Reaction Mechanisms and Kinetics for the Reaction of HO2＋CH2S

Acta Chimica Sinica ›› 2011, Vol. 69 ›› Issue (17): 1957-1964. Next Articles

Full Papers

过氧氢自由基HO₂与CH₂S的反应机理及动力学

刘占荣^1,2，许保恩^1,2，曾艳丽¹，李晓艳¹，孟令鹏*^,1，孙政¹，张雪英¹，张萍²

(¹河北师范大学计算量子化学研究所石家庄 050016)
(²石家庄学院化工学院石家庄 050035)

投稿日期:2010-12-23 修回日期:2011-04-12 发布日期:2011-05-11
通讯作者: 孟令鹏 E-mail:menglp@mail.hebtu.edu.cn
基金资助:
AIM和ELF理论方法及应用的新拓展;取代元素对镁基储氢合金结构和性质影响的理论研究;电子密度拓扑分析理论方法研究弱键结构;金属氢化物储氢材料的结构、成键作用及稳定性的理论研究;用电子密度拓扑分析理论研究有机金属簇合物中的化学键;大气化学中光化学氧化剂的反应活性研究;镁基储氢合金结构、性质及储氢机制的理论研究

Reaction Mechanisms and Kinetics for the Reaction of HO₂＋CH₂S

Liu Zhanrong^1,2 Xu Baoen^1,2 Zeng Yanli¹ Li Xiaoyan¹ Meng Lingpeng*^,1 Sun Zheng¹ Zhang Xueying¹ Zhang Ping²

(¹Institute of Quantum Chemistry, Hebei Normal University, Shijiazhuang 050016)
(²College of Chemical Engineering, Shijiazhuang University, Shijiazhuang 050035)

Received:2010-12-23 Revised:2011-04-12 Published:2011-05-11

The reaction mechanism of HO₂ with CH₂S was investigated at the B3LYP/6-311＋＋G(d,p) level. Energetic information of stationary points and the points along the minimum energy path is further refined at the CCSD(T)/6-311＋＋G(d,p) level. The rate constants of these channels in the temperature range of 200～2500 K were evaluated by means of the classical transition state theory (TST) and the canonical variational transition state theory (CVT) conjunction with the small-curvature tunneling correction (SCT). Six possible reaction channels have been identified for the title reaction. Based on the potential energy surface and the kinetics, it can be concluded that HOOCH₂S, formed via the end O atom of the HO₂ radical attacking on the C atom of the CH₂S molecule, and its isomer OOCH₂SH are the major products. When the temperature is lower than 1400 K, the channel (1a) HO₂＋CH₂S→TS1/P1→HOOCH₂S is the major reaction path, while the channel (2a) HO₂＋CH₂S→TS2/P1→HOOCH₂S becomes the favorable reaction path when the temperature is higher than 1400 K.

Key words: HO₂, CH₂S, reaction mechanism, rate constant

CLC Number:

O641
O643

Cite this article

LIU Zhan-Rong, XU Bao-En, ZENG Yan-Li, LI Xiao-Yan, MENG Ling-Peng, SUN Zheng, ZHANG Xue-Ying, ZHANG Ping. Reaction Mechanisms and Kinetics for the Reaction of HO₂＋CH₂S[J]. Acta Chimica Sinica, 2011, 69(17): 1957-1964.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

[1]	Guanglong Huang, Xiao-Song Xue. Computational Study on the Mechanism of Chen’s Reagent as Trifluoromethyl Source [J]. Acta Chimica Sinica, 2024, 82(2): 132-137.
[2]	Guoqing Cui, Yiyang Hu, Yingjie Lou, Mingxia Zhou, Yuming Li, Yajun Wang, Guiyuan Jiang, Chunming Xu. Research Progress on the Design, Preparation and Properties of Catalysts for CO₂ Hydrogenation to Alcohols [J]. Acta Chimica Sinica, 2023, 81(8): 1081-1100.
[3]	Xinpu Fu, Xiuling Wang, Weiwei Wang, Rui Si, Chunjiang Jia. Fabrication and Mechanism Study of Clustered Au/CeO₂ Catalyst for the CO Oxidation Reaction^★ [J]. Acta Chimica Sinica, 2023, 81(8): 874-883.
[4]	Luocong Wang, Zhewei Li, Caiwei Yue, Peihuan Zhang, Ming Lei, Min Pu. Theoretical Study on the Isomerization Mechanism of Azobenzene Derivatives under Electric Field [J]. Acta Chimica Sinica, 2022, 80(6): 781-787.
[5]	Siming Yang, Airong Liu, Jing Liu, Zhaoli Liu, Weixian Zhang. Advance of Sulfidated Nanoscale Zero-Valent Iron: Synthesis, Properties and Environmental Application [J]. Acta Chimica Sinica, 2022, 80(11): 1536-1554.
[6]	Yilong Hua, Donghan Li, Tianhang Gu, Wei Wang, Ruofan Li, Jianping Yang, Wei-xian Zhang. Enrichment of Uranium from Aqueous Solutions with Nanoscale Zero-valent Iron: Surface Chemistry and Application Prospect [J]. Acta Chimica Sinica, 2021, 79(8): 1008-1022.
[7]	Huang Rongyi, Shen Qiong, Zhang Chao, Zhang Shaoyong, Xu Heng. Studies on the Mechanism of the Transition Metal-Catalyzed Reaction of Organonitrile with Sodium Azide [J]. Acta Chimica Sinica, 2020, 78(6): 565-571.
[8]	Chen Fangfang, Sun Xiaohui, Yao Qian, Li Zerong, Wang Jingbo, Li Xiangyuan. Accurate Calculation of the Energy Barriers and Rate Constants of the Large-size Molecular Reaction System for Abstraction from Alkyl Hydroperoxides [J]. Acta Chim. Sinica, 2018, 76(4): 311-318.
[9]	Wu Weirong, Yuan Xiaomin, Hou Hua, Wang Baoshan. Theoretical Investigations on the Mechanisms for the Reactions of Sevoflurane Radicals[(CF₃)₂C(·)OCH₂F, (CF₃)₂CHOC(·)HF] with O₂and the OH· Radicals Regeneration [J]. Acta Chim. Sinica, 2018, 76(10): 793-801.
[10]	Mu Weihua, Ma Yao, Fang Decai, Wang Rong, Zhang Haina. Computational Insights into the Diels-Alder-alike Reactions of 1-Iodo-2-Lithio-o-Carborane with Fulvenes [J]. Acta Chim. Sinica, 2018, 76(1): 55-61.
[11]	Tang Jing, Tang Lin, Feng Haopeng, Dong Haoran, Zhang Yi, Liu Sishi, Zeng Guangming. Research Progress of Aqueous Pollutants Removal by Sulfidated Nanoscale Zero-valent Iron [J]. Acta Chim. Sinica, 2017, 75(6): 575-582.
[12]	Huang Xiao-yue, Wang Wei, Ling Lan, Zhang Wei-xian. Heavy Metal-nZVI Reactions: the Core-shell Structure and Applications for Heavy Metal Treatment [J]. Acta Chim. Sinica, 2017, 75(6): 529-537.
[13]	Ding Shuang, Ge Qingfeng, Zhu Xinli. Research Progress in Ketonization of Biomass-derived Carboxylic Acids over Metal Oxides [J]. Acta Chim. Sinica, 2017, 75(5): 439-447.
[14]	Yang Zhen, Xue Yijiang, He Yuanhang. Thermal Sensitivity of CL20/DNB Co-crystal Research via Molecular Dynamics Simulations [J]. Acta Chim. Sinica, 2016, 74(7): 612-619.
[15]	Ma Jun, Li Rong, Ren Kuiwei, Ma Xilong, Zhu Kaili, Geng Zhiyuan. Mechanism and Spin-orbit Coupling Study for Two State Reaction Ni₂⁺ with Cyclohexane [J]. Acta Chim. Sinica, 2015, 73(5): 431-440.

过氧氢自由基HO₂与CH₂S的反应机理及动力学

Reaction Mechanisms and Kinetics for the Reaction of HO₂＋CH₂S

PDF

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

过氧氢自由基HO2与CH2S的反应机理及动力学