Kinetics and Rate Constants of the Reaction CH2OH + O2→ CH2O + HO2in the Temperature Range of 236−600 K

Schocker, Alexander; Uetake, Masanori; Kanno, Nozomu; Koshi, Mitsuo; Tonokura, Kenichi

doi:10.1021/jp0682513

Cited by 40 publications

(37 citation statements)

References 47 publications

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“…The reaction of the hydroxy methyl radical (CH 2 OH) with O 2 was studied by Grotheer et al (1988), Nesbitt et al (1988), and more recently by Olivella et al (2001) and Schocker et al (2007). A complete overview of the available measurements of the rate coefficient of this reaction can be found in Atkinson et al (2006).…”

Section: B5 Ch 2 Oh+o 2 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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Section: B5 Ch 2 Oh+o 2 Reactionmentioning

confidence: 99%

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

2009

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“…In particular, the hydrogen-bond complex between HO 2 and water [28][29][30][31][32][33][34][35][36][37] has also attracted much attention as it potentially affects the photochemistry of atmosphere. Furthermore, there are some theoretical and experimental investigations [38][39][40][41][42] on the reactions of CH 2 OH, CH 3 CHOH with molecular oxygen responsible for the formation of the HO 2 radical.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls

Long

Wang

et al. 2011

Int J of Quantum Chemistry

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ABSTRACT:The initial reactions of HO 2 with oxalyl dichloride, oxalyl dibromide, acetyl chloride, and acetyl bromide are studied for the first time using the density functional theory with CAM-B3LYP and wB97XD, CBS-QB3, and G3 theoretical methods and the transition state theory. The reactions occur via the similar mechanism that the prereactive complex is formed before the transition state and product. The calculated results demonstrate that the HO 2 radical with ClC(O)C(O)Cl and BrC(O)C(O)Br reactions is feasible and could play a significant role in the atmosphere because the barriers are 0.13 kcal/mol, À0.05 kcal/mol with respect to the free reactants, respectively at the CBS-QB3 level of theory. In addition, the rate constants of the HO 2 þ ClC(O)C(O)Cl and HO 2 þ BrC(O)C(O)Br reactions are computed to be 1.37 Â 10 À15 cm 3 mol À1 s À1 , 1.70 Â 10 À15 cm 3 mol À1 s À1 at 298 K. However, the HO 2 reactions with acetyl chloride and acetyl bromide are of no importance because of higher activated barrier and slower rate constant.

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Section: B5 Ch 2 Oh+o 2 Reactionmentioning

confidence: 99%

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

Pieterse¹,

Krol²,

Röckmann³

2009

Preprint

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Abstract. The isotopic composition of molecular hydrogen (H2) produced by photochemical oxidation of methane (CH4) and Volatile Organic Compounds (VOCs) is a key quantity in the global isotope budget of (H2). 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 CH4 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 CH4+Cl. The same approach is applied to VOCs, which are important precursors of H2 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 H2 product. The reaction scheme is directly applicable in global chemistry models, which can thus include the isotope pathway of H2 produced from CH4 and VOCs in a consistent way.

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Kinetics and Rate Constants of the Reaction CH₂OH + O₂→ CH₂O + HO₂in the Temperature Range of 236−600 K

Cited by 40 publications

References 47 publications

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

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

Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls

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

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Kinetics and Rate Constants of the Reaction CH2OH + O2→ CH2O + HO2in the Temperature Range of 236−600 K

Cited by 40 publications

References 47 publications

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

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

Theoretical study on HO2‐initiated atmospheric oxidation of halogenated carbonyls

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

Contact Info

Product

Resources

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Kinetics and Rate Constants of the Reaction CH₂OH + O₂→ CH₂O + HO₂in the Temperature Range of 236−600 K

Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls