过渡态理论对Arrhenius公式的诠释——以硝酸异丙酯与自由基反应为例

doi:10.3866/PKU.DXHX202306057

Abstract

Abstract:

In the teaching of university-level physical chemistry, the Arrhenius formula elucidates the relationship between the rate constant of a reaction, temperature, and activation energy. However, it is difficult for students to understand and master the formula simply from its expression. Taking the reaction of isopropyl nitrate with Cl atoms, OH and NO₃ radicals as examples, the rate constants of the reactions at different temperatures were calculated based on the potential energy surface by the Transition State Theory. The change trends of rate constants with temperature for the reactions with different energy barriers have been visually analyzed. We hope to help students understand Arrhenius formula in essence by analyzing specific cases, so as to broaden their knowledge and cultivate their scientific inquiry ability.

Key words: Kinetics, Potential energy surface, Rate constant, Temperature

Cuihong Sun, Baoen Xu, Ying Liu, Jing Yang, Liqiang Lv. Interpretation of Arrhenius Formula by Transition State Theory: Taking the Reaction of Isopropyl Nitrate with Radicals as an Example[J].University Chemistry, 2024, 39(1): 320-324.

Figures/Tables 4

References 10

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反应体系	IPN + Cl		IPN + OH		IPN + NO₃
反应体系	R	TS	R	TS	R	TS
ε_ele/(a.u.)	−857.5943	−677.6695	−857.5996	−677.6777	−857.5801	−677.6596
ε_{ele, rel}/(kJ∙mol⁻¹)	0.00	15.77	0.00	7.98	0.00	25.88
ZPE/(a.u.)	0.1120	0.1251	0.1123	0.1265	0.1042	0.1229
ε_ele + ZPE/(a.u.)	−857.4823	−677.5444	−857.4872	−677.5512	−857.4759	−677.5368
(ε_ele + ZPE)_rel/(kJ∙mol⁻¹)	0.00	−5.03	0.00	2.27	0.00	20.10

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Interpretation of Arrhenius Formula by Transition State Theory: Taking the Reaction of Isopropyl Nitrate with Radicals as an Example

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