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Effects of olefins on the thermal decomposition of propane part V. Effect of butene‐2‐ Cis
Author(s) -
Dombi A.,
Huhn P.
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.550180305
Subject(s) - chemistry , radical , propane , decomposition , chain termination , thermal decomposition , butene , olefin fiber , photochemistry , organic chemistry , catalysis , ethylene , polymerization , radical polymerization , polymer
The thermal decomposition of butene‐2‐ cis at low conversion and its effect on the pyrolysis of propane have been studied in the temperature range 779‐812 K. It was established that 2‐butene decomposes in a long‐chain process, with the chain cycle\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2 - C}_{\rm 4} {\rm H}_{\rm 8} + {}^.{\rm CH}_{\rm 3} \to {}^.{\rm C}_{\rm 4} {\rm H}_{\rm 7} + {\rm CH}_{\rm 4} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2 - C}_{\rm 4} {\rm H}_{\rm 8} + {}^.{\rm CH}_{\rm 3} \to {}^.{\rm C}_{\rm 4} {\rm H}_{\rm 7} + {\rm CH}_{\rm 4} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2 - C}_{\rm 4} {\rm H}_{\rm 8} + {}^.{\rm CH}_{\rm 3} \to {}^.{\rm C}_{\rm 4} {\rm H}_{\rm 7} + {\rm CH}_{\rm 4} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {}^.{\rm C}_{\rm 4} {\rm H}_{\rm 7} \to {}^.{\rm H} + 1,3 - {\rm C}_{\rm 4} {\rm H}_{\rm 6} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2 - C}_{\rm 4} {\rm H}_{\rm 8} + {}^.{\rm H} \to {}^.{\rm C}_{\rm 4} {\rm H}_{\rm 7} + {\rm H}_{\rm 2} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ \to 2 - {\rm \dot C}_{\rm 4} {\rm H}_{\rm 9} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2 - C}_{\rm 4} {\rm H}_{\rm 8} \to + 1,3 - {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {\rm H}_{\rm 2} $$\end{document}(Besides the radical path, the molecular reactioncan also play a role in the formation of the products.) The thermal decomposition of propane is considerably inhibited by 2‐butene, which can be explained by the fact that the less reactive radicals formed in the reactions between the olefin and the chain‐carrying radicals regenerate the chain cycle more slowly than the original radicals in the above chain cycle or in the reactions\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 8} + {}^.{\rm C}_{\rm 4} {\rm H}_{\rm 7} \to 1 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} + {\rm C}_{\rm 4} {\rm H}_{\rm 8} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ \to 2 - {\rm \dot C}_{\rm 4} {\rm H}_{\rm 7} + {\rm C}_{\rm 3} {\rm H}_{\rm 8} $$\end{document}The reactions of the 2‐propyl radical\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2 - \dot C}_{\rm 3} {\rm H}_{\rm 7} + 2 - {\rm C}_{\rm 4} {\rm H}_{\rm 8} \to {}^.{\rm C}_{\rm 4} {\rm H}_{\rm 7} + {\rm C}_{\rm 3} {\rm H}_{\rm 8} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ \to 2 - {\rm \dot C}_{\rm 4} {\rm H}_{\rm 9} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} $$\end{document}are further initiation steps. The ratios of the rate coefficients of the elementary steps of the decomposition (Table III) have been determined via the ratios of the products. Estimation of the radical concentrations indicated that only the methyl, 2‐propyl and methylallyl radicals are of importance in the chain termination. On the basis of the inhibition‐influenced curves, the role of the bimolecular initiation steps.\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2 - C}_{\rm 4} {\rm H}_{\rm 8} + {\rm C}_{\rm 3} {\rm H}_{\rm 8} \to {\rm \dot C}_{\rm 4} {\rm H}_{\rm 9} + {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2 - C}_{\rm 4} {\rm H}_{\rm 8} + 2 - {\rm C}_{\rm 4} {\rm H}_{\rm 8} \to {}^.{\rm C}_{\rm 4} {\rm H}_{\rm 9} + {\rm C}_{\rm 4} {\rm H}_{\rm 7} $$\end{document}could be clarified in the presence of 2‐butene.