A Kinetic Study of a Photo-Oxidation Reaction between α-Terpinene and Singlet Oxygen in a Novel Oscillatory Baffled Photo Reactor

Abstract

By planting LEDs on the surfaces of orifice baffles, a novel batch oscillatory baffled photoreactor (OBPR) together with polymer-supported Rose Bengal (Ps-RB) beads are here used to investigate the reaction kinetics of a photo-oxidation reaction between α-terpinene and singlet oxygen (1O2). In the mode of NMR data analysis that is widely used for this reaction, α-terpinene and ascaridole are treated as a reaction pair, assuming kinetically singlet oxygen is in excess or constant. We have, for the first time, here examined the validity of the method, discovered that increasing α-terpinene initially leads to an increase in ascaridole, indicating that the supply of singlet oxygen is in excess. Applying a kinetic analysis, a pseudo-first-order reaction kinetics is confirmed, supporting this assumption. We have subsequently initiated a methodology of estimating the 1O2 concentrations based on the proportionality of ascaridole concentrations with respect to its maximum under these conditions. With the help of the estimated singlet oxygen data, the efficiency of 1O2 utilization and the photo efficiency of converting molecular oxygen to 1O2 are further proposed and evaluated. We have also identified conditions under which a further increase in α-terpinene has caused decreases in ascaridole, implying kinetically that 1O2 has now become a limiting reagent, and the method of treating α-terpinene and ascaridole as a reaction pair in the data analysis would no longer be valid under those conditions.