DFT Calculation on polychlorinated phenarsazines: Their gas phase thermodynamic functions and the implications of Cl substituted position

Authors

  • Jia Q. Shi,

    1. State Key Laboratory of Pollution Control and Resources Reuse, Department of Environment, Nanjing University, Jiangsu Nanjing 210093, PR China
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  • Hong X. Liu,

    1. School of Biological and Chemical Engineering, Jiaxing University, Zhejiang Jiaxing 314001, PR China
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  • Ying Xu,

    1. State Key Laboratory of Pollution Control and Resources Reuse, Department of Environment, Nanjing University, Jiangsu Nanjing 210093, PR China
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  • Hui Liu,

    1. School of Biological and Chemical Engineering, Jiaxing University, Zhejiang Jiaxing 314001, PR China
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  • Alison Flamm,

    1. U.S. Fulbright Student Grantee, School of Social and Behavioral Sciences, Nanjing University, Jiangsu Nanjing 210093, PR China
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  • Zun Y. Wang

    Corresponding author
    1. State Key Laboratory of Pollution Control and Resources Reuse, Department of Environment, Nanjing University, Jiangsu Nanjing 210093, PR China
    • State Key Laboratory of Pollution Control and Resources Reuse, Department of Environment, Nanjing University, Jiangsu Nanjing 210093, PR China.
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Abstract

The thermodynamic properties of 136 polychlorinated phenarsazines (PCPAZs) have been calculated by density functional theory at the B3LYP/6-31G* level. Then, isodesmic reactions are designed to calculate ΔfH° and ΔfG° of PCPAZs. The relations of these thermodynamic parameters with the number and position of Cl atom substitution (NPCS) are discussed and a relative stability order of PCPAZs is theoretically proposed according to the relative magnitude of their ΔfG°. In addition, the values of molar heat capacities at constant pressure from 200 to 1000 K for PCPAZs are calculated, and the temperature dependence relations of this parameter are obtained using the least-squares method.

Abstract

Les propriétés thermodynamiques de 136 phénarzanines polychlorés (PAZPC) ont été calculées en utilisant la théorie de la densité fonctionnelle au niveau B3LYP/6-31G*. Ensuite, des réactions isodesmiques ont été conçues pour calculer ΔfH° et ΔfG° des PAZPC. Les liens entre ces paramètres thermodynamiques et le nombre et la position de la substitution de l'atome CI (NPSC) ont été discutés et un indice de stabilité relative des PAZPC a été théoriquement proposé sur la base de l'ampleur relative des ΔfG°. Par ailleurs, les valeurs des capacités thermiques molaires à pression constante, de 200 à 1000 K, ont été calculées pour les PAZPC. Les relations de dépendance de la température pour ce paramètre ont été déterminées en utilisant la méthode des moindres carrés.

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