Thermal decomposition of acetate: III. Catalysis by mineral surfaces

Abstract

The kinetics of thermal decarboxylation of aqueous solutions of acetic acid and sodium acetate were evaluated at 335 and 355°C in contact with various surfaces as potential catalysts. Quartz, fused quartz, calcite, natural pyrite, titanium oxide, and Au apparently do not catalyze aqueous decarboxylation reactions, in contrast to Pyrex, Ca-montmorillonite, Fe-bearing montmorillonite, hematite, synthetic pyrite, and magnetite. The dependence of the rate of acetic acid decarboxylation on the surface area of pyrite per unit solution volume was also studied. The results show that the decarboxylation of acetic acid and acetate is catalyzed heterogeneously, with the cleavage of the C-C bond occurring while the acetate molecule is adsorbed onto a surface. Entropies and enthalpies of activation obtained from these experiments are compatible with the isokinetic relationship established previously for acetic acid and acetate under similar experimental conditions, indicating the existence of a common rate-determining step. Experimental evidence indicates that oxidation of acetic acid can occur with hematite and defected magnetite. These oxidative decomposition reactions differ from the decarboxylation reaction in that CO 2 and polycondensates are produced instead of CO 2 and CH 4.