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Kinetics and Catalysis

, Volume 41, Issue 2, pp 201–210 | Cite as

Cyclohexane oxidation catalyzed by variable-valence metal compounds in the presence of propionic aldehyde

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

Abstract

The effect of propionic aldehyde additives on the kinetics and mechanism of cyclohexane oxidation by molecular oxygen catalyzed by variable-valence metal salts is studied. The effect of the catalyst metal (M) on the rate of oxygen consumption, yield, and ratio of reaction products (cyclohexanol, cyclohexanone, cyclohexyl hydroperoxide (CHHP), and propionic acid and peracid) is studied. The catalytic functions of the variable-valence metal salts are determined by their ability to influence the rate of the homolysis of the O–O bonds of peroxide compounds, which correlates with the redox potential of the metal ion for most of the catalysts studied. The fact that other salts of variable-valence metals do not fit this correlation is due to the multifunctional action of catalysts involved in chain initiation, termination, and degenerate branching. The main role of aldehyde in the process under consideration is to promote oxidation. According to the quantum-chemical studies, the catalyst cation largely determines both the structure of the [Mn+-CHHP] transition complex and the rates of competitive homolysis and heterolysis of cyclohexyl hydroperoxide.

Keywords

Target Product Cyclohexanone Cyclohexanol Cyclohexyl Homolysis 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© MAIK “Nauka/Interperiodica” 2000

Authors and Affiliations

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

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