Skip to main content
SpringerLink
Log in

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

  • Published:
Research on Chemical Intermediates Aims and scope Submit manuscript

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.

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.

Institutional subscriptions

Similar content being viewed by others

References

  1. F.D. Lewis and J.G. Magyar, J. Org. Chem. 37, 2102 (1972).

    Article  CAS  Google Scholar 

  2. M.V. Encina, E.A. Lissi, E. Lemp, A. Zanocco, and J.C. Scaiano, J. Am. Chem. Soc. 105, 1856 (1983).

    Article  CAS  Google Scholar 

  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.

    Article  Google Scholar 

  4. K. Akiyama, S. Tero-Kubota, and Y. Ikegami, J. Am. Chem. Soc., 106, 8322 (1984).

    Article  CAS  Google Scholar 

  5. K. Munger and H. Fischer, Int. J. Chem. Kinetics 17, 809 (1985).

    Article  Google Scholar 

  6. 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).

    Article  CAS  Google Scholar 

  7. T. Ikoma, K. Akiyama, S. Tero-Kubota, and Y. Ikegami, Chem. Lett. 1491 (1990).

  8. 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).

    Article  CAS  Google Scholar 

  9. J.P. Fouassier, Prog. Org. Coating 18, 229 (1990).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute for Chemical Reaction Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, 980, Sendai, Japan

    K. Akiyama & S. Tero-Kubota

Authors
  1. K. Akiyama
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. S. Tero-Kubota
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Akiyama, K., Tero-Kubota, S. Time-resolved and fourier transform EPR studies of type I photochemical reaction. Direct determination of kinetic parameters of C−C bond cleavage. Res. Chem. Intermed. 22, 103–113 (1996). https://doi.org/10.1163/156856796X00557

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1163/156856796X00557

Keywords

Search

Navigation