Direct kinetic studies of the reactions of 2-butoxy radicals with NO and O2

Deng, Wei; Wang, Chuji; Katz, David R.; Gawinski, Gregory R.; Davis, Andrew; Dibble, Theodore S.

doi:10.1016/s0009-2614(00)01136-2

Cited by 27 publications

(48 citation statements)

References 20 publications

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“…The authors also found that the reaction was independent of total pressure from 5 to 80 torr. Work by Dibble and co‐workers 30 and Seakins and co‐workers 31 also support a pressure‐independent rate constant of 3 × 10 −11 cm 3 molecule −1 s −1 . For the decomposition of the alkoxy radical we find that the data can be best fit with a rate constant of (3.0 ± 0.5) × 10 4 s −1 , which agrees fairly well with the rate of 1.5 × 10 5 s −1 used by Stevens et al 5.…”

Section: Resultsmentioning

confidence: 77%

The fate of the hydroxyalkoxy radical in the OH‐initiated oxidation of isoprene

Reitz

McGivern

Church

et al. 2002

Int J of Chemical Kinetics

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Rate constants for several intermediate steps in the OH-initiated oxidation of isoprene were determined using laser-photolysis/laser-induced fluorescence of OH radicals at total pressures between 3 and 4 Torr at 295 K. The rate constant for decomposition of the hydroxyalkoxy radical was determined to be (3.0 ± 0.5) × 10 4 s −1 in this pressure range, which is in fair agreement with previous work. The presence of a prompt alkoxy decomposition pathway was also investigated and found to contribute less than 10% to the total hydroxyalkoxy radical decomposition. The rate constant for the reaction of the hydroxyperoxy radical with NO was determined to be (2.5 ± 0.5) × 10 −11 cm 3 molecule −1 s −1 , which is moderately higher than previously reported.

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Section: Resultsmentioning

confidence: 77%

The fate of the hydroxyalkoxy radical in the OH‐initiated oxidation of isoprene

Reitz

McGivern

Church

et al. 2002

Int J of Chemical Kinetics

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“…The reaction with NO has been studied twice using the same technique of LP/LIF by Deng et al 9 and Lotz et al 10 Both found in the temperature range 223 K o T o 311/305 K a negative activation energy and no pressure dependence.…”

Section: Introductionmentioning

confidence: 99%

“…The rate constant k 2 for the reaction with O 2 has been the subject of two papers: Deng et al 9 studied this reaction between 223 and 311 K, using the direct LIF technique, while Hein et al 11 measured at 293 K and 50 mbar in a somewhat indirect experiment. They fit NO 2 and OH concentration-time profiles, obtained during pulse initiated oxidation of 2-bromobutane in the presence of O 2 and NO, to a complex mechanism.…”

Section: Introductionmentioning

confidence: 99%

Rate constants for the decomposition of 2-butoxy radicals and their reaction with NO and O2

Falgayrac

Caralp

Sokolowski-Gomez

et al. 2004

Phys. Chem. Chem. Phys.

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The reactivity of 2-butoxy radicals has been investigated using the laser photolysis/laser induced fluorescence technique. Three reactions have been studied: (i) The rate constants for the reaction with NO have been measured by the same technique at total pressures between 0.03 o p o 0.4 bar of helium and at five temperatures between 295-348 K. No pressure dependence has been found within the experimental error, and a small negative temperature dependence has been found, in agreement with earlier studies: k 1 ¼ (4.4 AE 0.6) Â 10 À12 exp((4.9 AE 0.3) kJ mol À1 /RT) cm 3 s À1 . (ii) The rate constant with O 2 has been measured at room temperature and 0.131 bar of helium: k 2 ¼ (9 AE 2) Â 10 À15 cm 3 s À1 . Significant quenching of 2-butoxy fluorescence by O 2 prevented experiments in a larger temperature range: k q,O 2 ¼ (4 AE 1) Â 10 À11 cm 3 s À1 . (iii) The temperature and pressure dependence of the unimolecular decomposition at total pressures between 0.01 o p o 0.8 bar of helium and at four temperatures between 291-348 K. The low and the high pressure limiting rate constants as well as the broadening factor F cent have been extracted from a falloff analysis of the experimental results: k 3,0,He ¼ 3.2 Â 10 À8 exp(À35.9 kJ mol À1 /RT) cm 3 s À1 , k 3,N ¼ 1.1 Â 10 14 exp(À53.6 kJ mol À1 /RT) s À1 , and F 3,c ¼ 0.87 À T/870 K. We anticipate an uncertainty of AE30% for these rate constants. These results are in excellent agreement with earlier predictions (C.

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“…Several timeresolved probing methods were developed over the last few decades and the most popular methods available in the literature are based on laser induced fluorescence (LIF) spectroscopy, UV/ Visible/ NIR absorption spectroscopy, mass spectrometry, etc. [7][8][9][10][11][12][13][14][15][16] Each of these probing techniques has its own merits as well as limitations. For example, laser induced fluorescence (LIF) is * For correspondence known to be an extremely sensitive method for detection of fluorescent radicals, but for non-fluorescent species, viz.…”

Section: Introductionmentioning

confidence: 99%

“…organic peroxy radicals, the method cannot be used directly. 7,8,13,14 Likewise, in spite of being extremely sensitive, simple mass spectrometric technique cannot be used in differentiating isomeric species present in a gas mixture. Organic radicals usually have strong absorption bands in ultraviolet, and for that reason UV spectroscopy is being used extensively over a long period for probing different radical species.…”

Section: Introductionmentioning

confidence: 99%

Mid-infrared quantum cascade laser spectroscopy probing of the kinetics of an atmospherically significant radical reaction, $$\hbox {CH}_{3}\hbox {O}_{2}+\hbox {NO}_{2}+\hbox {M}\rightarrow \hbox {CH}_{3}\hbox {O}_{2}\hbox {NO}_{2}+\hbox {M}$$ CH 3

et al. 2018

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The kinetic parameters of an important atmospheric reaction, CH 3 O 2 +NO 2 +M → CH 3 O 2 NO 2 + M, have been recorded by monitoring directly the changes in concentrations of methylperoxy radicals (CH 3 O 2) in the gas phase employing a new mid-infrared quantum cascade laser (QCL)-based apparatus. CH 3 O 2 radicals in our apparatus have been generated by pulsed UV laser (266 nm) photolysis of CH 3 I in a gaseous mixture with oxygen. The absorption band corresponding to the mid-infrared O-O stretching fundamental of the peroxy radical, within a narrow spectral range, 1070-1120 cm −1 , has been recorded by tuning the wavelength of the QCL operated in CW mode. The kinetics of the aforementioned reaction of CH 3 O 2 with NO 2 has been followed by analyzing the changes of the infrared (QCL) decay profile of CH 3 O 2 at 9.1 μm (1098.9 cm −1) maintaining a pseudo first order reaction condition. We noticed that the rate constant of the reaction at 298 K varies in the range of (1.21-3.08) ×10 −12 cm 3 molecule −1 s −1 for changing the total pressure in the range of 75-730 mbar. The absorption cross-section of CH 3 O 2 at the probe wavelength (1098.9 cm −1), has been estimated for the first time to be 8.3 ± 0.4 × 10 −20 cm 2 .

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Direct kinetic studies of the reactions of 2-butoxy radicals with NO and O2

Cited by 27 publications

References 20 publications

The fate of the hydroxyalkoxy radical in the OH‐initiated oxidation of isoprene

The fate of the hydroxyalkoxy radical in the OH‐initiated oxidation of isoprene

Rate constants for the decomposition of 2-butoxy radicals and their reaction with NO and O2

Mid-infrared quantum cascade laser spectroscopy probing of the kinetics of an atmospherically significant radical reaction, $$\hbox {CH}_{3}\hbox {O}_{2}+\hbox {NO}_{2}+\hbox {M}\rightarrow \hbox {CH}_{3}\hbox {O}_{2}\hbox {NO}_{2}+\hbox {M}$$ CH 3

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