慢对峙反应的热动力学对比参量法

Thermokinetic Reduced Parameter Method for Slower Opposing Reactions

根据热动力学基本理论,推导了对峙反应的热动力学对比参量方程,建立了对峙反应对比参量法的数学模型.该法利用特征时间tm和2tm时对应的热谱数据计算反应的对比参量,进而解析出较慢对峙反应的速率常数和平衡常数.利用该法分别研究了硝基乙烷与氨和三（羟甲基）氨基甲烷质子转移反应的热动力学,实验结果表明了较慢对峙反应对比参量法的正确性.

According to the theoretical basis of thermokinetics, the thermokinetic reduced parameter equation of opposing reaction has been derived, and the mathematical models of the reduced parameter method for opposing reaction have been established. Only needing the thermoanalytical data at the characteristic time parameter tm and 2tm from a single thermoanalytical curve, both the reduced energy and the reduced time parameter can be easily obtained, and then the rate constants and the equilibrium constant of slower opposing reaction can be calculated conveniently. In order to test the validity of this method, the thermokinetics for the proton-transfer reaction of nitroethane with ammonia at 15 and 25 ℃ , and with Tris at 15 and 30℃ have been studied, respectively. The experimental results indicate that the theory and method of the reduced parameter method for slower opposing reactions are correct.