丁烯/丁醇异构体低温氧化 Waddington 反应机制理论研究

The Waddington mechanism is crucial for the low-temperature oxidation of both alkenes and alcohols. In this study, the Waddington mechanism in the oxidation of butene and butanol isomers was systematically investigated. Fundamental quantum chemical calculations were conducted for the rate constants and thermodynamic properties of the reactions and species in this mechanism. Temperature- and pressure-dependent rate constants were obtained based on the transition state theory, associated with the Rice Ramsperger Kassel Marcus and master equation theories. Temperature-dependent thermodynamic parameters (enthalpies of formation, entropy, and heat capacity) of all major species were also calculated based on the statistical thermodynamics. The comparative study reveals that the rate coefficients and thermodynamic parameters of isobutene (R4 and R5 reaction systems) show good agreement with the corresponding values obtained from the literature. All the calculated results can be directly used for developing the kinetic model of low-temperature oxidation of butene and butanol isomers.