https://doi.org/10.1351/goldbook.K03405
The effect of isotopic substitution on a rate constant is referred to as a kinetic isotope effect. For example, in the reaction:
the effect of isotopic substitution in reactant A is expressed as the ratio of rate constants , where the superscripts and represent reactions in which the molecules A contain the light and heavy isotopes, respectively. Within the framework of transition state theory in which the reaction is rewritten as:
and with neglect of isotopic mass on tunnelling and the transmission coefficient, can be regarded as if it were the equilibrium constant for an isotope exchange reaction between the transition state [TS]‡ and the isotopically substituted reactant A, and calculated from their vibrational frequencies as in the case of a thermodynamic isotope effect. Isotope effects like the above, involving a direct or indirect comparison of the rates of reaction of isotopologues, are called 'intermolecular', in contrast to intramolecular isotope effects, in which a single substrate reacts to produce a non-statistical distribution of isotopomeric product molecules.


See also: isotope effect