ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Experiments with propane-ethylene mixtures in the temperature range 760-830 K resulted in refinement of the role of ethylene inhibition in the decomposition of propane. The source of the rate-reducing effect of ethylene is the reaction This replaces the decomposition chains more slowly by means of the reactions than H-atoms do by direct H-abstraction from propane. Analysis of the ratios of the product formation rates showed that the selectivity of the ethyl radical for the abstraction of hydrogen of different bond strengths from propane was practically the same as that of the H-atom. The ratio of the rate constants of hydrogen addition to ethylene and methyl-hydrogen abstraction from propane by the H-atom (3) was determined \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{k_3 }}{{k_8 }} = 10^{5.89 \pm 0.05} \exp ( - 30.8 \pm 1.1{\rm kJ mol}^{{\rm - 1}} /RT) $$\end{document} as was that of the decomposition and the similar H-abstraction of the ethyl radical \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{k_3 }}{{k_8 }} = 10^{5.11 \pm 0.61} \exp ( - 129 \pm 10{\rm kJ mol}^{{\rm - 1}} /RT){\rm mol}^{{\rm - 1}} {\rm dm}^{\rm 3}. $$\end{document}Interpretation of the influence of ethylene required the completion of the mechanism with further initiation of the reaction besides termination via ethyl radicals.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550180209
