关键词: 热动力学, 热动力学研究法, 对比参量法, 简单级数反应

Abstract: According to the theoretical basis of thermokinetics and chemical kinetics, the thermokinetically reduced parameter equation for simple order reaction has been derived and a novel thermokinetic research method, reduced parameter method, has been proposed in this paper. The mathematical models for determining the kinetic parameters and rate constants have been established. The method has simple principle and concise expression form. It only needs two time points and corresponding thermoanalytical data obtained from the same thermoanalytical curve measured by a calorimeter, both the half life time and the rate constant of studied reaction can conveniently be calculated. In the light of the reduced parameter method, a method to determine the cooling constants of calorimetric system by using the thermoanalytical data of reaction studied has been developed, which decrease the experimental errors of determining the kinetic parameter due to the difference of dynamic properties between the calorimetric measurement and the electric calibration. In order to test the validith of the reduced parameter method, the thermokinetics of the oxidation reaction of isopropyl alcohol by N-bromosuccinimide(NBS) in aqueous acetic acid solvent, the saponification of ethyl acetate in aqueous ethanol solvent and the ring-opening reaction of epichlorohydrin by hydrobromic acid in aqueous solution have been studied, respectively, the rate constants calculated with this method of reactions studied are in agreement with those published in the literature, and the reduced-parameter method is therefore believed to be correct.

Key words: Thermo-kinetics, Themo-kinetic research method, Reduced parameter method, Simple order reactions