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Fenton Oxidation of Gaseous Isoprene on Aqueous Surfaces

Kameel, F. Rifkha and Riboni, F. and Hoffmann, M. R. and Enami, Shinichi and Colussi, A. J. (2014) Fenton Oxidation of Gaseous Isoprene on Aqueous Surfaces. Journal of Physical Chemistry C, 118 (50). pp. 29151-29158. ISSN 1932-7447. http://resolver.caltech.edu/CaltechAUTHORS:20140728-091128705

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Abstract

We report that gaseous isoprene ISO(g) is oxidized into soluble species on the surface of aqueous acidic FeCl_2 solutions simultaneously exposed to H_2O_2(g). In our experiments, ISO(g) and/or H_2O_2(g) streams intersect aqueous pH 2 FeCl_2 microjets for 10 μs. The products formed in these reactive encounters are identified in situ via online electrospray ionization mass spectrometry. We found that the (ISO)nH^+ oligomers generated from ISO(g) on the surface of pH < 4 water are oxidized into myriad products whose combined yields exceed 5%. MS^2 analysis reveals that the positive ions derived from the protonation of neutral products split H_2O and O neutrals, whereas the less abundant negative carboxylate ion products undergo CO, H_2O, and CO_2 losses. Significantly, all products are fully quenched by ·OH scavenger tert-butyl alcohol. These results are consistent with an oxidation process initiated by the addition of ·OH from (Fe^(2+)(aq) + H_2O_2(g)) to (ISO)nH^+, followed by fast reactions involving dissolved H_2O_2, HO_2·, and O_2 that lead to polyols; carbonyls; and, to a lesser extent, carboxylic acids. Our experiments demonstrate that gas-phase olefins are oxidized upon colliding on the surface of Fe-containing acidic aqueous media under typical tropospheric conditions.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp505010eDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp505010ePublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jp505010ePublisherSupporting Information
ORCID:
AuthorORCID
Hoffmann, M. R.0000-0002-0432-6564
Enami, Shinichi0000-0002-2790-7361
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 2014 American Chemical Society. Received: May 21, 2014; revised: July 9, 2014. F.R.K., M.R.H., and A.J.C. acknowledge financial support from the National Science Foundation (U.S.A.) Grant AC-1238977. F.R. gratefully acknowledges her tutor, Prof. E. Selli, and financial support from the Doctorate School in Chemistry of the University of Milan. S.E. is grateful to Kurita Water and Environment Foundation and the Japan Science and Technology Agency (JST) PRESTO program.
Funders:
Funding AgencyGrant Number
NSFAC-1238977
University of MilanUNSPECIFIED
Kurita Water and Environment FoundationUNSPECIFIED
Japan Science and Technology Agency (JST) PRESTO programUNSPECIFIED
Record Number:CaltechAUTHORS:20140728-091128705
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140728-091128705
Official Citation:Fenton Oxidation of Gaseous Isoprene on Aqueous Surfaces F. Rifkha Kameel, F. Riboni, M. R. Hoffmann, Shinichi Enami, and A. J. Colussi The Journal of Physical Chemistry C 2014 118 (50), 29151-29158 DOI: 10.1021/jp505010e
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:47512
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:28 Jul 2014 22:59
Last Modified:26 Sep 2017 18:11

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