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While the potential for product inhibition in catalytic reactions is well known, the impact of neglected inhibition on measured kinetic parameters is often overlooked. The presence of product inhibition, most often caused by the competitive adsorption of products with reactants on catalytic active sites, is difficult to determine a priori for an arbitrary catalytic system. The significance of product inhibition relies on the concentration of the products, their adsorption thermodynamics on catalytically relevant sites, and process parameters such as temperature and pressure. When inhibition is significant, however, apparent activation energies and reaction orders vary from the differential-reactor apparent activation energy by a factor of 1/(1 − δ), where δ is the total inhibition order (e.g., the factor (1 − δ) = 1.6 for a system with product inhibition of −0.6 order). This is illustrated here with the kinetics of NO oxidation over Cu ion clusters (CuxOy) in Cu-SSZ-13, for which the product NO2 inhibits the forward reaction. Furthermore, in the presence of inhibition, when only reactants are fed to a flow reactor or placed in a batch reactor, there is often no practical conversion that is low enough to guarantee differential behavior. Inclusion of products in the feed solves this problem, allowing accurate determination of kinetic parameters such as apparent reaction orders and activation energies. We also demonstrate that evaluation of the necessity of co-feeding products to assure measurement of differential-reactor data in a given catalytic system is straightforward from a plot of the log of the rate (or conversion) versus the log of the space time in a flow reactor or elapsed time in a batch reactor. We encourage inclusion of this test in all kinetic analyses that are reasonably approximated by power law rate expressions. |
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