Determination of kinetic expressions from the frequency response of a catalytic reactor - theoretical and experimental investigations

A new technique is presented for the investigation of non-stationary reacti on systems. Reliable quantitative information is obtained for the descripti on of non-stationary operation. A detailed description of the reaction mech anism is possible and different mechanisms with the same steady-state behav ior can be discriminated. Two models for the evaluation are presented, an a nalytical expression for a fast parameter determination and a rigorous appr oach for the determination of the elementary kinetic expressions. The new t echnique is used for the investigation of the total combustion of diluted m ethane on a Pd-support catalyst. A Langmuir-Hinshelwood mechanism was found , a Eley-Rideal mechanism could be excluded. The detailed chemical mechanis m is presented and kinetic constants for the elementary steps are determine d. (C) 2001 Elsevier Science Ltd. All rights reserved.