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Updated: Jul 16, 2025

Unraveling Entropic Rate Acceleration Induced by Solvent Dynamics in Membrane Enzymes
Published on: January 16, 2016
Continuous addition kinetic elucidation: catalyst and reactant order, rate constant, and poisoning from a single
Peter J H Williams1, Charles Killeen1, Ian C Chagunda1
1Department of Chemistry, University of Victoria PO Box 1700 STN CSC Victoria BC V8W 2Y2 Canada mcindoe@uvic.ca +1 250 721-7166.
Abstract:
Kinetic analysis of catalytic reactions is a powerful tool for mechanistic elucidation but is often challenging to perform, limiting understanding and therefore development of these reactions. Establishing order in a catalyst is usually achieved by running several reactions at different loadings, which is both time-consuming and complicated by the challenge of maintaining consistent run-to-run experimental conditions. Continuous addition kinetic elucidation (CAKE) was developed to circumvent these issues by continuously injecting a catalyst into a reaction, while monitoring reaction progress over time. For reactions that are mth order in a single yield-limiting reactant and nth order in catalyst, a plot of reactant concentration against time has a shape dependent only on the orders m and n. Therefore, fitting experimental CAKE data (using open access code or a convenient web tool) allows the reactant and catalyst orders, rate constant, and the amount of complete catalyst inhibition to be determined from a single experiment. Kinetic information obtained from CAKE experiments showed good agreement with the literature.
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