HETEROGENEOUS CATALYSIS IN THE LIQUID-PHASE OXIDATION OF OLEFINS. - 4. THE ACTIVITY OF A SUPPORTED VANADIUM OR CHROMIUM OXIDE CATALYST IN THE DECOMPOSITION OF t-BUTYL HYDROPEROXIDE.

The liquid-phase decomposition of t-butyl hydroperoxide (t-BuOOH) has been carried out in benzene under an N//2 atmosphere using a vanadium or chromium oxide, supported on gamma -Al//2O//3 or SiO//2 as the catalyst, for the purpose of clarifying the reaction mechanism of the cyclohexane oxidation. The decomposition of t-BuOOH on the supported oxide catalyst was a first-order reaction; the main products were t-butyl alcohol, di-ti-butyl peroxide, and acetone, suggesting that t-BuOOH is decomposed homolytically on the catalyst by the Haber-Weiss mechanism. The effect of the vanadium-chromium binary system formation was small, but the interaction between metal oxides and the supports appeared to be important in the t-BuOOH decomposition.