CH<sub>3</sub>SO<sub>3</sub>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(06): 1161-1167. doi: 10.3866/PKU.WHXB201304021 shu

Citation: CAO Jia, WANG Wen-Liang, GAO Lou-Jun, FU Feng. Mechanism and Thermodynamic Properties of CH₃SO₃ Decomposition[J]. Acta Physico-Chimica Sinica, 2013, 29(06): 1161-1167. doi: 10.3866/PKU.WHXB201304021 shu

CH₃SO₃裂解反应的机理和热力学性质

曹佳 ^1,2, ,
王文亮 ^2, ,
高楼军 ^1, ,
付峰 ^1,

基金项目:
国家自然科学基金(21173139) (21173139)

陕西省教育厅科学研究计划(2013JK0667)资助项目 (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k_total=1.40×10¹²T^0.15exp(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(D_fH^Θ_{298 K}, D_fH_{0 K}), 熵(S^Θ_{298 K})和热容(C_p, 298-2000 K), 计算的结果与实验值较接近.

关键词:

English

Mechanism and Thermodynamic Properties of CH₃SO₃ Decomposition

1.
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
Received Date: 17 December 2012
Available Online: 17 May 2013
Fund Project:
国家自然科学基金(21173139)

陕西省教育厅科学研究计划(2013JK0667)资助项目

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 k_total=1.40×10¹²T^0.15exp(7831.58/T). Thermodynamic properties including enthalpies of formation (D_fH^Θ_{298 K}, D_fH_{0 K}), entropies (S^Θ_{298 K}), and heat capacities (C_p, 298-2000 K) of all the minima and transition states are predicted from statistical mechanics, and found to be in od agreement with the available experimental values.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

CH₃SO₃裂解反应的机理和热力学性质

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