SCI和EI收录∣中国化工学会会刊

›› 2009, Vol. 17 ›› Issue (6): 999-1008.

• THERMODYNAMICS AND chemical engineering data • Previous Articles     Next Articles

Thermodynamic Properties for Polybrominated Dibenzothiophenes by Density Functional Theory

LI Jiayou1, LIU Hongxia1, YU Hongxia2, WANG Zunyao1, WANG Liansheng2   

  1. 1. School of Biological and Chemical Engineering, Jiaxing University, Jiaxing 314001, China;
    2. Department of Environment, Nanjing University, Nanjing 214007, China
  • Received:2008-12-22 Revised:2009-04-28 Online:2009-12-28 Published:2009-12-28
  • Supported by:
    Supported by the National Natural Science Foundation of China (20737001)

Thermodynamic Properties for Polybrominated Dibenzothiophenes by Density Functional Theory

李加友1, 柳红霞1, 于红霞2, 王遵尧1, 王连生2   

  1. 1. School of Biological and Chemical Engineering, Jiaxing University, Jiaxing 314001, China;
    2. Department of Environment, Nanjing University, Nanjing 214007, China
  • 通讯作者: WANG Zunyao,E-mail:wangzun315cn@163.com
  • 基金资助:
    Supported by the National Natural Science Foundation of China (20737001)

Abstract: The thermodynamic properties of 135 polybrominated dibenzothiophenes(PBDTs) in the gaseous state at 298.15 K and 1.013×105 Pa,are calculated using the density functional theory(the B3LYP/6-311G**) with Gaussian 03.Based on these data,the isodesmic reactions are designed to calculate the standard enthalpy of formation(ΔfHθ) and the standard Gibbs energy of formation(ΔfGθ) of PBDTs.The relations of these thermodynamic parameters with the number and position of bromine substituents(NPBS) are discussed,and it is found that there exist good correlations between thermodynamic parameters(including heat capacity at constant volume,entropy,enthalpy,free energy,ΔfHθfGθ) and NPBS.The relative stability order of PBDT congeners is proposed theoretically b ased on the relative magnitude of their ΔfGθ.In addition,the values of molar heat capacities at constant pressure(Cp,m) for PBDT congeners are calculated.

Key words: polybrominated dibenzothiophenes, density functional theory, method of position of substituted Br atom, thermodynamic parameters, relative stability

摘要: The thermodynamic properties of 135 polybrominated dibenzothiophenes(PBDTs) in the gaseous state at 298.15 K and 1.013×105 Pa,are calculated using the density functional theory(the B3LYP/6-311G**) with Gaussian 03.Based on these data,the isodesmic reactions are designed to calculate the standard enthalpy of formation(ΔfHθ) and the standard Gibbs energy of formation(ΔfGθ) of PBDTs.The relations of these thermodynamic parameters with the number and position of bromine substituents(NPBS) are discussed,and it is found that there exist good correlations between thermodynamic parameters(including heat capacity at constant volume,entropy,enthalpy,free energy,ΔfHθfGθ) and NPBS.The relative stability order of PBDT congeners is proposed theoretically b ased on the relative magnitude of their ΔfGθ.In addition,the values of molar heat capacities at constant pressure(Cp,m) for PBDT congeners are calculated.

关键词: polybrominated dibenzothiophenes, density functional theory, method of position of substituted Br atom, thermodynamic parameters, relative stability