AUTOXIDATION OF 1-OCTENE WITH T-BUTYL HYDROPEROXIDE AND CHROMIUM(3) ACETYLACETONATE .I. KINETICS

The system chromium(III) acetylacetonate-t-butyl hydroperoxide has been used to initiate autoxidation of 1-octene in 1-chlorooctane solvent in the temperature range 0-60°. Emperical kinetic equations are presented based upon spectrophotometrically determined disappearance rates of chromium (III) acetylacetonate, titrimetrically determined t-butyl hydroperoxide decomposition rates, and oxygen absorption data. Activation parameters for the kinetic data have been calculated. The data are interpreted in terms of two superimposed chain reactions, one involving peroxide decomposition through chromium complexes, the other involving chain autoxidation of the 1-octene. Products of the autoxidation are compared with azo-initiated olefin autoxidation products. © 1969, American Chemical Society. All rights reserved.