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CH3SO3裂解反应的机理和热力学性质
引用本文:曹佳,王文亮,高楼军,付峰.CH3SO3裂解反应的机理和热力学性质[J].物理化学学报,2013,29(6):1161-1167.
作者姓名:曹佳  王文亮  高楼军  付峰
作者单位:1.College of Chemistry & Chemical engineering, Yan’an University, Yan’an 716000, P. R. China;2.Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry &Chemical engineering, Shaanxi Normal University, Xi’an 710062, P. R. China
基金项目:supported by the National Natural Science Foundation of China(21173139);Foundation of Shaanxi Education Department(2013JK0667)~~
摘    要:在G3XMP2//B3LYP/6-311+G(3df,2p)水平上对CH3SO3裂解反应的机理进行了研究, 获得了6 条通道(10 条路径), 并构建了其势能剖面. 同时采用单分子反应理论计算了各个通道在温度200-3000 K区间的速率常数. 研究结果表明, 在计算温度范围内, CH3SO3裂解反应的主产物为P1(CH3+SO3), 产物P2(CH3O+SO2)和P3(HCHO+HOSO)仅在温度大于3000 K时对总产物有贡献, 而产物P4(CHSO2+H2O), P5(CH2SO3+H)和P6(CHSO3+H2)贡献相对较少. 将裂解反应总的速率常数拟合为ktotal=1.40×1012T0.15exp(7831.58/T). 此外, 根据统计热力学原理, 预测了所有物种的生成焓(DfHΘ298 K, DfH0 K), 熵(SΘ298 K)和热容(Cp, 298-2000 K), 计算的结果与实验值较接近.

关 键 词:CH3SO3  裂解机理  热力学性质  速率常数  
收稿时间:2012-12-17
修稿时间:2013-04-02

Mechanism and Thermodynamic Properties of CH3SO3 Decomposition
CAO Jia,WANG Wen-Liang, GAO Lou-Jun,FU Feng.Mechanism and Thermodynamic Properties of CH3SO3 Decomposition[J].Acta Physico-Chimica Sinica,2013,29(6):1161-1167.
Authors:CAO Jia  WANG Wen-Liang  GAO Lou-Jun  FU Feng
Institution:1.College of Chemistry & Chemical engineering, Yan’an University, Yan’an 716000, P. R. China;2.Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry &Chemical engineering, Shaanxi Normal University, Xi’an 710062, P. R. China
Abstract:The mechanism and kinetics of unimolecular decomposition of CH3SO3 are studied at the G3XMP2//B3LYP/6-311+G(3df,2p) level of theory. Six possible dissociation channels and potential energy surface for the CH3SO3 decomposition are investigated. Rate constants over the temperature range of 200-3000 K are calculated using Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The results indicate that the product P1(CH3+SO3) is dominant between 200-3000 K. Products P2(CH3O+SO2) and P3(HCHO+HOSO) increase significantly at higher temperatures (>3000 K). Products P4(CHSO2+H2O), P5(CH2SO3+H) and P6(CHSO3+H2) show little formation in the temperature range (200-3000 K). The total rate constant can be expressed as ktotal=1.40×1012T0.15exp(7831.58/T). Thermodynamic properties including enthalpies of formation (DfHΘ298 K, DfH0 K), entropies (SΘ298 K), and heat capacities (Cp, 298-2000 K) of all the minima and transition states are predicted from statistical mechanics, and found to be in good agreement with the available experimental values.
Keywords:3SO3'  ')  CH3SO3" target="_blank">">CH3SO3  Decomposition mechanism  Thermodynamic property  Rate constant
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