COBALT-BROMIDE CATALYSIS IN THE OXIDATION OF ORGANIC-COMPOUNDS .4. MECHANISM OF CATALYTIC DECOMPOSITION OF HYDROPEROXIDE

The kinetics of decomposition of various hydroperoxides (ethylbenzene, diphenylmethane, tetralin, and toluene) catalyzed by cobalt(II) aceta te in an acetic acid-hydrocarbon solution is studied by the chemilumin escence and volumetric methods both in the presence and absence of bro mide. The influence of temperature, medium composition, and bromide ad ditives on the parameters and the mechanism of hydroperoxide decomposi tion is studied in terms of the scheme involving the reaction of the c omplex ROOH . Co(II) with the second Co(II) ion (binuclear interaction ). Change in the composition medium strongly influences the rate of th e reaction between ROOH . Co(II) and Co(II), but has a negligible effe ct on the rate of complex formation. The activation energy of complex formation is equal to 75 kJ/mol. The participation of cobalt bromide i n hydroperoxide decomposition is established.