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A direct investigation of the reaction CH3+OH: Overall rate constant and CH2formation atT=298 K

 

作者: R. Deters,   M. Otting,   H. Gg. Wagner,   F. Temps,   B. László,   S. Dóbé,   T. Bérces,  

 

期刊: Berichte der Bunsengesellschaft für physikalische Chemie  (WILEY Available online 1998)
卷期: Volume 102, issue 1  

页码: 58-72

 

ISSN:0005-9021

 

年代: 1998

 

DOI:10.1002/bbpc.19981020108

 

出版商: Wiley‐VCH Verlag GmbH&Co. KGaA

 

关键词: Chemical Kinetics;Molecular Interactions;Radicals

 

数据来源: WILEY

 

摘要:

AbstractThe rate constant and the product distribution of the reaction CH3+OH r̊ products (1) were studied at room temperature over a range of pressures (0.7 mbar ≤p≤467 mbar) with M= He as inert bath gas. At pressures of 45 to 467 mbar, towards the high pressure range of the reaction, experimental determinations were performed using the laser flash photolysis technique with transient UV absorption spectrometry (LFP/TAS) for direct monitoring of the CH3and OH radicals. In this range, the overall rate constant for the reaction was found to be practically independent of pressure atk1(298 K)=(4.4±0.8)x1013cm3mol−1s−1. At pressures of 0.7 mbar to 4.0 mbar, the reaction was studied using the discharge flow (DF) technique with laser magnetic resonance (LMR) for the direct detection of the reactants CH3and OH and the reaction product CH2. The measured overall rate constants at the low pressures were found to increase slightly with increasing pressure and approach the value at “high” pressure from the LFP/TAS experiments. From simulations of the measured concentration‐versus‐time profiles of the CH3, OH, and CH2radicals, the branching ratio for the reaction channel CH3+OHr̊ CH2+H2O (1.1) was determined atp=1.33 mbar,T=298 K to bek1.1lk1=(0.89±0.09). Implications of the results are discussed considering the fall‐off curve for the reaction, the reaction mechanism and the product distribution, and the availabl

 

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