Document Detail


Methyl vinyl ketone+OH and methacrolein+OH oxidation reactions: a master equation analysis of the pressure- and temperature-dependent rate constants.
MedLine Citation:
PMID:  17066494     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
High-level electronic structure calculations and master equation analyses were carried out to obtain the pressure- and temperature-dependent rate constants of the methyl vinyl ketone+OH and methacrolein+OH reactions. The balance between the OH addition reactions at the high-pressure limit, the OH addition reactions in the fall-off region, and the pressure-independent hydrogen abstractions involved in these multiwell and multichannel systems, has been shown to be crucial to understand the pressure and temperature dependence of each global reaction. In particular, the fall-off region of the OH addition reactions contributes to the inverse temperature dependence of the rate constants in the Arrhenius plots, leading to pressure-dependent negative activation energies. The pressure dependence of the methyl vinyl ketone+OH reaction is clearly more important than in the case of the methacrolein+OH reaction owing to the weight of the hydrogen abstraction process in this second system. Comparison of the theoretical rate constants and the experimental measurements shows quite good agreement.
Authors:
Montserrat Ochando-Pardo; Ignacio Nebot-Gil; Angels González-Lafont; José M Lluch
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  13     ISSN:  0947-6539     ISO Abbreviation:  Chemistry     Publication Date:  2007  
Date Detail:
Created Date:  2007-01-17     Completed Date:  2007-03-29     Revised Date:  2009-08-04    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  Germany    
Other Details:
Languages:  eng     Pagination:  1180-90     Citation Subset:  -    
Affiliation:
Universitat de València, Institut de Ciència Molecular, Apdo. 22085, 46071 València, Spain.
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