Thermodynamic Properties for Polybrominated Dibenzothiophenes by Density Functional Theory

摘要/Abstract

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

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

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.

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.

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