Peroxy radical isomerization in the oxidation of isoprene

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Peroxy radical isomerization in the oxidation of isoprene.

We report experimental evidence for the formation of C(5)-hydroperoxyaldehydes (HPALDs) from 1,6-H-shift isomerizations in peroxy radicals formed from the hydroxyl radical (OH) oxidation of 2-methyl-1,3-butadiene (isoprene). At 295 K, the isomerization rate of isoprene peroxy radicals (ISO2•) relative to the rate of reaction of ISO2• + HO2 is k(isom)(295)/(k(ISO2•+HO2)(295)) = (1.2 ± 0.6) x 10(...

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Isoprene Peroxy Radical Dynamics.

Approximately 500 Tg of 2-methyl-1,3-butadiene (isoprene) is emitted by deciduous trees each year. Isoprene oxidation in the atmosphere is initiated primarily by addition of hydroxyl radicals (OH) to C4 or C1 in a ratio 0.57 ± 0.03 (1σ) to produce two sets of distinct allylic radicals. Oxygen (O2) adds to these allylic radicals either δ (Z or E depending on whether the allylic radical is cis or...

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Electronic Supporting Information (ESI) Peroxy radical isomerization in the oxida- tion of isoprene

We estimate the CIMS sensitivity for the hydroxyhydroperoxides (ISOPOOH) and hydroperoxyaldehydes (HPALD) from the ion-molecule collision rate, calculated using the parameterization of Su and Chesnavich [1]. This requires knowledge of the average dipole moment and polarizibility of the neutral species. We obtain these parameters for the species of interest from ab initio calulations. For accura...

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Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene

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 (...

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HOx Radical Regeneration in Isoprene Oxidation via Peroxy Radical Isomerisation. II: Experimental Evidence and Global Impact - Electronic Supporting Information (ESI) -

p. 2: Revised isoprene oxidation mechanism for low to moderate NOx conditions as proposed earlier (Peeters et al., PCCP, 2009), with 303 K rate coefficients from first principles; Figs. S1 and S2 p. 3: Temperature-dependent rate coefficient expressions for the unimolecular reactions of isoprene hydroxyperoxy radicals, T = 280 to 320 K, as used in this work; Table S1 p. 4: Effects of allyl-stabi...

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ژورنال

عنوان ژورنال: Physical Chemistry Chemical Physics

سال: 2011

ISSN: 1463-9076,1463-9084

DOI: 10.1039/c1cp21330j