Kinetics of Pinane Oxidation to Pinane Hydroperoxide by Dioxygen
Kinetics and Catalysis
, E-ISSN: 1608-3210
Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk, 630090 Russia
The liquid-phase oxidation of pinane to pinane hydroperoxide (PHP) by dioxygen is studied at 353–373 K and under dioxygen pressures ranging from 2 to 4 atm. The rate of pinane oxidation is described by the equation w = wO2 + wPHP , where the term wO2 is independent of the PHP concentration, wPHP is a function of the concentration [PHP]n, and n ranges from 0.5 at low [PHP] to 1.0 at high [PHP]. The cis-isomer of 2-hydroperoxopinane generates free radicals during autooxidation. The ratio of the rate constants of cis- and trans-pinane oxidation is found (kcis /ktrans = 4.0). The selectivity of the oxidation of pinane to PHP can reach 90–95%.