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Acetaldehyde oxidation in the negative temperature coefficient regime: Experimental and modeling results
Author(s) -
Kaiser E. W.,
Westbrook C. K.,
Pitz W. J.
Publication year - 1986
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.550180606
Subject(s) - chemistry , acetaldehyde , decomposition , radical , kinetic energy , thermodynamics , reaction mechanism , temperature coefficient , computational chemistry , organic chemistry , ethanol , catalysis , physics , quantum mechanics
Acetaldehyde oxidation has been studied in experiments at temperatures of 553 and 713 K carried out in a low pressure, static reactor and in numerical modeling calculations using a detailed chemical kinetic reaction mechanism. The results of the experimental study were used to construct and validate the reaction mechanism, which was then used to examine acetaldehydeoxidation in the negative temperature coefficient regime between 550 and 900 K. This mechanism was also tested against independent measurements of acetaldehyde oxidation carried out by Baldwin, Matchan, and Walker. The overall rate of reaction and the properties of the negative temperature coefficient regime were found to be sensitive to the competition between radical decomposition reactions and the addition of molecular oxygen to acetyl and methyl radicals, including particularly\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm O}_2 + {\rm M = CH}_{\rm 3} {\rm O}_{\rm 2} + {\rm M} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm CO} + {\rm M = CH}_{\rm 3} {\rm + CO} + {\rm M} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm CO} + {\rm O}_{\rm 2} {\rm = CH}_{\rm 3} {\rm CO}_{\rm 3} $$\end{document}During these experiments, an upper limit to the rate of decomposition ofCH 3 O 2 H was measured at 553 K. Implications of the results for future kinetic modeling of engine knock are discussed.