Journal of Molecular Catalysis A-Chemical, Vol.245, No.1-2, 132-140, 2006
Effect of water on sulfuric acid catalyzed esterification
This paper reports on an investigation into the impact of water on liquid-phase sulfuric acid catalyzed esterification of acetic acid with methanol at 60 degrees C. In order to diminish the effect of water on the catalysis as a result of the reverse reaction, initial reaction kinetics were measured using a low concentration of sulfuric acid (1 x 10(-3) M) and different initial water concentrations. It was found that the catalytic activity of sulfuric acid was strongly inhibited by water. The catalysts lost up to 90% activity as the amount of water present increased. The order of water effect on reaction rate was determined to be -0.83. The deactivating effect of water also manifested itself by changes in the activation energy and the pre-exponential kinetic factor. The decreased activity of the catalytic protons is suggested to be caused by preferential solvation of them by water over methanol. A proposed model successfully predicts esterification rate as reaction progresses. The results indicate that, as esterification progresses and byproduct water is produced, deactivation of the sulfuric acid catalyst occurs. Autocatalysis, however, was found to be hardly impacted by the presence of water, probably due to compensation effects of water on the catalytic activity of acetic acid, a weak acid. (c) 2005 Elsevier B.V. All rights reserved.