which rapidly react with additional I• to produce trihalides I_2Br^–/Ibr_2^–/I_3^– plus I_3O_n^– (n = 1, 2) species within ∼10 μs. Our findings point to a new halogen activation pathway initiated by photogenerated I•.
|Additional Information:||© 2016 American Chemical Society. Received: April 26, 2016; Revised: June 11, 2016; Published: July 14, 2016. S.E. is grateful to the Kurita Water and Environment Foundation, the Japan Science and Technology Agency (JST) PRESTO program, and the Hakubi Project of Kyoto University. We thank Dr. Yosuke Sakamoto of Kyoto University for stimulating discussions. M.R.H. and A.J.C. acknowledge support from the National Science Foundation (U.S.A.) Grant AC-1238977. The authors declare no competing financial interest.|
|Official Citation:||Halogen Radical Chemistry at Aqueous Interfaces Shinichi Enami, Michael R. Hoffmann, and A. J. Colussi The Journal of Physical Chemistry A 2016 120 (31), 6242-6248 DOI: 10.1021/acs.jpca.6b04219|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||15 Aug 2016 22:10|
|Last Modified:||15 Aug 2016 22:10|
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