热动力学的研究 X. 一级反应的热谱峰高法

本文根据一级反应的热谱曲线方程、建立了速度常数的一种新算法。这种新方法,只需要热谱曲线在各个特征时刻的峰高,而不需要任何峰面积,即可算得反应体系的无量纲参数和速度常数,称为一级反应的热谱峰高法。

Studies on Thermokinetics X. Thermogram's Peak-Heights Method for First Order Reactions

In the previous articles,a data processing method for studies on thermokinetics of a first order reaction in liquid phase had been developed. It was called the dimensionless parameter method, in which the dimensionless parameter and the rate constant of a reaction system were calculated from the thermogram's peak-area.In this paper in the light of a theoretical thermogram's equation of a first order reaction, a novel data processing method is proposed,in which the dimensionless parameter and the rate constant are calculated from the thermogram's peak-heights without using any peak-area. Thereby the problems arisen from the peak-area-computation can be avoided.In order to test the validity of this novel method, the saponiflcations of ethyl propionate and butyrate in aqueous ethanol solvent have been studied. The rate constants calculated with this novel method are in agreement with those in the literature, and therefore the basic principles of this thermogram's peak-heights method are believed to be correct.