Products of the Gas-Phase Reaction of OH Radicals with Cyclohexane:  Reactions of the Cyclohexoxy Radical

Aschmann, Sara M.; Chew, Andrew A.; Arey, Janet; Atkinson, Roger

doi:10.1021/jp971869f

Cited by 79 publications

(216 citation statements)

References 26 publications

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“…A large relative detection sensitivity of 0.48 ± 0.14 is measured, but model calculations predict only a small conversion efficiency of 0.14. This may be due to fast production of HO 2 from decomposition of the cyclohexoxy radical that competes with the ring maintaining reaction with O 2 (Aschmann et al, 1997;Orlando et al, 2000), but HO 2 production from this reaction has not been investigated so far. The yield of other ring-opening decomposition products was estimated to be nearly 0.50 for atmospheric conditions (Aschmann et al, 1997) similar to the relative conversion efficiency measured here.…”

Section: Interference From Alkyl Peroxy Radicalsmentioning

confidence: 99%

Detection of HO2 by laser-induced fluorescence: calibration and interferences from RO2 radicals

Fuchs¹,

Bohn²,

Hofzumahaus³

et al. 2011

Atmos. Meas. Tech.

205

219

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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.

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Section: Interference From Alkyl Peroxy Radicalsmentioning

confidence: 99%

Detection of HO2 by laser-induced fluorescence: calibration and interferences from RO2 radicals

Fuchs¹,

Bohn²,

Hofzumahaus³

et al. 2011

Atmos. Meas. Tech.

205

219

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“…In the troposphere these biogenic VOCs react with OH radicals, NO3 radicals, and O3 [Atkinson, 1997], with the OH radical reaction being an important loss process for all of these compounds [Atkinson and Amy, 1998]. …”

mentioning

confidence: 99%

“…The C•oH•r, monoterpene hydrocarbons are important constituents of biogenic VOC emissions [Guenther et al, 1995], and rate constants for the gas phase reactions of OH radicals, NO3 radicals, and O3 with 14 monoterpenes have been measured [Atkinson, 1997]. While the reaction rate constants are reasonably well understood, the reaction products and mechanisms of these reactions are less well understood [Atkinson, 1997] [1991] (56 _+ 4% and 79 __+ 8%, respectively).…”

mentioning

confidence: 99%

“…While the reaction rate constants are reasonably well understood, the reaction products and mechanisms of these reactions are less well understood [Atkinson, 1997] [1991] (56 _+ 4% and 79 __+ 8%, respectively). It has been suggested that the carbonyl yields derived from the FTIR spectroscopic analyses include product species other than pinonaldehyde and nopinone, and that these other products may include hydroxycarbonyls formed after isomerization of the /3-hydroxyalkoxy radicals formed after OH radical addition to the }C•C( bond [Hakola et al, 1994;Atkinson, 1994Atkinson, , 1997.…”

mentioning

confidence: 99%

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Products of the gas phase reactions of the OH radical with α‐ and β‐pinene in the presence of NO

Aschmann¹,

Reisseil²,

Atkinson³

et al. 1998

J. Geophys. Res.

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100

129

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Abstract. Products of the gas phase reactions of the OH radical with a-and/3-pinene in the presence of NO have been investigated using gas chromatography and in situ atmospheric pressure ionization mass spectrometry (API-MS). Acetone was identified and quantified by gas chromatography with flame ionization detection and combined gas pinene reaction and 0.085 m 0.018 from the •-pinene reaction. Acetone is a firstgeneration product and may arise after initial H atom abstraction from the tertiary allylic C-H bond at the 1 position and/or after OH radical addition at the 2 and 3 positions. Using •I-MS and API-MS/MS analyses, in addition to the formation of pinonaldehyde from a-pinene and nopinone from •-pinene, we have observed the formation of hydro,nitrates, dihydro•nitrates and dihydro•carbonyl products of molecular weights 215, 231 and 184, respectively, from both a-and •-pinene. Reaction schemes leading to the formation of these multifunctional product species, consistent with our understanding of the atmospheric chemistry of organic pero• and alkoxy radicals, are presented.

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“…Under ambient conditions the cyclohexoxy radical produced from cyclohexane reacts directly with O 2 to give cyclohexanone with yields of 25-39 % and by CÀC bond cleavage leading to ring opening products. [15,[21][22][23] In contrast, cyclopentoxy and cycloheptoxy radicals almost exclusively react by ring opening, and the yields of the corresponding cycloalkanones are < 5 %. [15,21,23] .…”

Section: Discussionmentioning

confidence: 99%

Product Study of the OH Radical and Cl Atom Initiated Oxidation of 1,3‐Dioxane

2010

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The products of the hydroxyl (OH) radical and chlorine (Cl) atom initiated oxidation of 1,3-dioxane are determined under various reaction conditions in a 50 L teflon reaction chamber using FTIR spectroscopy for analysis. The major products detected in all experiments are (2-oxoethoxy)methyl formate, formic acid and methylene glycol diformate with average molar yields of 0.50±0.05, 0.41±0.02 and 0.03±0.01 respectively for the OH initiated oxidation in the presence of NO(x). The yields of these products do not vary significantly with O(2) partial pressure or oxidising agent (OH or Cl). However, the yield of formic acid decreased by at least a factor of two in the absence of NO(x). The results of these experiments are used to elucidate a simplified gas-phase atmospheric degradation scheme for 1,3-dioxane and also provide valuable information on the atmospheric fate of the cyclic and linear alkoxy radicals produced in these and similar reactions. The available experimental data suggests that the relative importance of the competing pathways (reaction with O(2) and ring opening by C-C or C-O bond fission) is a strong function of the ring strain in the cycloalkoxy radicals.

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Products of the Gas-Phase Reaction of OH Radicals with Cyclohexane: Reactions of the Cyclohexoxy Radical

Cited by 79 publications

References 26 publications

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

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

Products of the gas phase reactions of the OH radical with α‐ and β‐pinene in the presence of NO

Product Study of the OH Radical and Cl Atom Initiated Oxidation of 1,3‐Dioxane

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Products of the Gas-Phase Reaction of OH Radicals with Cyclohexane: Reactions of the Cyclohexoxy Radical

Cited by 79 publications

References 26 publications

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

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

Products of the gas phase reactions of the OH radical with α‐ and β‐pinene in the presence of NO

Product Study of the OH Radical and Cl Atom Initiated Oxidation of 1,3‐Dioxane

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

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