Kinetics of the reactions of the hydroxyl radical with CH3OH and C2H5OH between 235 and 360 K

Jiménez, Elena; Gilles, Mary K.; Ravishankara, A. R.

doi:10.1016/s1010-6030(03)00073-x

Cited by 93 publications

(117 citation statements)

References 21 publications

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“…As seen in Table 1, our result agrees well with the previous values obtained in absolute methods [18][19][20][21][22] and the result obtained by Wu et al [23] by similar technique. We could believe that our smog chamber system is suitable for the simulation of gas phase reactions of OH radicals with VOC.…”

Section: Kinetics Of Oh Radicals With Ethanolsupporting

confidence: 92%

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

Wang

2011

Chin. Sci. Bull.

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Using an improved smog chamber system, the temperature dependence of OH radical reaction with EMS was investigated over the temperature range of 297-346 K at 1.01×10 5 Pa pressure of air. The Arrhenius expression of the reaction was obtained for the first time. The mechanism of the reaction was also investigated. smog chamber, temperature dependence, OH radicals, mechanism, sulfide Citation:Wang K, Ge M F, Wang W G. Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS.

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Section: Kinetics Of Oh Radicals With Ethanolsupporting

confidence: 92%

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

Wang

2011

Chin. Sci. Bull.

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“…Hess and Tully, 1989;McCaulley et al, 1989;Jiménez et al, 2003;Atkinson et al, 2006). In the proposed hydrogen isotope scheme, the reaction of deuterated methyl peroxide with non-deuterated methyl peroxide leads to the formation of two types of deuterated methanol molecules, i.e.…”

Section: B4 Ch 3 Oh+oh Reactionmentioning

confidence: 99%

A consistent molecular hydrogen isotope chemistry scheme based on an independent bond approximation

2009

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Abstract. The isotopic composition of molecular hydrogen (H 2 ) produced by photochemical oxidation of methane (CH 4 ) and Volatile Organic Compounds (VOCs) is a key quantity in the global isotope budget of (H 2 ). The many individual reaction steps involved complicate its investigation. Here we present a simplified structure-activity approach to assign isotope effects to the individual elementary reaction steps in the oxidation sequence of CH 4 and some other VOCs. The approach builds on and extends the work by Gerst and Quay (2001) and Feilberg et al. (2007b). The description is generalized and allows the application, in principle, also to other compounds. The idea is that the C-H and C-D bonds -seen as reactive sites -have similar relative reaction probabilities in isotopically substituted, but otherwise identical molecules. The limitations of this approach are discussed for the reaction CH 4 +Cl. The same approach is applied to VOCs, which are important precursors of H 2 that need to be included into models. Unfortunately, quantitative information on VOC isotope effects and source isotope signatures is very limited and the isotope scheme at this time is limited to a strongly parameterized statistical approach, which neglects kinetic isotope effects. Using these concepts we implement a full hydrogen isotope scheme in a chemical box model and carry out a sensitivity study to identify those reaction steps and conditions that are most critical for the isotope composition of the final H 2 product. The reaction scheme is directly applicable in global chemistry models, which can thus include the isotope pathway of H 2 produced from CH 4 and VOCs in a consistent way.

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“…[1][2][3][4][5][6] The reaction's non-Arrhenius behaviour in the temperature range between 210 K and 870K results from characteristic features of the potential energy surface, 7 including a loose pre-reaction complex (before the activation barrier), OH…O(H)CH 3 , and transition states with low barrier heights formed by the roaming OH abstracting either the H atom of the hydroxyl group (TS-H) or one of the H atoms of the methyl group (TS-M). 8 Reaction complexes which form after these barriers then fall apart to yield: (R1a) (R1b) where the enthalpies of reaction have been calculated from up-to-date standard compilations of heats of formation.…”

Section: Introductionmentioning

confidence: 99%

Low Temperature Kinetics of the CH₃OH + OH Reaction

et al. 2014

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The rate constant of the reaction between methanol and the hydroxyl radical has been studied in the temperature range 56-202 K by pulsed laser photolysis-laser induced fluorescence in two separate experiments using either a low temperature flow tube coupled to a time of flight mass spectrometer or a pulsed Laval nozzle apparatus. The two independent techniques yield rate constants which are in mutual agreement and consistent with the results reported previously below 82 K [Shannon et al., Nature Chemistry, 2013, 5, 745-749] and above 210 K [Dillon et al., Phys. Chem. Chem. 2005, 7, 349-355], showing a very sharp increase with decreasing temperature with an onset around 180 K. This onset is also signalled by strong chemiluminescence tentatively assigned to formaldehyde, which is consistent with the formation of the methoxy radical at low temperature by quantum tunnelling, and its subsequent reaction with H and OH. Our results add confidence to the previous low temperature rate constant measurements and consolidate the experimental reference dataset for further theoretical work required to describe quantitatively the tunnelling mechanism operating in this reaction. An additional measurement of the rate constant at 56 K yielded a value of (4.9 ± 0.8) × 10 −11 cm 3 molecule −1 s −1 (2σ), showing that the rate constant is increasing less rapidly at temperatures below 70 K.

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Kinetics of the reactions of the hydroxyl radical with CH3OH and C2H5OH between 235 and 360 K

Cited by 93 publications

References 21 publications

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

A consistent molecular hydrogen isotope chemistry scheme based on an independent bond approximation

Low Temperature Kinetics of the CH₃OH + OH Reaction

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Kinetics of the reactions of the hydroxyl radical with CH3OH and C2H5OH between 235 and 360 K

Cited by 93 publications

References 21 publications

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

A consistent molecular hydrogen isotope chemistry scheme based on an independent bond approximation

Low Temperature Kinetics of the CH3OH + OH Reaction

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Product

Resources

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Low Temperature Kinetics of the CH₃OH + OH Reaction