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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (06): 540-550. 上一篇    下一篇

研究论文

多溴代二苯硫醚系列化合物的热力学性质和稳定性的理论研究

刘红玲1，陈建挺2，王甫洋2，王遵尧*,1，王连生1   

  1. (1南京大学环境学院 污染控制与资源化研究国家重点实验室 南京 210093)
    (2江苏工业学院环境与安全工程学院 常州 213164)
  • 投稿日期:2009-07-19 修回日期:2009-10-12 发布日期:2010-03-28
  • 通讯作者: 王遵尧 E-mail:wangzun315cn@163.com

Theoretical Study on the Thermodynamic Properties and Stability of Polybrominated Diphenyl Sulfide Catena

Liu Hongling1 Chen Jianting2 Wang Fuyang2 Wang Zunyao*,1 Wang Liansheng1   

  1. (1 State Key Laboratory of Pollution Control and Resources Reuse, Department of Environment, Nanjing University, Nanjing 210093)
    (2 School of Environmental and Safety Engineering, Jiangsu Polytechnic University, Changzhou, Jiangsu 213164)
  • Received:2009-07-19 Revised:2009-10-12 Published:2010-03-28
  • Contact: WANG Zun-Yao E-mail:wangzun315cn@163.com

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被引次数

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在B3LYP/6-31G*水平上对209个多溴代二苯硫醚(PBDS)系列化合物进行了全优化和振动分析计算, 得到各分子在298.15 K, 1.013×105 Pa标准状态下的热力学参数. 研究了热力学参数S(与溴原子的取代位置及取代数目(NPBS)之间的关系, 结果表明: S(与NPBS之间有很强的相关性(R2＝0.993). 设计等键反应, 计算了PBDS系列化合物的标准生成热(ΔfH()和标准生成自由能(ΔfG(). 根据异构体标准生成自由能的相对大小, 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PBDS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, 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: 多溴代二苯硫醚, 密度泛函理论(DFT), 溴原子取代位置方法, 热力学性质, 相对稳定性

Fully optimized calculation and frequency analysis of 209 polybrominated diphenyl sulfide (PBDS) were carried out by using a DFT method at the B3LYP/6-31G* level and their thermodynamic parameters were obtained. The isodemic reactions were designed to calculate standard enthalpy of formation (ΔfH() and standard free energy of formation (ΔfG() of PBDS congeners. The relationships of these thermodynamic parameters with the number and the position of Br atom substitution (NPBS) was established, finding that there exists high correlation between entropy (S(), standard enthalpy of formation (ΔfH() and standard free energy of formation (ΔfG() with NPBS (R2≥0.993). The stability of PBDS congeners was theoretically proposed based on the relative magnitude of their ΔfG(. The values of Cp,m were calculated by using statistical thermodynamics calculation program at the temperatures from 200 to 1000 K based on Gaussian 03 output files, and a relative equation between Cp,m and temperature was obtained by the least square method, finding that Cp,m has a very good relationship with T, T－1 and T－2 (R2＝1.000).

Key words: polybrominated diphenyl sulfide, density functional theory (DFT), method of position of Br atom substitution, thermodynamic property, relative stability