Conclusions
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1.
An investigation of the value of the kinetic isotopic effect (KIE) within the framework of the quantum mechanical theory of chemical reactions made it possible to explain the observed experimental ratio of the preexponential factors less than one. The analysis gives evidence that the transfer of a proton occurs non-adiabatically, whereas the deuteron is transferred either adiabatically or nonadiabatically, but with a distance less than that for the proton.
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2.
The experimentally observed tendency for a decrease in the value of the KIE when the equilibrium constant deviates from one can be explained by the influence of the contribution to the KIE from the excited states of a proton and deuteron.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1031–1038, May, 1972.
The authors would like to express their gratitude to Professor R. R. Dogonadze for his discussion of the work and his valuable suggestions.
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German, É.D., Kharkats, Y.I. Theory of the kinetic isotopic effect in reactions of proton transfer. Russ Chem Bull 21, 987–993 (1972). https://doi.org/10.1007/BF00853753
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DOI: https://doi.org/10.1007/BF00853753