| 郭汉贤,樊惠玲,林建英.化学通报,2023,86(4):465-468. |
| 补偿效应研究的一个新视角 |
| A New Perspective for the Study of Compensation Effect |
| 投稿时间：2022-08-27 修订日期：2022-10-06 |
| DOI： |
| 中文关键词: Arrhenius方程 活化能 等动力学关系 序参量 Boltzmann能量分布律 |
| 英文关键词:Arrhenius equation Activation energy Isokinetic relation Order parameter Boltzmann energy distribution law |
| 基金项目:国家自然科学基金项目(22078223)资助 |
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| 中文摘要: |
| 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。用几何图形分析了Arrhenius方程,指出,过去认为方程只表示速率与温度关系是片面的,忽视了速率与活化能关系。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随其相似的连续变化,从而连通所有A,E的内在联系,lnk-1/T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lnA, 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。 |
| 英文摘要: |
| 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 lnA and E change with similar continuous changes, so as to connect all the internal relations of A and E. All the lines in the lnk-1/T graph intersect at a point. Exponential distribution is the most universal distribution function for heterogenous 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. |
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