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 $\ce{A}$ is expressed as the ratio of rate constants \(\frac{k^{\rm{l}}}{k^{\rm{h}}}\), where the superscripts \(\rm{l}\) and \(\rm{h}\) represent reactions in which the molecules $\ce{A}$ 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, \(\frac{k^{\rm{l}}}{k^{\rm{h}}}\) can be regarded as if it were the equilibrium constant for an isotope exchange reaction between the transition state $\ce{[TS]^{\ddagger}}$ and the isotopically substituted reactant $\ce{A}$, 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