ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
High-temperature (〉1000°K) pyrolysis of acetaldehyde (∼1% in an atmosphere of pure nitrogen) was examined in a turbulent flow reactor which permits accurate determination of the spatial distribution of the stable species. Results show that the products in order of decreasing importance are CO, CH4, H2, C2H6, and C2H4. Rates of formation were consistent with the Rice-Herzfeld mechanism by including reactions to explain C2H4 formation and the possible presence of ketene. A steady-state treatment of the complete mechanism indicates that the overall reaction order decreases from \documentclass{article}\pagestyle{empty}\begin{document}$ \frac{3}{2} $\end{document} to 1, which is supported by the new experimental data. Using earlier low-temperature results, the rate constant for the reaction CH3CHO → CH3 + CHO (1) was found as k1=1015.85±0.21 exp (-81,775±1000/RT) sec-1. Also, data for the ratio of rate constants for reactions CH3CHO + CH3 → CH4 + CH3CO (4) and 2CH3 → C2H6(6) were fitted to the empirical expression k4/k61/2=10-13.89±0.03T6.1 exp(-1720±70/RT) (cm3/mole·sec)1/2 and causes for the curvature are discussed. The noncatalytic effect of oxygen on acetaldehyde pyrolysis at high temperature is explained.
Additional Material:
11 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550070207
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