A discontinuously operated chromatographic reactor and a reaction calorimeter were used to study experimentally and theoretically the heterogeneously catalyzed hydrolysis reactions of four esters (methyl formate, methyl acetate, ethyl formate, and ethyl acetate). Two different batches of an acidic ion-exchange resin were used as catalyst and adsorbent. The relevant distribution equilibria were quantified using pulse chromatographic experiments. The reaction rates were quantified from (a) the shape of the elution profiles and (b) the course of the heat fluxes. To this end, systematic experiments were carried out using fixed beds packed with the catalysts and a reaction calorimeter containing catalyst suspensions. Advantages and disadvantages of these two types of experimental approaches in terms of their potential to extract reliable kinetic parameters were evaluated. A simplified pseudohomogeneous model and the determined parameters were found to be capable of describing the concentration profiles in the chromatographic reactor for all reactions studied under diverse operation conditions.
