thermodynamic isotope effect

The effect of isotopic substitution on an equilibrium constant is referred to as a thermodynamic (or equilibrium) isotope effect. For example, the effect of isotopic substitution in reactant A that participates in the equilibrium: is the ratio of the equilibrium constant for the reaction in which A contains the light isotope to that in which it contains the heavy isotope. The ratio can be expressed as the equilibrium constant for the isotopic exchange reaction: in which reactants such as B that are not isotopically substituted do not appear. The potential energy surfaces of isotopic molecules are identical to a high degree of approximation, so thermodynamic isotope effects can only arise from the effect of isotopic mass on the nuclear motions of the reactants and products, and can be expressed quantitatively in terms of partition function ratios for nuclear motion: Although the nuclear partition function is a product of the translational, rotational and vibrational partition functions, the isotope effect is determined almost entirely by the last named, specifically by vibrational modes involving motion of isotopically different atoms. In the case of light atoms (i.e. protium vs. deuterium or tritium) at moderate temperatures, the isotope effect is dominated by zero-point energy differences.