大学化学 >> 2022, Vol. 37 >> Issue (7): 2204035.doi: 10.3866/PKU.DXHX202204035

师生笔谈 上一篇    下一篇

关于Arrhenius公式的几点讨论

张晨曦, 苏涵, 张树永()   

  • 收稿日期:2022-04-12 录用日期:2022-05-09 发布日期:2022-05-20
  • 通讯作者: 张树永 E-mail:syzhang@sdu.edu.cn
  • 作者简介:张树永, Email: syzhang@sdu.edu.cn

Discussions on the Arrhenius Equation

Chenxi Zhang, Han Su, Shuyong Zhang()   

  • Received:2022-04-12 Accepted:2022-05-09 Published:2022-05-20
  • Contact: Shuyong Zhang E-mail:syzhang@sdu.edu.cn

摘要:

Arrhenius公式是最重要的化学动力学经验公式,提出百余年来,科学家对其的讨论从未停止。本文溯源了该公式产生的历史过程,进一步说明其与van't Hoff方程的联系。针对普遍接受的Tolman活化能的物理意义进行了讨论,给出了修正建议。对活化能随温度变化的情况进行了讨论,对Arrhenius公式的适用温度范围进行了量化说明,建议对于分子结构较复杂的反应,即便在通常温度范围内,亦应采用三常数公式。对物理化学教材中与Arrhenius公式具有相似形式的公式进行了概括,说明了其相似性的本质。相关讨论有助于师生更正确地理解和使用Arrhenius公式。

关键词: Arrhenius公式, Tolman活化能, 温度适用范围, 热力学关系

Abstract:

The Arrhenius equation is one of the most important equations in chemical kinetics and has been discussed by scientists for more than a century since its establishment. The historical process of the equation and further explanations of its relationship with the van't Hoff equation are traced. The physical meaning of the Tolman activation energy is discussed with some suggested modifications. The variation of the activation energy with temperature is discussed, and the temperature range for applying the Arrhenius equation is quantitatively analyzed. It is suggested that the three-constant equation be used even in the normal temperature range for reactants with a complex molecular structure. The similarity between some thermodynamic equations and the Arrhenius equation in physical chemistry textbooks are explained. These discussions will help with correctly understanding and applying the Arrhenius equation.

Key words: Arrhenius equation, Tolman activation energy, Temperature validity range, Thermodynamic relation

MSC2000: 

  • G64