Advertisement

Research on Chemical Intermediates

, Volume 22, Issue 2, pp 103–113 | Cite as

Time-resolved and fourier transform EPR studies of type I photochemical reaction. Direct determination of kinetic parameters of C−C bond cleavage

  • K. Akiyama
  • S. Tero-Kubota
Article

Abstract

Continuous wave time-resolved EPR (CW-TREPR) and pulsed Fourier transform EPR (FT-EPR) experiments with a resolution of ≈10 ns were carried out to investigate the Type I photocleavage. A two-pulse echo detection method was used to eliminate the dead-time problem in the FID measurements. An analysis of the buildup kinetics of the FT-EPR signal intensity due to t-butyl radicals provided the rates of the α-cleavage of t-butylphenyl ketone at various temperatures. We obtained two kinetic parameters at low and high temperatures which correspond to the non-radiative decay rate of the excited triplet state of the ketone and the rate of the Type I photocleavage, respectively.

Keywords

Free Induction Decay Microwave Pulse Excited Triplet State Laser Flash Photolysis Benzoyl Radical 
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.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    F.D. Lewis and J.G. Magyar, J. Org. Chem. 37, 2102 (1972).CrossRefGoogle Scholar
  2. 2.
    M.V. Encina, E.A. Lissi, E. Lemp, A. Zanocco, and J.C. Scaiano, J. Am. Chem. Soc. 105, 1856 (1983).CrossRefGoogle Scholar
  3. 3.
    For Recent Reviews see H. van Willingen, P.R. Levestein, and M.H. Ebersole, Chem. Rev., 93, 173 (1993) and also M.K. Bowman, In: Modern Pulsed and Continuous-Wave Electron Spin Resonance; L. Kevan, and M.K. Bowman, (Eds.), Wiley New York, 1990, pp 1–42.CrossRefGoogle Scholar
  4. 4.
    K. Akiyama, S. Tero-Kubota, and Y. Ikegami, J. Am. Chem. Soc., 106, 8322 (1984).CrossRefGoogle Scholar
  5. 5.
    K. Munger and H. Fischer, Int. J. Chem. Kinetics 17, 809 (1985).CrossRefGoogle Scholar
  6. 6.a)
    H. Fischer, J. Phys. Chem. 73, 3834 (1969); b) P.W. Atkins, A.J. Dobbs, and K.A. McLauchlan, J. Chem. Soc., Faraday Trans. 2 71, 1269 (1975).CrossRefGoogle Scholar
  7. 7.
    T. Ikoma, K. Akiyama, S. Tero-Kubota, and Y. Ikegami, Chem. Lett. 1491 (1990).Google Scholar
  8. 8.a)
    P. Jaegermann, F. Lendzian, G. Rist, and K. Mobius, Chem. Phys. Lett., 140, 615 (1987); b) M. Koyanagi, H. Futami, M. Mukai, and S. Yamauchi, Chem. Phys. Lett., 154, 577 (1989).CrossRefGoogle Scholar
  9. 9.
    J.P. Fouassier, Prog. Org. Coating 18, 229 (1990).CrossRefGoogle Scholar

Copyright information

© Springer 1996

Authors and Affiliations

  • K. Akiyama
    • 1
  • S. Tero-Kubota
    • 1
  1. 1.Institute for Chemical Reaction ScienceTohoku UniversitySendaiJapan

Personalised recommendations