Thermodynamic Properties for Polybrominated Dibenzothiophenes by Density Functional Theory

Abstract

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(Δ_fH^θ) and the standard Gibbs energy of formation(Δ_fG^θ) of PBDTs.The relations of these thermodynamic parameters with the number and position of bromine substituents(N_PBS) are discussed,and it is found that there exist good correlations between thermodynamic parameters(including heat capacity at constant volume,entropy,enthalpy,free energy,Δ_fH^θ,Δ_fG^θ) and NPBS.The relative stability order of PBDT congeners is proposed theoretically b ased on the relative magnitude of their Δ_fG^θ.In addition,the values of molar heat capacities at constant pressure(C_p,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(Δ_fH^θ) and the standard Gibbs energy of formation(Δ_fG^θ) of PBDTs.The relations of these thermodynamic parameters with the number and position of bromine substituents(N_PBS) are discussed,and it is found that there exist good correlations between thermodynamic parameters(including heat capacity at constant volume,entropy,enthalpy,free energy,Δ_fH^θ,Δ_fG^θ) and NPBS.The relative stability order of PBDT congeners is proposed theoretically b ased on the relative magnitude of their Δ_fG^θ.In addition,the values of molar heat capacities at constant pressure(C_p,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

LI Jiayou, LIU Hongxia, YU Hongxia, WANG Zunyao, WANG Liansheng. Thermodynamic Properties for Polybrominated Dibenzothiophenes by Density Functional Theory[J]. , 2009, 17(6): 999-1008.

李加友, 柳红霞, 于红霞, 王遵尧, 王连生. Thermodynamic Properties for Polybrominated Dibenzothiophenes by Density Functional Theory[J]. , 2009, 17(6): 999-1008.

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