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| Titel |
Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene |
| VerfasserIn |
A. J. Kwan, A. W. H. Chan, N. L. Ng, H. G. Kjaergaard, J. H. Seinfeld, P. O. Wennberg |
| Medientyp |
Artikel
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| Sprache |
Englisch
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| ISSN |
1680-7316
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| Digitales Dokument |
URL |
| Erschienen |
In: Atmospheric Chemistry and Physics ; 12, no. 16 ; Nr. 12, no. 16 (2012-08-17), S.7499-7515 |
| Datensatznummer |
250011399
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| Publikation (Nr.) |
 copernicus.org/acp-12-7499-2012.pdf |
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| Zusammenfassung |
| Peroxy radical reactions (RO2 + RO2) from the
NO3-initiated oxidation of isoprene are studied with both gas
chromatography and a chemical ionization mass spectrometry technique that
allows for more specific speciation of products than in previous studies of
this system. We find high nitrate yields (~ 80%), consistent with
other studies. We further see evidence of significant hydroxyl radical (OH)
formation in this system, which we propose comes from RO2 + HO2
reactions with a yield of ~38–58%. An additional OH source is the
second generation oxidation of the nitrooxyhydroperoxide, which produces OH
and a dinitrooxyepoxide with a yield of ~35%. The branching ratio of
the radical propagating, carbonyl- and alcohol-forming, and organic peroxide-forming
channels of the RO2 + RO2 reaction are found to be
~18–38%, ~59–77%, and ~3–4%, respectively. HO2
formation in this system is lower than has been previously assumed. Addition
of RO2 to isoprene is suggested as a possible route to the formation
of several isoprene C10-organic peroxide compounds (ROOR). The nitrooxy, allylic, and
C5 peroxy radicals present in this system exhibit different behavior
than the limited suite of peroxy radicals that have been studied to date. |
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