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Kinetic Isotope Effect Predicted by the Marcus Electrochemistry Model


Nov. 21, 2019, 3:30 p.m. - 4:30 p.m.
Slichter 3853

Presented By:
Abby Kavner
UCLA

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A series of recent stable isotope electrodeposition experiments has demonstrated a rate-dependent kinetic isotope effect in a variety of different stable isotope systems, including Fe, Zn, and Li. In this presentation, I present a simplified model for kinetic isotope fractionation resulting from electrochemical reactions, based on a Marcus-type model for electron transfer. The model predicts a rate-dependent kinetic isotope effect, which depends on a small group of dimensionless parameters that define the activation energy trajectory. The model allows predictions of kinetic isotope fractionations as a function of temperature, rate, mass, and thermodynamic properties of the transition state. Finally, I present a “wish-list” of experiments designed to test the models’ hypotheses.