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Thermal reaction of hydrogen–butene‐2‐ cis mixtures at 500°C: Hydrogenation, hydrogenolysis, and thermal reaction of the olefin
Author(s) -
Collongues C.,
Richard C.,
Martin R.
Publication year - 1983
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.550150103
Subject(s) - hydrogenolysis , chemistry , olefin fiber , hydrogen , reaction rate constant , 2 butene , stoichiometry , reaction mechanism , catalysis , photochemistry , reaction rate , butene , methane , organic chemistry , kinetics , ethylene , physics , quantum mechanics
The thermal reaction of hydrogen–butene‐2‐ cis mixtures has been studied in a static system at low extent of reaction around 500°C. Hydrogen does not affect the thermal reaction itself of the olefin, but gives rise to new stoichiometries of hydrogenolysis and hydrogenation, which are specified:\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm H}_2 + cis - 2 - {\rm C}_4 {\rm H}_8 = {\rm CH}_4 + {\rm C}_3 {\rm H}_6 \\ {\rm H}_2 + cis - 2 - {\rm C}_4 {\rm H}_8 = {\rm H}_2 + 1 - {\rm C}_4 {\rm H}_8 \\{\rm H}_2 + cis - 2 - {\rm C}_4 {\rm H}_8 = n - {\rm C}_4 {\rm H}_{10} \\ \end{array} $$\end{document}The reaction is described in terms of a molecular and free‐radical mechanism. It is shown that the key process for the hydrogenolysis–hydrogenation reaction isand that the rate constant of this process can be determined from either propylene, or methane, or butene‐1 formations:\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm k}_{{\rm 7'}} \simeq {\rm 10}^{{\rm 13}{\rm .1 - 24}{\rm .2/}\theta } \,{\rm cm}^{\rm 3} {\rm /mol} \cdot {\rm s} $$\end{document}with θ = 4.57 × 10 −3 T kcal/mol. Other rate constants are estimated and agree with literature data.