OH-initiated oxidation of benzene

Volkamer, Rainer; Klotz, Björn; Barnes, Ian; Igarashi, Takashi; Wirtz, Klaus; Washida, Nobuaki; Becker, K. H.; Platt, U.

doi:10.1039/b108747a

Cited by 157 publications

(181 citation statements)

References 47 publications

Supporting

Mentioning

158

Contrasting

Order By: Relevance

“…It is worth noting that this addition followed by the addition to oxygen of the adduct mainly controls the chemistry of the decomposition of aromatic compounds under atmospheric conditions [290]. One could wonder if such reactions, which are similar to those considered for alkenes, could be of importance during the oxidation of benzene and toluene at much lower temperatures than what has been investigated during the validation of the present models.…”

Section: 4a/ Additions To the Aromatic Cycles And Derived Reactionsmentioning

confidence: 77%

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

Battin‐Leclerc

2008

Progress in Energy and Combustion Science

581

379

View full text Add to dashboard Cite

show abstract

Section: 4a/ Additions To the Aromatic Cycles And Derived Reactionsmentioning

confidence: 77%

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

Battin‐Leclerc

2008

Progress in Energy and Combustion Science

581

379

View full text Add to dashboard Cite

show abstract

“…Products are phenol plus HO 2 (yield: 0.53, Volkamer et al, 2002) and RO 2 radicals, part of which most likely decomposes to epoxides and HO 2 (yield: 0.12, Bloss et al, 2005b). Only 0.35 of the products in the reaction of benzene with OH is a bicyclic peroxy radical which behaves similar to hydroxyalkyl peroxy radicals.…”

Section: Interference From Ro 2 Produced By Benzene + Ohmentioning

confidence: 99%

Detection of HO<sub>2</sub> by laser-induced fluorescence: calibration and interferences from RO<sub>2</sub> radicals

Fuchs¹,

Bohn²,

Hofzumahaus³

et al. 2011

Atmos. Meas. Tech.

214

224

View full text Add to dashboard Cite

Abstract. HO 2 concentration measurements are widely accomplished by chemical conversion of HO 2 to OH including reaction with NO and subsequent detection of OH by laser-induced fluorescence. RO 2 radicals can be converted to OH via a similar radical reaction sequence including reaction with NO, so that they are potential interferences for HO 2 measurements. Here, the conversion efficiency of various RO 2 species to HO 2 is investigated. Experiments were conducted with a radical source that produces OH and HO 2 by water photolysis at 185 nm, which is frequently used for calibration of LIF instruments. The ratio of HO 2 and the sum of OH and HO 2 concentrations provided by the radical source was investigated and was found to be 0.50 ± 0.02. RO 2 radicals are produced by the reaction of various organic compounds with OH in the radical source. Interferences via chemical conversion from RO 2 radicals produced by the reaction of OH with methane and ethane (H-atom abstraction) are negligible consistent with measurements in the past. However, RO 2 radicals from OH plus alkene-and aromaticprecursors including isoprene (mainly OH-addition) are detected with a relative sensitivity larger than 80 % with respect to that for HO 2 for the configuration of the instrument with which it was operated during field campaigns. Also RO 2 from OH plus methyl vinyl ketone and methacrolein exhibit a relative detection sensitivity of 60 %. Thus, previous measurements of HO 2 radical concentrations with this instrument were biased in the presence of high RO 2 radical concentrations from isoprene, alkenes or aromatics, but were not affected by interferences in remote clean environment with no significant emissions of biogenic VOCs, when the OH reactivity was dominated by small alkanes. By reducing the NO concentration and/or the transport time betweenCorrespondence to: H. Fuchs (h.fuchs@fz-juelich.de) NO addition and OH detection, interference from these RO 2 species are suppressed to values below 20 % relative to the HO 2 detection sensitivity. The HO 2 conversion efficiency is also smaller by a factor of four, but this is still sufficient for atmospheric HO 2 concentration measurements for a wide range of conditions.

show abstract

“…Again, an exponential expression for the OH concentration, Full lines correspond to fitted decays according to eqn (2), (4), (7) and (8 . Because of the potential RO 2 interference (eqn (R6) and (R7)), S HO x may contain an additional term compared to eqn (6):…”

Section: Data Evaluationmentioning

confidence: 99%

“…The experimentally confirmed main product of these reactions is phenol. The phenol yield of the benzene + OH reaction in air was investigated in several studies during the last decade [7][8][9][10][11] and the currently proposed value for NO x free reaction conditions is 0.53 AE 0.07. 12,13 The importance of the reaction pathways forming epoxide products 14 ( Fig.…”

Section: Introductionmentioning

confidence: 99%

HO2 formation from the OH + benzene reaction in the presence of O2

Nehr

Bohn

Fuchs

et al. 2011

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

In this study we investigated the secondary formation of HO 2 following the benzene + OH reaction in N 2 with variable O 2 content at atmospheric pressure and room temperature in the absence of NO. After pulsed formation of OH, HO x (= OH + HO 2 ) and OH decay curves were measured by means of a laser-induced fluorescence technique (LIF). In synthetic air the total HO 2 yield was determined to be 0.69 AE 0.10 by comparison to results obtained with CO as a reference compound. HO 2 is expected to be a direct product of the reaction of the intermediately formed OH-benzene adduct with O 2 . The HO 2 yield is slightly greater than the currently recommended yield of the proposed HO 2 co-product phenol (B53%). This hints towards other, minor HO 2 forming channels in the absence of NO, e.g. the formation of epoxide species that was proposed in the literature. For other test compounds upper limits of HO 2 yields of 0.10 (isoprene) and 0.05 (cyclohexane) were obtained, respectively. In further experiments at low O 2 concentrations (0.06-0.14% in N 2 ) rate constants of (2.4 AE 1.1) Â 10 À16 cm 3 s À1 and (5.6 AE 1.1) Â 10 À12 cm 3 s À1were estimated for the OH-benzene adduct reactions with O 2 and O 3 , respectively. The rate constant of the unimolecular dissociation of the adduct back to benzene + OH was determined to be (3.9 AE 1.3) s À1. The HO 2 yield at low O 2 was similar to that found in synthetic air, independent of O 2 and O 3 concentrations indicating comparable HO 2 yields for the adduct + O 2 and adduct + O 3 reactions.

show abstract

OH-initiated oxidation of benzene

Cited by 157 publications

References 47 publications

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

Detection of HO<sub>2</sub> by laser-induced fluorescence: calibration and interferences from RO<sub>2</sub> radicals

HO2 formation from the OH + benzene reaction in the presence of O2

Contact Info

Product

Resources

About

OH-initiated oxidation of benzene

Cited by 157 publications

References 47 publications

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

Detection of HO&lt;sub&gt;2&lt;/sub&gt; by laser-induced fluorescence: calibration and interferences from RO&lt;sub&gt;2&lt;/sub&gt; radicals

HO2 formation from the OH + benzene reaction in the presence of O2

Contact Info

Product

Resources

About

Detection of HO<sub>2</sub> by laser-induced fluorescence: calibration and interferences from RO<sub>2</sub> radicals