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Cavity ringdown spectroscopy of chlorine-​substituted peroxy radicals: Reaction kinetics with nitric oxide

Smarte, Matthew D. and Dodson, Leah G. and Okumura, Mitchio (2014) Cavity ringdown spectroscopy of chlorine-​substituted peroxy radicals: Reaction kinetics with nitric oxide. In: 248th American Chemical Society National Meeting & Exposition, August 10-14, 2014, San Francisco, CA. http://resolver.caltech.edu/CaltechAUTHORS:20140814-131156147

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Abstract

Peroxy radicals (RO_2) are ubiquitous intermediates in the oxidn. of volatile org. compds. Their competing fates govern subsequent free radical chem. in the troposphere. Reaction of RO_2 with nitric oxide (NO) has two product channels: assocn. to an org. nitrate (RONO_2) or oxidn./redn. to nitrogen dioxide (NO_2) and an alkoxy radical (RO). In this work, we present measurements of the RO_2 + NO rate const. at several pressures for peroxy radicals formed in the chlorine-initiated oxidn. of ethene, propene, 2-butene, and isoprene. We monitor the decay of peroxy radicals through their weak and structured A-X transition in the near-IR using cavity ringdown spectroscopy (CRDS) and the simultaneous kinetics and ringdown (SKaR) technique. Chlorine is a minor tropospheric oxidant found in marine regions and its substitution yields insight into the structure and reactivity of RO_2 species. We compare our results to prior work in the literature at a fixed pressure and to measurements on hydroxyl-substituted peroxy radicals.


Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription
http://www.acs.org/content/acs/en/meetings/fall-2014.htmlOrganizationConference Website
ORCID:
AuthorORCID
Okumura, Mitchio0000-0001-6874-1137
Additional Information:© 2014 American Chemical Society.
Record Number:CaltechAUTHORS:20140814-131156147
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140814-131156147
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:48570
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:14 Aug 2014 20:24
Last Modified:14 Sep 2015 23:30

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