Kinetics and Catalysis

, Volume 41, Issue 2, pp 159–165 | Cite as

Kinetics and mechanism of cyclohexane oxidation with molecular oxygen in the presence of propionic aldehyde

  • V. I. Timokhin
  • M. T. Lisovska
  • A. P. Pokutsa


The kinetics and mechanism of the liquid-phase oxidation of cyclohexane with molecular oxygen in the presence of the additives of propionic aldehyde are studied at 303.0, 322.5, and 341.5 K by measuring the rates of oxygen and propionic aldehyde consumption and the yields of the main reaction products (cyclohexanol (COL), cyclohexanone (CON), cyclohexyl hydroperoxide, and propionic acid and peracid). A kinetic scheme is proposed and rate constants of elementary reactions are estimated based on the analysis of their rates and the yields of the main cyclohexane products. The key reactions of the main steps (including chain initiation, propagation, and termination) are determined. An increase in the rate of cyclohexane oxidation and the yield of the target products (cyclohexanol, cyclohexanone, and cyclohexyl hydroperoxide) in the presence of propionic aldehyde suggests that highly active acylperoxy radicals participate in chain propagation. The [CON]/[COL] ratio indicates that these products are mainly formed in chain propagation. The strong effect of the Baeyer-Villiger rearrangement on both the rate of oxygen consumption and the yield of the target products at the initial stages of the process and at high propionic aldehyde concentrations is explained.


Cyclohexane Target Product Cyclohexanone Cyclohexanol Chain Propagation 
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Copyright information

© MAIK “Nauka/Interperiodica” 2000

Authors and Affiliations

  • V. I. Timokhin
    • 1
  • M. T. Lisovska
    • 1
  • A. P. Pokutsa
    • 1
  1. 1.Pisarzhevskii Institute of Physical ChemistryNational Academy of Sciences of UkraineLvovUkraine

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