Kinetics Study of OH Radical Reactions withn-Octane,n-Nonane, andn-Decane at 240−340 K Using the Relative Rate/Discharge Flow/Mass Spectrometry Technique

2006 ◽  
Vol 110 (44) ◽  
pp. 12150-12157 ◽  
Author(s):  
Zhuangjie Li ◽  
Sumitpal Singh ◽  
William Woodward ◽  
Lan Dang
Keyword(s):  
Mass Spectrometry ◽  
Relative Rate ◽  
Radical Reactions ◽  
Oh Radical ◽  
Kinetics Study ◽  
Discharge Flow ◽  
Mass Spectrometry Technique ◽  
Rate Discharge ◽  
Spectrometry Technique

scholarly journals Peroxy radical chemistry and OH radical production during the NO<sub>3</sub>-initiated oxidation of isoprene

2012 ◽  
Vol 12 (1) ◽  
pp. 2259-2302 ◽  
Author(s):  
A. J. Kwan ◽  
A. W. H. Chan ◽  
N. L. Ng ◽  
H. G. Kjaergaard ◽  
J. H. Seinfeld ◽  
...  
Keyword(s):  
Chemical Ionization ◽  
Branching Ratio ◽  
Peroxy Radical ◽  
Radical Reactions ◽  
Ionization Mass ◽  
Oh Radical ◽  
Peroxy Radicals ◽  
Radical Production ◽  
Mass Spectrometry Technique ◽  
Spectrometry Technique

Abstract. 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 ~42–62%. 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 dimer-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 dimer 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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