Decyclization of Cyclohexene, 4-Methylcyclohexene, and 4-Vinylcyclohexene in a Single-Pulse Shock Tube

1 March 1965

journal article
conference paper
Published by AIP Publishing in The Journal of Chemical Physics

Vol. 42 (5) , 1805-1809
https://doi.org/10.1063/1.1696193

Abstract

Several cyclohexene compounds have been decomposed in a single‐pulse shock tube. Rate constants for the decyclization reactions

\begin{matrix} C_{6} H_{10} (cyclohexene)→ C_{2} H_{4} + C_{4} H_{6},(1,3− butadiene) \\ C_{7} H_{12} (4− methylcyclohexene)→ C_{3} H_{6} + C_{4} H_{6},(1,3− butadiene) \\ C_{8} H_{12} (4− vinylcyclohexene)→2 C_{4} H_{6},(1,3− butadiene) \end{matrix}

are compared with the rate of dehydrochlorination of hydrogen chloride from isopropyl chloride. The Arrhenius expression for the latter reaction has previously been found to be

k(i− C_{3} H_{7} Cl {)=10}^{13.64} \exp (−51 100/RT).

On this basis, the following rate expressions have been obtained:

\begin{matrix} k(C_{6} H_{10} {)=10}^{15.02} \exp (−66 700/RT) \sec^{−1} {(900}^{\circ} {−1150}^{\circ} K), \\ k(C_{7} H_{12} {)=10}^{15.13} \exp (−66 600/RT) \sec^{−1} {(900}^{\circ} {−1150}^{\circ} K), \\ k(C_{8} H_{12} {)=10}^{15.20} \exp (−62 000/RT) \sec^{−1} {(900}^{\circ} {−1050}^{\circ} K). \end{matrix}

Keywords

This publication has 14 references indexed in Scilit:

Thermal Decomposition of Cyclohexene
The Journal of Physical Chemistry, 1964
The magnetic dipole character and the optical rotatory power of crystal field electronic absorption spectra. Part. 1.—the oxalate and tartrate complexes of chromium(III)
Transactions of the Faraday Society, 1963
Thermal unimolecular decomposition of isopropenylcyclobutane
Transactions of the Faraday Society, 1963
A STUDY OF THE PYROLYSIS OF CYCLOHEXENE¹
The Journal of Physical Chemistry, 1961
The Thermal Decomposition of Methylcyclobutane¹
Zeitschrift für Physikalische Chemie, 1958
Diene durch Pyrolyse von cyclischen Verbindungen III. Die Kinetik der Spaltung von Cyclohexen und Cyclohexylacetat
Collection of Czechoslovak Chemical Communications, 1957
The Thermal Decomposition of Cyclobutane^1,2
Journal of the American Chemical Society, 1953
The Thermal Dimerization of Butadiene, and the Equilibrium between Butadiene and Vinylcyclohexene
The Journal of Chemical Physics, 1952
Kinetics of diene reactions at high temperatures
Discussions of the Faraday Society, 1951
Homogenous thermal decomposition of some cyclic hydrocarbons
Transactions of the Faraday Society, 1939