Acta Chimica Sinica ›› 2011, Vol. 69 ›› Issue (06): 617-626. Previous Articles     Next Articles

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  1. (1污染控制与资源化研究国家重点实验室 南京大学环境学院 南京 210093)
    (2常州大学环境与安全工程学院 常州 213164)
  • 投稿日期:2010-08-26 修回日期:2010-10-12 发布日期:2010-11-23
  • 通讯作者: 王遵尧
  • 基金资助:


Comparative Studies on Some Properties of Polyfluorinated, Polychlorinated and Polybrominated Dibenzo-p-dioxins

Hou Haifeng1,2 Chen Binyuan2 Zhang Xuesheng2 Wang Zunyao*,1   

  1. (1 State Key Laboratory of Pollution Control and Resources Reuse, School of Environment, Nanjing University, Nanjing 210093)
    (2 Department of Environmental and Safety Engineering, Changzhou University, Changzhou 213164)
  • Received:2010-08-26 Revised:2010-10-12 Published:2010-11-23
  • Contact: WANG Zun-Yao

The thermodynamic properties of 76 polyfluorinated dibenzo-p-dioxins (PFDDs) in the ideal gas state at 298.15 K and 1.013×105 Pa have been calculated at the B3LYP/6-311G** and B3LYP/6-31G* levels using Gaussian 03 program, and it was found that values of standard enthalpy of formation (ΔfH?), standard free energy of formation (ΔfG?) and standard entropy (S?) were broadly consistent under the two base groups. According to the relative magnitude of their ΔfG? at the B3LYP/6-311G** level, the relative stability order of PFDD congeners was theoretically proposed. Octanol-water partition coefficients (lg Kow) of polybrominated dibenzofurans (PBDDs), polychlorinated dibenzofurans (PCDDs) and PFDDs were calculated by group contributions. Comparison of the properties (including lg Kow, S?, ΔfH? and ΔfG?) between PFDDs and PCDDs, PBDDs was carried out. Moreover, the relative rate constants of formation reactions of PFDDs and the values of molar heat capacity at constant pressure (Cp,m) from 200 to 1800 K for PFDDs congeners were calculated using a statistical thermodynamics calculation program. The temperature dependence relation of Cp,m was obtained using the least-squares method. The result shows that there exists very good relationship between Cp,m and temperature (T, T-1 and T-2) for almost all PFDD congeners.

Key words: polyfluorinated dibenzo-p-dioxins, DFT method, thermodynamic property, octanol-water partition coefficient (lg Kow), molar heat capacity at constant pressure (Cp,m)