节点文献
补偿效应研究的一个新视角
A New Perspective for the Study of Compensation Effect
【摘要】 补偿效应与Arrhenius方程关系密切。本文为补偿效应研究提供了新视野。用几何图象分析了Arrhenius方程,指出过去认为此方程只表示速率与温度关系是不全面的,忽视了速率常数与活化能关系的研究。从图形看出,指前因子与活化能本身就具有互补关系,虽仅限于每两个不同活化能的情况。反应是一自组织过程。补偿效应的成立有必要条件和充分条件。欲实现补偿效应,从协同学角度考虑,E/T作为参变量必需小于一阈值,以使反应起活。并有一自变量做系列改变,以使A、E随其相似地连续变化,从而连通所有A、E的内在联系,1/T-lnk图中诸直线交于一点。指数分布是非均匀体系最具有普遍意义的分布函数。概率分析指出,补偿效应是A、E在固体表面和内部均呈相似指数分布的产物。对催化反应与非催化反应有普适性。在速率常数中体现为结构分布概率因子及能量分布概率因子。
【Abstract】 Compensation effect is closely related to Arrhenius equation. This paper provides a new perspective for the study of compensation effect. The Arrhenius equation is analyzed by geometric graph. It is pointed out that the relationship between rate and temperature is considered one-sided in the past and the relationship between rate and activation energy is neglected. It can be seen from the graph that the pre-exponential factor and the activation energy themselves are complementary, although only in the case of two different activation energies. Reaction is a self-organizing process. There are necessary and sufficient conditions for the establishment of compensation effect. In order to realize the compensation effect, E/T as a order parameter must be less than a threshold from the perspective of synetics in order to make the reaction active. And an independent variable makes a series of changes to make A and E change with similar continuous changes, so as to connect all the internal relations of A and E. All the lines in the 1/T-lnk graph intersect at a point. Exponential distribution is the most universal distribution function for heterogeneous systems. The probability analysis shows that the compensation effect is the product of similar exponential distribution of A and E on the surface and inside of the solid. It has universal applicability to catalytic and non-catalytic reactions. In the rate constant, the structure distribution probability factor and the energy distribution probability factor are reflected.
【Key words】 Arrhenius equation; Activation energy; Isokinetic relation; Order parameter; Boltzmann energy distribution law;
- 【文献出处】 化学通报 ,Chemistry , 编辑部邮箱 ,2023年04期
- 【分类号】O643.12
- 【下载频次】6