Spectroscopy and kinetics of the peroxy radicals formed by chlorine-initiated oxidation of isoprene
2014
Peroxy radicals dominate atm. chem. as important reaction intermediates in the oxidn. of volatile org. compds. (VOCs).
Biogenic alkene emissions such as isoprene and 2-methyl-3-buten-2-ol (MBO-232) react rapidly with free radicals to form β-
substituted alkylperoxy radicals. Chlorine-initiated oxidn. of VOCs has recently become of interest as more in-land sources
of chlorine atoms are discovered. We have directly detected the A-X electronic transition spectrum of chlorine-substituted
atmospherically-relevant alkyl peroxy radicals from 7000-9000 cm^(-1) using cavity ringdown spectroscopy. Spectra of peroxy
radicals formed by chlorine-initiated oxidn. of isoprene, 2-butene, 3-methyl-1-butene, and MBO-232 are presented here.
Kinetic rate consts. of peroxy radical self-reactions and peroxy radical reactions with HO_2 and NO were obtained by
directly observing the near-IR absorption spectrum of the peroxy radical intermediate. These rate consts. will be reported
here.
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