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Abstract

The kinetics of the aldol condensation of cyclohexanone in decalin were investigated at 210 °C on catalysts prepared by drying and calcining the aluminium and iron hydroxides at 110-850 °C. The effect of catalyst poisoning by benzoic acid and pyridine on the course of the condensation reaction and aldol retroaldolisation was also examined. The kinetics of the cyclohexanone condensation can be described by means of Langmuir-Hinshelwood equations which are in agreement with a mechanism involving adsorption of cyclohexanone on a basic site to form a transient complex, reaction of this complex with a cyclohexanone molecule affording the aldol, the rate determining interaction of the aldol with free basic and acid sites yielding 2-(1-cyclohexen-1-yl)cyclohexanone and water and desorption of these products from the catalyst surface. The proposed kinetic model is supported by the results of catalyst poisoning. The activity of aluminium and iron oxides in the condensation of cyclohexanone is a complex function of their basicity and acidity depending strongly on the calcination temperature.