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Kinetics of Pinane Oxidation to Pinane Hydroperoxide by Dioxygen

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Abstract

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 = w O 2 + w PHP , where the term w O 2 is independent of the PHP concentration, w PHP 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 (k cis /k trans = 4.0). The selectivity of the oxidation of pinane to PHP can reach 90–95%.

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk, 630090, Russia

    I. I. Il'ina, I. L. Simakova & V. A. Semikolenov

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  1. I. I. Il'ina
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  2. I. L. Simakova
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  3. V. A. Semikolenov
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Il'ina, I.I., Simakova, I.L. & Semikolenov, V.A. Kinetics of Pinane Oxidation to Pinane Hydroperoxide by Dioxygen. Kinetics and Catalysis 42, 41–45 (2001). https://doi.org/10.1023/A:1004896512191

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  • DOI: https://doi.org/10.1023/A:1004896512191

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