Jump to main content
Jump to site search

Issue 30, 2011
Previous Article Next Article

Peroxy radical isomerization in the oxidation of isoprene

Author affiliations

Abstract

We report experimental evidence for the formation of C5-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 Image ID:c1cp21330j-t1.gif relative to the rate of reaction of Image ID:c1cp21330j-t2.gif is Image ID:c1cp21330j-t3.gif, or k295isom ≃ 0.002 s−1. The temperature dependence of this rate was determined through experiments conducted at 295, 310 and 318 K and is well described by Image ID:c1cp21330j-t4.gif. The overall uncertainty in the isomerization rate (relative to Image ID:c1cp21330j-t5.gif) is estimated to be 50%. Peroxy radicals from the oxidation of the fully deuterated isoprene analog isomerize at a rate ∼15 times slower than non-deuterated isoprene. The fraction of isoprene peroxy radicals reacting by 1,6-H-shift isomerization is estimated to be 8–11% globally, with values up to 20% in tropical regions.

Graphical abstract: Peroxy radical isomerization in the oxidation of isoprene

Back to tab navigation

Supplementary files

Additions and corrections

Publication details

The article was received on 26 Apr 2011, accepted on 08 Jun 2011 and first published on 24 Jun 2011


Article type: Communication
DOI: 10.1039/C1CP21330J
Citation: Phys. Chem. Chem. Phys., 2011,13, 13607-13613
  •   Request permissions

    Peroxy radical isomerization in the oxidation of isoprene

    J. D. Crounse, F. Paulot, H. G. Kjaergaard and P. O. Wennberg, Phys. Chem. Chem. Phys., 2011, 13, 13607
    DOI: 10.1039/C1CP21330J

Search articles by author

Spotlight

Advertisements