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Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH 3 OH+OH reaction
Author(s) -
Rasmussen Christian Lund,
Wassard Karin Hedebo,
DamJohansen Kim,
Glarborg Peter
Publication year - 2008
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20323
Subject(s) - chemistry , branching (polymer chemistry) , methanol , kinetic energy , reaction rate , reaction rate constant , analytical chemistry (journal) , kinetics , atmospheric temperature range , branching fraction , chemical kinetics , thermodynamics , organic chemistry , catalysis , physics , quantum mechanics , atomic physics
Abstract The oxidation of methanol in a flow reactor has been studied experimentally under diluted, fuel‐lean conditions at 650–1350 K, over a wide range of O 2 concentrations (1%–16%), and with and without the presence of nitric oxide. The reaction is initiated above 900 K, with the oxidation rate decreasing slightly with the increasing O 2 concentration. Addition of NO results in a mutually promoted oxidation of CH 3 OH and NO in the 750–1100 K range. The experimental results are interpreted in terms of a revised chemical kinetic model. Owing to the high sensitivity of the mutual sensitization of CH 3 OH and NO oxidation to the partitioning of CH 3 O and CH 2 OH, the CH 3 OH + OH branching fraction could be estimated as α = 0.10 ± 0.05 at 990 K. Combined with low‐temperature measurements, this value implies a branching fraction that is largely independent of temperature. It is in good agreement with recent theoretical estimates, but considerably lower than values employed in previous modeling studies. Modeling predictions with the present chemical kinetic model is in quantitative agreement with experimental results below 1100 K, but at higher temperatures and high O 2 concentration the model underpredicts the oxidation rate. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 423–441, 2008