Perceptions on the treatment of apparent isotope effects during the analyses of reaction rate and mechanism

Isotope substitution, a fascinating tool of physical chemistry, has been broadly applied in the research field of heterogeneous catalysis. In general, due to the differences in the mass-related atomic vibrational frequencies and zero-point energy of isotopic molecules, the apparent isotope effect (AIE) or observed kinetic isotope effect (observed KIE) from isotope substitution examination could provide unique knowledge regarding the reaction rate and mechanism of a catalytic reaction, such as the rate-determining step, key reaction intermediate, or catalyst design and synthesis. However, the treatment of the AIE is not as straightforward as the isotopic switch experiment, and needs sufficient care and comprehensive identification to deal with the influences from the equilibrium isotope effects (EIEs) of quasi-equilibrium elementary steps, kinetic isotope effect (KIE) of the pseudo rate-determining step, transition states, intrinsic reaction barriers, etc. Fundamentally, the key factors affecting the AIE could be the partition function part and the zero-point energy part of each single elementary step. Theoretically, the classification of the KIE could be based on the quantity of KIE (including normal KIE and inverse KIE) or the molecular transformation (including primary KIE, secondary KIE, tunneling KIE, and solvent KIE) involved. This article presents a recap of the fundamental concepts and relations of KIE, EIE and AIE, and a concise review on the selected applications of isotope effects throughout heterogeneous catalysis. Lastly, the meaningful perspectives regarding the critical factors that impact the AIE and the appropriate treatment of the AIE are discussed meticulously.