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Deuterium Kinetic Isotope Effect in the Oxidation of Deuteriated Butyric Acid-D7 with Chromium Trioxide in 85% Orthophosphoric Acid

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Abstract

A comparative study of the deuterium kinetic isotope effect in the oxidation of the deuteriated butyric acid-D7 with Cr(VI) in 85% orthophosphoric acid has been carried out.The (k HH/k DD) KIE values between 5.7 and 7.0 indicate that the tunnelling is not involved in oxidation of deuteriated aliphatic carboxylic acids with chromium trioxide in acidic media and the oxidation KIE is determined by the zero point energy difference corresponding to the C-H/C-D stretching vibrations lost in the transition state.The results were compared with the large D-KIE observed in the oxidation of butyrate-D7 with alkaline manganate caused by the simultaneous operation of zeropoint energy effect and tunnelling.

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References

  1. R. Stewart, Isotopes in oxidation reactions, in: Isotopes in Organic Chemistry, Vol. 2: Isotopes in Hydrogen Transfer Processes, E. Buncel,C. C. Lee (Eds), Elsevier, Amsterdam, 1976, p. 271.

    Google Scholar 

  2. G. A. Ropp,E. M. Hodnett, J. Chem. Phys., 25 (1956) 587.

    Google Scholar 

  3. K. B. Wiberg,R. J. Evans, Tetrahedron, 8 (1960) 313.

    Google Scholar 

  4. R. P. Bell, The Proton in Chemistry, Cornell University Press, Ithaca, New York, 2nd ed., 1973, chap. 12.

    Google Scholar 

  5. E. F. Caldin, Chem. Rev., 69 (1969) 135.

    Google Scholar 

  6. M. Zielinski, Isotope Effects in Chemistry, Polish Sci. Publ., Warsaw, 1979, p. 112.

    Google Scholar 

  7. M. Zielinski,M. Kanska, Syntheses and uses of isotopically labelled acid derivatives, in: S. Patai (Ed.), Supplement B: The Chemistry of Acid Derivatives, Vol. 2, John Wiley, Chichester, New York, 1992, p. 371.

    Google Scholar 

  8. M. Zielinski, Nukleonika, 34 (1989) 3.

    Google Scholar 

  9. A. Zielinska,M. Zielinski, Nukleonika, 44 (1999) 529, and the references cited therein.

    Google Scholar 

  10. M. Zielinski, Isotope Effects in Chemistry, Polish Sci. Publ., Warsaw, 1979, p. 102.

    Google Scholar 

  11. A. Fry, Heavy atom isotope effects in organic reaction mechanism studies, in: Isotope Effects in Chemical Reactions, C. J. Collins andN. S. Bowman (Eds), Van Nostrand Reinhold Co., New York, Cincinnati, Toronto, London, Melbourne, 1971, p. 364.

    Google Scholar 

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  1. Faculty of Chemistry, Jagiellonian University, 3 R. Ingardena Str., 30–060, Kraków, Poland

    A. Zielińska & M. Zieliński

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  1. A. Zielińska
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  2. M. Zieliński
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Zielińska, A., Zieliński, M. Deuterium Kinetic Isotope Effect in the Oxidation of Deuteriated Butyric Acid-D7 with Chromium Trioxide in 85% Orthophosphoric Acid. Journal of Radioanalytical and Nuclear Chemistry 250, 347–351 (2001). https://doi.org/10.1023/A:1017916200739

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