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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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)|
|Additional Information:||© 2014 American Chemical Society.|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||14 Aug 2014 20:24|
|Last Modified:||14 Sep 2015 23:30|
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