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Kinetics and near-​infrared spectroscopy of chlorine-​substituted peroxy radicals

Smarte, Matthew D. and Dodson, Leah G. and Takematsu, Kana and Eddingsaas, Nathan C. and Okumura, Mitchio (2014) Kinetics and near-​infrared spectroscopy of chlorine-​substituted peroxy radicals. In: 248th American Chemical Society National Meeting & Exposition, 10-14 August 2014, San Francisco, CA.

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Peroxy radicals form in the atm. oxidn. of nearly every volatile org. compd. (VOC). Their competing fates propagate or terminate free radical chem. in the troposphere. Atomic chlorine is a minor tropospheric oxidant, found in marine and coastal regions, which reacts with volatile alkenes to yield chlorine-substituted peroxy radicals. In this work, we present the near-IR absorption spectra of peroxy radicals formed in the chorine-initiated oxidn. of a variety of VOCs including isoprene, the most important nonmethane hydrocarbon emitted into the troposphere. We use cavity ringdown spectroscopy to observe the weak A-X electronic transition of peroxy radicals in the near-IR region. By monitoring the temporal decay of absorption features under varying radical environments, we report rate consts. for the self reaction of chlorine-substituted peroxy radicals as well as their dominant atm. fates: reaction with HO_2 and NO. Reaction with HO_2 is important in pristine environments while reaction with NO dominates in polluted regions. We compare our results to those available for hydroxyl-substituted and alkyl peroxy radicals to elucidate the effect of chlorine substitution on peroxy radical reactivity. To our knowledge, these results report the first near-IR absorption spectrum of a peroxy radical derived from isoprene oxidn. The real-time kinetic measurements of the reaction with HO_2 and NO provide insight into the highly atmospherically relevant isoprene system.

Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription Website
Dodson, Leah G.0000-0001-5960-056X
Takematsu, Kana0000-0002-2334-336X
Eddingsaas, Nathan C.0000-0003-1539-5415
Okumura, Mitchio0000-0001-6874-1137
Additional Information:© 2014 American Chemical Society.
Record Number:CaltechAUTHORS:20140811-133255291
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:48324
Deposited By: Tony Diaz
Deposited On:11 Aug 2014 20:48
Last Modified:21 Feb 2020 23:07

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