Peroxy radical isomerization in the oxidation of isoprene

John D. Crouse; Fabien Paulot; Henrik Grum Kjærgaard; Paul O. Wennberg

Peroxy radical isomerization in the oxidation of isoprene

John D. Crouse, Fabien Paulot, Henrik Grum Kjærgaard, Paul O. Wennberg

Department of Chemistry

208 Citations (Scopus)

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 relative to the rate of reaction of, or k. ²⁹⁵_isom ≃ 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 . The overall uncertainty in the isomerization rate (relative to) 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.

Original language	English
Journal	Physical chemistry chemical physics : PCCP
Volume	13
Pages (from-to)	13607-13613
Number of pages	7
Publication status	Published - 2011

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title = "Peroxy radical isomerization in the oxidation of isoprene",

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 relative to the rate of reaction of, or k. 295isom ≃ 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 . The overall uncertainty in the isomerization rate (relative to) 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.",

author = "Crouse, {John D.} and Fabien Paulot and Kj{\ae}rgaard, {Henrik Grum} and Wennberg, {Paul O.}",

year = "2011",

language = "English",

volume = "13",

pages = "13607--13613",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - Peroxy radical isomerization in the oxidation of isoprene

AU - Crouse, John D.

AU - Paulot, Fabien

AU - Kjærgaard, Henrik Grum

AU - Wennberg, Paul O.

PY - 2011

Y1 - 2011

N2 - 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 relative to the rate of reaction of, or k. 295isom ≃ 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 . The overall uncertainty in the isomerization rate (relative to) 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.

AB - 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 relative to the rate of reaction of, or k. 295isom ≃ 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 . The overall uncertainty in the isomerization rate (relative to) 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.

M3 - Journal article

SN - 1463-9076

VL - 13

SP - 13607

EP - 13613

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

ER -

Peroxy radical isomerization in the oxidation of isoprene

Abstract

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