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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
Article

Abstract

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.

Keywords

Cyclohexane Target Product Cyclohexanone Cyclohexanol Chain Propagation 
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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References

  1. 1.
    Berezin, I.V., Denisov, E.T., and Emanuel’, N.M.,Okislenie tsiklogeksana (Cyclohexane Oxidation), Moscow: Mosk. Gos. Univ., 1962.Google Scholar
  2. 2.
    Furman, M.S., Badrian, A.S., Gol’dman, A.M.,et al., Proizvodstvo tsiklogeksanona i adipinovoi kisloty okisleniem tsiklogeksana (Cyclohexanone and Adipic Acid Manufacturing by Cyclohexane Oxidation), Moscow: Khimiya, 1967.Google Scholar
  3. 3.
    Sittig, M.,Prvtsessy okisleniya uglevodowdnogo syr’ya (Oxidation of Hydrocarbon Materials), Moscow: Khimiya, 1970.Google Scholar
  4. 4.
    Davis, J.A., Watson, P.L., and Grenberg, A.,Selective Hydrocarbon Oxidation and Functionalization, New York: VCH, 1990.Google Scholar
  5. 5.
    Parshall, G.W. and Ittel, S.D.,Homogenous Catalysis, New York: Wiley, 1992, ch. 10.Google Scholar
  6. 6.
    Denisov, E.T., Mitskevich, N.I., and Agabekov, V.E.,Mekhanizm zhidkofaznogo okisleniya kislorodsoderzhashchikh soedinenii (The Mechanism of Oxidation of Oxygen-Containing Compounds), Minsk: Nauka Tekhnika, 1975.Google Scholar
  7. 7.
    Kucher, R.V. and Opeida, I.A.,Sookislenie organicheskikh veshchestv vzhidkoi faze (Cooxidation of Organic Compounds in the Liquid Phase), Kiev: Naukova Dumka, 1989.Google Scholar
  8. 8.
    Kucher, R.V. and Opeida, I.A.,Usp. Khim, 1985, vol. 54, no. 5, p. 765.Google Scholar
  9. 9.
    Kucher, R.V., Timokhin, V.I., Kravchuk, N.A.,et al., Neftekhimiya, 1987, vol. 27, no. 5, p. 661.Google Scholar
  10. 10.
    Timokhin, V., Lisovska, M., Zaborovskiy, A.,et al., 12th Conf. on Physical Organic Chemistry, Padova, 1994, p. 261.Google Scholar
  11. 11.
    Lisovska, M., Timokhin, V., and Pocutsa, A.,3rd Eur. Congr. on Catalysis (EumpaCat-3), Krakow, 1997, vol. 1, p. 195.Google Scholar
  12. 12.
    Opeida, I.A., Timokhin, V.I., Simonov, M.A.,et al., Available from VINITI, 1983, manuscript no. 2356.Google Scholar
  13. 13.
    Einhorn, C., Einhorn, J., Marcadal, C.,et al., Chem. Commun., 1997, p. 447.Google Scholar
  14. 14.
    Bravo, A., Bjorsvik, H.-R., Fontana, F.,et al., J. Org. Chem., 1996, vol. 61, no. 26, p. 9409.CrossRefGoogle Scholar
  15. 15.
    Tserpalov, V.F.,Zavod. Lab., 1964, no. 1, p. 111.Google Scholar
  16. 16.
    Pokutsa, A.P., Timokhin, V.I., and Suprun, V.Ya.,Zh. Anal. Khim., 1989, vol. 44, no. 3, p. 570.Google Scholar
  17. 17.
    Antonovskii, V.L. and Buzlanova, M.M.,Analiticheskaya khimiya organicheskikh peroksidnykh soedinenii (Analytical Chemistry of Organic Peroxide Compounds), Moscow: Khimiya, 1978.Google Scholar
  18. 18.
    Weisberger, A., Proskauer, E., Riddick, J., Toops, E.,Technique of Organic Chemistry, New York, 1958, vol. 7.Google Scholar
  19. 19.
    Chernyak, B.I. and Andrianova, L.A.,Zh. Org. Khim., 1975, vol. 11, no. 9, p. 1800.Google Scholar
  20. 20.
    Denisova, L.N. and Denisov, E.T.,Kinet. Ratal, 1969, vol. 10, no. 6, p. 1244.Google Scholar
  21. 21.
    McDade, E.C., Lenhardt, T.M., and Bayes, K.D.,J. Photochem., 1982, vol. 20, no. 1, p. 1.CrossRefGoogle Scholar
  22. 22.
    Brede, O. and Wojnarovits, N.,Radiat. Phys. Chem., 1991, vol. 37, no. 3, p. 537.Google Scholar
  23. 23.
    Schuh, H., Hamilton, E.J., Paul, H.,et al., Helv. Chim. Acta, 1974, vol. 57, no. 7, p. 2011.CrossRefGoogle Scholar
  24. 24.
    Benson, S.W.,Oxid. Commun., 1982, vol. 2, no. 3, p. 181.Google Scholar
  25. 25.
    Timokhin, V.I.,Doctoral (Chem.) Dissertation, Lvov: Lvov Polytechnic Institute, 1991.Google Scholar
  26. 26.
    Korcek, S., Cheneir, J.H.B., Howard, J.A.,et al., Can. J. Chem., 1972, vol. 50, no. 14, p. 2285.CrossRefGoogle Scholar
  27. 27.
    Handbook of Chemistry and Physics, Boca Raton, Florida: CRC, 1987/1988, p. F-178.Google Scholar
  28. 28.
    Paronikyan, D.G., Oganesyan, E.A., Vardanyan, I.A.,et al., Khim. Fiz., 1982, no. 10, p. 1357.Google Scholar
  29. 29.
    Semenchenko, A.E., Solyanikov, V.M., and Denisov, E.T.,Neftekhimiya, 1971, vol. 11, no. 4, p. 555.Google Scholar
  30. 30.
    Garbuzyuk, I.A., Levush, S.S., and Shevchuk, V.U.,Ukr. Khim. Zh., 1976, vol. 42, no. 6, p. 620.Google Scholar
  31. 31.
    Turetsskaya, E.A., Skakovskii, E.D., Rykov, S.V.,et al., Dokl. Akad. Nauk BSSR, 1980, vol. 24, no. 1, p. 57.Google Scholar
  32. 32.
    Chateauneuf, J., Lusztyk, J., and Ingold, K.U.,J. Am. Chem. Soc., 1988, vol. 110, no. 9, p. 2886.CrossRefGoogle Scholar
  33. 33.
    Semenchenko, A.E., Solyanikov, V.M., and Denisov, E.T.,Neftekhimiya, 1970, vol. 10, no. 6, p. 864.Google Scholar
  34. 34.
    Druliner, J.D., Krusic, P.J., Lehr, G.F.,et al., J. Org. Chem., 1985, vol. 50, no. 26, p. 5838.CrossRefGoogle Scholar
  35. 35.
    Huie, R.E. and Herron, Z.T.,Prog. React. Kinet., 1975, vol. 8, p. 1.Google Scholar
  36. 36.
    Atkinson, R.,Chem. Rev., 1985, vol. 85, no. 1, p. 69.Google Scholar
  37. 37.
    Maslov, S.A. and Blyumberg, E.A.,Usp. Khim., 1976, vol. 45, no. 2, p. 303.Google Scholar
  38. 38.
    Vinogradov, M.G., Kereselidze, R.V., and Nikishin, G.I.,Ihv. Akad. Nauk SSSR, Ser. Khim., 1970, no. 5, p. 1056.Google Scholar
  39. 39.
    Howard, J.A. and Ingold, K.U.,Can. J. Chem., 1967, vol. 45, no. 8, p. 785.CrossRefGoogle Scholar
  40. 40.
    Maslennikov, S.I., Galimova, L.G., and Komissarov, V.D.,Ihv. Akad. Nauk SSSR, Ser. Khim., 1979, no. 3, p. 631.Google Scholar
  41. 41.
    Zaikov, G.E., Howard, J.A., and Ingold, K.U.,Can. J. Chem., 1969, vol. 47, no. 16, p. 3017.CrossRefGoogle Scholar
  42. 42.
    Tavadyan, L.A., Tonikyan, A.K., and Nalbandyan, A.B.,Arm. Khim. Zh., 1987, vol. 40, no. 6, p. 347.Google Scholar
  43. 43.
    Moortgat, G.K., Veyret, B., and Lesclaux, R.,Chem. Phys. Lett., 1989, vol. 160, no. 4, p. 443.CrossRefGoogle Scholar
  44. 44.
    Starchevskii, V.L., Vasilina, T.V., and Mokryi, E.N.,Zh. Fiz. Khim., 1985, vol. 59, no. 9, p. 2300.Google Scholar
  45. 45.
    Murahashi, S.-I., Oda, Y., and Naota, T.,Tetrahedron Lett., 1992, vol. 33, no. 49, p. 7557.CrossRefGoogle Scholar

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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