AbstractDynamic reactor operations will gain interest with the increase of intermittent electricity from renewable sources. Periodic operation of catalytic reactors can also be used for kinetic studies with better parameter estimation than steady‐state operation. This methodology is exemplified for the case of acetylene hydrogenation over Pd/α‐Al2O3 using small amplitude flow oscillations. It allows the evaluation of several elementary kinetic parameters from one set of dynamic data for a reaction mechanism based on a single catalytic site. The optimized transient model is able to reproduce the time‐evolution of the reactant and product molar fractions at the outlet of a fixed bed operated with modulations of different amplitudes and frequencies. It further shows that the acetylene conversion is controlled by two steps, the hydrogen adsorption step and the hydrogenation of the surface vinyl intermediate into adsorbed ethylene.