Abstract
The disproportionation of cyclohexene to cyclohexane and benzene has been kinetically followed in tetrahydrofuran solution on palladium powder at 50 ° to 60 °C. The behavior of 1,3-cyclohexadiene under the same conditions has been studied too. Gas chromatography was used for the analytical determinations. The diene is noticeably more reactive than cyclohexene, and has been detected in low concentration in the reaction products from the latter. It is suggested that it is an intermediate of the reaction. Experimental results of the kinetics of cyclohexene are well accounted for by a second order rate law that takes into account the adsorption of cyclohexene and benzene on the catalyst. The adsorption coefficients for benzene are ca. five times larger than those of cyclohexene. Adsorption heats are 5.2 and 9.3 kcal/mole, respectively, for cyclohexene and benzene from the solution. The activation energy of the reaction is 14 kcal/mole. Details are given of the application of the steepest descent method for the leastsquares fitting of the kinetic equation to experimental data.
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