Skip to main content
SpringerLink
Log in

Reactions of alkoxy and peroxy radicals with carbon monoxide

  • Published:
Kinetics and Catalysis Aims and scope Submit manuscript

Abstract

Experimental rate constants of the reactions HO· + CO → H· + CO2, RO· + CO → R· + CO2, HO ·2 + CO → HO· + CO2, and RO ·2 + CO → RO· + CO2 are analyzed in the framework of the intersecting-parabolas model. The transition states of the additions of the methoxy and methylperoxy radicals to carbon monoxide were calculated by quantum-chemical methods. The reactions occur in two consecutive steps: first the HO· (RO·, RO ·2 ) radical adds to CO and then the resulting unstable intermediate radical decomposes to evolve CO2. The kinetic parameters of these reactions are calculated by two methods (using the intersecting-parabolas model and the quantum-chemical method). The activation energies and rate constants of a series of R i O· + CO and R i O ·2 + CO reactions are calculated. A comparison of the kinetic parameters suggests close similarity between the transition states in the additions of the O-centered radicals to CO and olefins.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Comprehensive Chemical Kinetics, vol. 17: Gas Phase Combustion, Bamford, C.H. and Tipper, C.F.H., Eds., Amsterdam: Elsevier, 1976.

    Google Scholar 

  2. Semenov, N.N., Izbrannye trudy (Selected Works), Moscow: Nauka, 2004, vol. 1, book 1.

    Google Scholar 

  3. Shtern, V.Ya., Mekhanizm okisleniya uglevodorodov v gazovoi faze (Mechanism of Hydrocarbon Oxidation in the Gas Phase), Moscow: Akad. Nauk SSSR, 1960.

    Google Scholar 

  4. Denisov, E.T. and Afanas’ev, I.B., Oxidation and Antioxidants in Organic Chemistry and Biology, Boca Raton, Fla.: Taylor and Francis, 2005.

    Book  Google Scholar 

  5. NIST Chemical Kinetics Database, Gaithersburg, Md.: National Inst. of Standards and Technology, 1998.

  6. Denisov, E.T., in General Aspects of the Chemistry of Radicals, Alfassi, Z.B., Ed., Chichester: Wiley, 1999, p. 79.

    Google Scholar 

  7. Denisov, E.T., Usp. Khim., 1997, vol. 66, no. 10, p. 953 [Russ. Chem. Rev. (Engl. Transl.), vol. 66, no. 10, p. 859].

    CAS  Google Scholar 

  8. Denisov, E.T., Usp. Khim., 2000, vol. 69, no. 2, p. 166 [Russ. Chem. Rev. (Engl. Transl.), vol. 69, no. 2, p. 166].

    Google Scholar 

  9. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Montgomery, J.A., Stratmann, R.E., Burant, J.C., Sapprich, S., Millam, J.M., Daniels, A.D., Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J., Barone, V., Cossi, M., Cammi, R., Mennucci, B., Pomelli, C., Adamo, C., Clifford, S., Ochterski, J., Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Cioslowski, J., Ortiz, J.V., Baboul, A.G., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Gomperts, R., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Gonzalez, C., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M., Andres, J.L., Gonzalez, C., Head-Gordon, M., Replogle, E.S., and Pople, J.A., Gaussian 98, Revision A.7, Pittsburg, Pa.: Gaussian Inc., 1998.

    Google Scholar 

  10. Lide, D., Handbook of Chemistry and Physics, Boca Raton, Fla.: Taylor and Francis, 2005.

    Google Scholar 

  11. Denisov, E.T. and Tumanov, V.E., Usp. Khim., 2005, vol. 74, no. 9, p. 905 [Russ. Chem. Rev. (Engl. Transl.), vol. 74, no. 9, p. 825].

    Google Scholar 

  12. Denisov, E.T., Denisova, T.G., and Pokidova, T.S., Handbook of Free Radical Initiators, Hoboken, N.J.: Wiley, 2003.

    Book  Google Scholar 

  13. Tsang, W. and Hampson, R.F., J. Phys. Chem. Ref. Data, 1986, vol. 15, p. 1087.

    Article  CAS  Google Scholar 

  14. Allen, T.L., Fink, W.H., and Volman, D.H., J. Photochem. Photobiol., A, 1995, vol. 85, p. 201.

    Article  CAS  Google Scholar 

  15. Lissianski, V., Yang, H., Qin, Z., Mueller, M.R., Shin, K.S., and Gardiner, W.C., Chem. Phys. Lett., 1995, vol. 240, p. 57.

    Article  CAS  Google Scholar 

  16. Frost, M.J., Sharkey, P., and Smith, W.M., J. Phys. Chem., 1993, vol. 97, p. 1224.

    Article  Google Scholar 

  17. Baulch, D.L., Cobos, C.J., Cox, R.A., Esser, C., Frank, P., Just, Th., Kerr, J.A., Pilling, M.J., Troe, J., Walker, R.W., and Warnatz, J., J. Phys. Chem. Ref. Data, 1992, vol. 21, p. 411.

    Article  CAS  Google Scholar 

  18. Smith, I.W.M. and Williams, M.D., Ber. Bunsen-Ges. Phys. Chem., 1985, vol. 89, p. 319.

    CAS  Google Scholar 

  19. Lissi, E.A. and Scaiano, J.C., J. Chem. Soc. D: Chem. Commun., 1971, p. 457.

  20. Warnatz, J., in Combustion Chemistry, Gardiner, W.C., Ed., New York: Springer, 1984.

    Google Scholar 

  21. Atri, G.M., Baldwin, R.R., Jackson, D., and Walker, R.W., Combust. Flame, 1977, vol. 30, p. 1.

    Article  CAS  Google Scholar 

  22. Agabekov, V.E., Korsak, I.I., Denisov, E.T., and Mitskevich, N.I., Dokl. Akad. Nauk SSSR, 1974, vol. 217, no. 1, p. 116.

    CAS  Google Scholar 

  23. Denisov, E.T., Sarkisov, O.M., and Likhtenshtein, G.I., Chemical Kinetics, Amsterdam: Elsevier, 2003.

    Google Scholar 

  24. Svensson, T. and Nelander, B., Chem. Phys. Lett., 2000, vol. 262, p. 445.

    CAS  Google Scholar 

  25. Hammond, G.S., J. Am. Chem. Soc., 1955, vol. 77, no. 2, p. 334.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432, Russia

    E. T. Denisov & A. F. Shestakov

Authors
  1. E. T. Denisov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. F. Shestakov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to E. T. Denisov.

Additional information

Original Russian Text © E.T. Denisov, A.F. Shestakov, 2008, published in Kinetika i Kataliz, 2008, Vol. 49, No. 1, pp. 5–14.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Denisov, E.T., Shestakov, A.F. Reactions of alkoxy and peroxy radicals with carbon monoxide. Kinet Catal 49, 1–10 (2008). https://doi.org/10.1134/S0023158408010011

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0023158408010011

Keywords

Search

Navigation