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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (06): 523-530. 上一篇    下一篇

研究论文

多氯10-氧吩噁噻系列化合物的热力学性质及稳定性的密度泛函理论方法研究

赵春松1，陈建挺2，单刚3，王甫洋2，李定龙*,2   

  1. (1北京工业大学环境与能源工程学院 北京 100124)
    (2江苏工业学院环境与安全工程学院 常州 213164)
    (3江西理工大学资源与环境工程学院 赣州 341001)
  • 投稿日期:2009-07-28 修回日期:2009-09-20 发布日期:2010-03-28
  • 通讯作者: 王甫洋 E-mail:wfyayz@163.com

Density Functional Theory Study on the Thermodynamic Properties and Stability of a Series of Polychlorinated Phenoxathiin 10-Oxides

Zhao Chunsong1 Chen Jianting2 Shan Gang3 Wang Fuyang2 Li Dinglong*,2   

  1. (1 College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124)
    (2 School of Environmental and Safety Engineering, Jiangsu Polytechnic University, Changzhou 213164)
    (3 Department of Environmental Engineering, Jiangxi University of Science and Technology, Ganzhou 341000)
  • Received:2009-07-28 Revised:2009-09-20 Published:2010-03-28

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采用Gaussian 03程序中的密度泛函理论(DFT)方法, 在BHandHLYP/6-311G**水平上对135个多氯10-氧吩噁噻系列化合物(PCPTO)进行了全优化和振动分析计算, 得到了各分子在298.15 K, 1.013×105 Pa标准状态下的热力学参数. 设计等键反应, 计算了PCPTO系列化合物的标准生成热(ΔfH()和标准生成自由能(ΔfG(), 同时研究了这些参数与氯原子的取代位置及取代数目(NPCS)之间的关系. 结果表明: 熵(S(), ΔfH(, ΔfG(与NPCS之间有很强的相关性(R2≥0.991). 根据ΔfG(的相对大小, 从理论上求得异构体的相对稳定性. 以Gaussian 03程序的输出文件为基础, 采用统计热力学程序计算了PCPTO化合物在200至1000 K的摩尔恒压热容(Cp,m), 并用最小二乘法求得Cp,m与温度之间的相关方程, 结果发现Cp,m与T, T－1和T－2之间有着很好的相关性(R2＝1.000).

关键词: 多氯10-氧吩噁噻, 密度泛函理论(DFT), 氯原子取代位置方法, 热力学性质, 相对稳定性

The thermodynamic properties of phenoxathiin 10-oxide (PTO) and 135 polychlorinated phenoxathiin 10-oxides (PCPTO) in the ideal gas state at 298.15 K and 1.013×105 Pa have been calculated at the BHandHLYP/6-311G** level using Gaussian 03 program. The isodesmic reactions were designed to calculate standard enthalpy of formation (ΔfH() and standard free energy of formation (ΔfG() of PCPTO congeners. The relations of these thermodynamic parameters with the number and position of Cl atom substitution (NPCS) were discussed, and it was found that there exist high correlation between the thermodynamic parameters [entropy (S(), ΔfH( and ΔfG(] and NPCS (R2≥0.991). According to the relative magnitude of their ΔfG(, the relative stability order of PCPTO congeners was theoretically proposed. Moreover, using a statistical thermodynamics calculation program based on Gaussian 03 output files, the values of molar heat capacity at constant pressure (Cp,m) from 200 to 1000 K for PCPTO congeners were calculated, and the temperature dependence relation of them was obtained, which suggests that there are very good relationships between Cp,m and temperature (T, T－1 and T－2) for almost all PCPTO congeners (R2＝1.000).

Key words: polychlorinated phenoxathiin 10-oxide, density functional theory (DFT), method of position of Cl atom substitution, thermodynamic property, relative stability