计算化学辅助物理化学实验的拓展设计——以“乙酸乙酯皂化反应”为例

doi:10.12461/PKU.DXHX202607118

大学化学

计算化学辅助物理化学实验的拓展设计——以“乙酸乙酯皂化反应”为例

白凤杨¹, 唐一文¹, 倪爽¹, 潘秀梅², 赵震^1,3

1 沈阳师范大学化学化工学院, 能源与环境催化研究所, 辽宁沈阳 110034;
2 东北师范大学化学学院, 动力电池国家地方联合工程实验室, 功能与材料化学研究所, 吉林长春 130024;
3 中国石油大学理学院, 重质油全国重点实验室, 北京昌平 102249

收稿日期:2026-07-27 录用日期:2026-08-31
通讯作者: 倪爽, 赵震 E-mail:nis223@nenu.edu.cn;zhenzhao@cup.edu.cn Shuang Ni, Zhen Zhao
基金资助:
国家自然科学基金(22306127,22476134)；辽宁省自然科学基金青年科学基金B类项目(2026JH6/101000020)；辽宁省兴辽英才计划青年拔尖人才项目(XLYC2503035)；辽宁省自然科学基金(2024-BS-106)；辽宁省基本科研项目(JYTQN2023419)

Computational chemistry-assisted expansion design of physical chemistry experiments: a case study of saponification reaction of ethyl acetate

Fengyang Bai¹, Yiwen Tang¹, Shuang Ni¹, Xiumei Pan², Zhen Zhao^1,3

1 Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, Liaoning Province, China;
2 Institute of Functional Material Chemistry, National & Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin Province, China;
3 State Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum, Beijing 102249, China

Received:2026-07-27 Accepted:2026-08-31
Contact: Shuang Ni, Zhen Zhao E-mail:nis223@nenu.edu.cn;zhenzhao@cup.edu.cn

摘要/Abstract

摘要： 将计算化学与物理化学实验课程相结合，可以克服传统教学中乙酸乙酯皂化反应耗时久、效率低、误差大及机理展示不足等问题。本文以经典实验为载体，针对传统实验教学难以揭示其反应微观机制的难点，采用量子化学计算构建反应势能面、可视化关键中间体与过渡态结构，从分子层面阐明反应热力学与动力学规律。本文旨在通过量子化学计算和过渡态理论，帮助学生直观理解乙酸乙酯皂化反应的微观历程，帮助学生理解反应本质与二级动力学特征，为物理化学实验教学改革提供实践参考。

关键词: 计算化学, 乙酸乙酯皂化反应, 反应机理, 物理化学实验教学改革

Abstract: Integrating computational chemistry into physical chemistry laboratory courses can overcome several limitations of the traditional ethyl acetate saponification experiment, such as its long duration, low efficiency, substantial errors, and inadequate demonstration of the reaction mechanism. Using this classic experiment as a vehicle, and addressing the difficulty of revealing the microscopic reaction mechanism through conventional laboratory teaching, this study employs quantum chemical calculations to construct the reaction potential energy surface, visualize the structures of key intermediates and transition states, and elucidate the thermodynamic and kinetic characteristics of the reaction at the molecular level. By combining quantum chemical calculations with transition state theory, this work aims to help students intuitively understand the microscopic pathway of the ethyl acetate saponification reaction, grasp the essence of the reaction and its second-order kinetic features, and provide practical references for the reform of physical chemistry laboratory teaching.

Key words: Computational chemistry, Saponification of ethyl acetate, Reaction mechanism, Teaching reform of physical chemistry experiments

白凤杨, 唐一文, 倪爽, 潘秀梅, 赵震. 计算化学辅助物理化学实验的拓展设计——以“乙酸乙酯皂化反应”为例[J]. 大学化学, 2026, (): 2607118.

Fengyang Bai, Yiwen Tang, Shuang Ni, Xiumei Pan, Zhen Zhao. Computational chemistry-assisted expansion design of physical chemistry experiments: a case study of saponification reaction of ethyl acetate[J]. University Chemistry, 2026, (): 2607118.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202607118

https://www.dxhx.pku.edu.cn/CN/Y2026/V/I/2607118

参考文献

[1] 葛欣, 席景科, 李政伟, 刘厚泉. 大学教育, 2015, No. 6, 2.
[2] 黄嘉博, 黎权鑫, 曹中艳, 党丽, 倪绍飞. 大学化学, 2025, 40 (3), 153.
[3] 张红, 霍树营, 任淑霞, 张春芳, 王海军. 实验室研究与探索, 2019, 38 (5), 136.
[4] 朱万春, 周兵, 谢腾峰, 管景奇, 赵旭. 大学化学, 2025, 40 (8), 33.
[5] 胡跃华, 尹力. 大学化学, 1989, 4 (5), 40.
[6] 张毅, 张喆, 柳明洙, 李锦, 秦燃, 王一杉, 郑炯, 郑申, 赖建豪, 陈然, 等. 大学化学, 2016, 31 (3), 55.
[7] 玉占君, 张文伟, 任庆云. 辽宁师范大学学报(自然科学版), 2006, 29 (4), 511.
[8] 王渭娜, 冯丽霞, 刘峰毅, 王文亮. 大学化学, 2025, 40 (3), 206.
[9] 叶同奇, 王艳青, 王琪, 从怀萍, 孔祥华, 叶跃雯. 大学化学, 2025, 40 (7), 387.
[10] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, et al., Gaussian 16, Revision A.03, Gaussian Inc.:Wallingford CT, USA, 2016.
[11] R. Dennington, T.A. Keith, J.M. Millam, GaussView, Version 5, Semichem Inc.:Shawnee Mission, KS, USA, 2008.
[12] R.G. Compton, C.H. Bamford, C.F.H. Tipper, Chemical Kinetics 1972, 10, iii.
[13] J.F. Mata-Segreda, J. Am. Chem. Soc. 2002, 124 (10), 2259.
[14] 马丽, 李雪, 张东菊. 高等学校化学学报, 2022, 43 (7), 2123.
[15] T. Mihaylov, T. Parac-Vogt, K. Pierloot, Inorg. Chem. 2012, 51 (18), 9619.
[16] A.V. Marenich, C.J. Cramer, D.G. Truhlar, J. Phys. Chem. B 2009, 113 (18), 6378.
[17] A. Einstein, Annalen der Physik 1905, 17, 891.
[18] F.C. Collins, G.E. Kimball, Ind. Eng. Chem. 1949, 41 (11), 2551.
[19] B.C. Garrett, D.G. Truhlar, J. Phys. Chem. 1979, 83 (1), 200.
[20] 印永嘉, 奚正楷, 张树永. 北京:高等教育出版社, 2016, 312-318.
[21] T. Lu, F. Chen, J. Comput. Chem. 2012, 33, 580.
[22] W. Humphrey, A. Dalke, K. Schulten, J. Mol. Graph. 1996, 14, 33.
[23] A. Petek, M. Krajnc, Int. J. Chem. Kinet. 2012, 44 (10), 692.
[24] 成昭, 范涛, 杨莉宁, 张雪娇. 化工时刊, 2019, 33 (11), 10.