Session: Undergraduate Research Posters: Physical Chemistry:

The ability to more readily and reliably manufacture biofuels could lead to using a cleaner, renewable, and more reliable as well as cost efficient source of energy. Decarboxylative ketonization is an important reaction for the production of biofuels and industrial ketones. Improvement in the catalysis of these reactions could drastically reduce cost and heighten viability. The mechanistic step of interest is the enolization reaction, which has not been studied previously. It is the first step of the decarboxylative ketonization mechanism. We have compared the catalytic performance of ZrO₂ catalyst before (marked as ZR) and after its treatment with KOH (marked as ZK). The rate of enolization was found through a process of alpha-hydrogen exchange for deuterium in iso-butyric acid solution in D₂O. A low concentration of acid in D₂O solution was kept for maintaining pseudo first order reaction conditions. First-order dependence of the reaction rate on the concentration of iso-butyric acid was found. Catalytic performance was evaluated under a range of comparable set of conditions in terms of concentration, feed rate, and temperature. Performance results were analyzed by measuring the reaction rate and calculating the enthalpy, Gibbs free energy, and entropy of activation. ZK catalyst was found to have a higher reaction rate than the ZR catalyst. Both Gibbs free energy and the enthalpy of activation were about 2 kcal/mol lower for the ZK catalyst, while the entropy of activation was comparable.

Dr. Alexey V. Ignatchenko

Associate Professor, St. John Fisher College

Appearances