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kinetic isotope effect

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 k l k h, where the superscripts l and h 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, k l k h 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
PAC, 1994, 66, 1077 (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1130
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IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8.
Last update: 2014-02-24; version: 2.3.3.
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