Application of an He I photoelectron spectroscopic (UPS) technique to the kinetic study of chemical reactions. Determination of the kinetic parameters of the conversion reaction of 2(3H) furanone to 2(5H) furanone

Abstract

The application of He I photoelectron spectroscopy (UPS) technique to the kinetic study of chemical reactions has been performed. The conversion reaction of 2(3H) furanone to 2(5H) furanone at 150°C and 100°C, determined by UPS, was found to be first order and can be expressed as (150°C) ln R 423K = −(2.41 ± 0.07) × 10 −4 s −1 t + 0.7735, and (100°C) ln R 373K = −(9.1 ± 0.6) × 10 −5 s −1 t + 0.7748. The rate constants of the reaction at 150°C and 100°C are (2.41 ± 0.07) × 10 −4 s −1 and (9.1 ± 0.6) × 10 −5 s −1, respectively. The activation energy calculated is 25.50 kJ mol −1. The reaction mechanism from the 2(3H) furanone to 2(5H) furanone can be explained as the [1,3] σ migration of a hydrogen atom in the homogeneous plane. This is the first successful example of a determination of the kinetic parameters of a chemical reaction using UPS.