化工学报
化工學報
화공학보
JOURNAL OF CHEMICAL INDUSY AND ENGINEERING (CHINA)
2010年
1期
1-9
,共9页
王甫洋%陈建挺%朱维廷%李定龙
王甫洋%陳建挺%硃維廷%李定龍
왕보양%진건정%주유정%리정룡
多氯代二苯并噻吩亚砜%密度泛函理论%氯原子取代位置方法%热力学性质%相对稳定性
多氯代二苯併噻吩亞砜%密度汎函理論%氯原子取代位置方法%熱力學性質%相對穩定性
다록대이분병새분아풍%밀도범함이론%록원자취대위치방법%열역학성질%상대은정성
polychlorinated dibenzothiophenes sulfoxide%density functional theory (DFT)%method of position of Cl atom substitution%thermodynamic property%relative stability
在BHandHLYP/6-31G~*水平上对135个多氯代二苯并噻吩亚砜(PCDBTOs)系列化合物进行了全优化和振动分析计算,得到各分子在298.15 K、101.3 kPa标准状态下的热力学参数.设计等键反应,计算了PCDBTOs系列化合物的标准生成热(Δ_fH~(⊙))和标准生成自由能(Δ_fG~(⊙)).研究了热力学参数S~(⊙)与氯原子的取代位置及取代数目(N_(PCS))之间的关系,结果表明:PCDBTOs系列化合物的S~(⊙)、Δ_fH~(⊙)和Δ_fG~(⊙)与N_(PCS)之间有较好的相关性.根据异构体标准生成自由能的相对大小,从理论上求得异构体的相对稳定性.以Gaussian 03程序的输出文件为基础,采用统计热力学程序计算了PCDBTOs化合物在200～1000 K的摩尔定压热容(c_(p,m)),并用最小二乘法求得c_(p,m)与温度之间的相关方程,发现c_(p,m)与T、T~(-1)和T~(-2)之间有着很好的相关性(R~2=1.000).同时,根据分子体积推测了化合物的毒性,结果表明:PCDBTOs系列化合物中,毒性最大的异构体可能在4取代中.
在BHandHLYP/6-31G~*水平上對135箇多氯代二苯併噻吩亞砜(PCDBTOs)繫列化閤物進行瞭全優化和振動分析計算,得到各分子在298.15 K、101.3 kPa標準狀態下的熱力學參數.設計等鍵反應,計算瞭PCDBTOs繫列化閤物的標準生成熱(Δ_fH~(⊙))和標準生成自由能(Δ_fG~(⊙)).研究瞭熱力學參數S~(⊙)與氯原子的取代位置及取代數目(N_(PCS))之間的關繫,結果錶明:PCDBTOs繫列化閤物的S~(⊙)、Δ_fH~(⊙)和Δ_fG~(⊙)與N_(PCS)之間有較好的相關性.根據異構體標準生成自由能的相對大小,從理論上求得異構體的相對穩定性.以Gaussian 03程序的輸齣文件為基礎,採用統計熱力學程序計算瞭PCDBTOs化閤物在200～1000 K的摩爾定壓熱容(c_(p,m)),併用最小二乘法求得c_(p,m)與溫度之間的相關方程,髮現c_(p,m)與T、T~(-1)和T~(-2)之間有著很好的相關性(R~2=1.000).同時,根據分子體積推測瞭化閤物的毒性,結果錶明:PCDBTOs繫列化閤物中,毒性最大的異構體可能在4取代中.
재BHandHLYP/6-31G~*수평상대135개다록대이분병새분아풍(PCDBTOs)계렬화합물진행료전우화화진동분석계산,득도각분자재298.15 K、101.3 kPa표준상태하적열역학삼수.설계등건반응,계산료PCDBTOs계렬화합물적표준생성열(Δ_fH~(⊙))화표준생성자유능(Δ_fG~(⊙)).연구료열역학삼수S~(⊙)여록원자적취대위치급취대수목(N_(PCS))지간적관계,결과표명:PCDBTOs계렬화합물적S~(⊙)、Δ_fH~(⊙)화Δ_fG~(⊙)여N_(PCS)지간유교호적상관성.근거이구체표준생성자유능적상대대소,종이론상구득이구체적상대은정성.이Gaussian 03정서적수출문건위기출,채용통계열역학정서계산료PCDBTOs화합물재200～1000 K적마이정압열용(c_(p,m)),병용최소이승법구득c_(p,m)여온도지간적상관방정,발현c_(p,m)여T、T~(-1)화T~(-2)지간유착흔호적상관성(R~2=1.000).동시,근거분자체적추측료화합물적독성,결과표명:PCDBTOs계렬화합물중,독성최대적이구체가능재4취대중.
Fully optimized calculation and frequency analysis of 135 polychlorinated dibenzothiophenes sulfoxide (PCDBTOs) compounds were carried out by using density functional theory(DFT) method at the BHandHLYP/6-31G~* level and their thermodynamic parameters in the ideal gas state at 298.15 K and 101.3 kPa were obtained.The isodesmic reactions were designed to calculate standard enthalpy of formation (Δ_fH~(⊙)) and standard free energy of formation (Δ_fG~(⊙)) of PCDBTOs congeners.The relationships of these thermodynamic parameters with the number and the position of Cl atom substitution (N_(PCS)) were established.There exists good correlation between entropy (S~(⊙)),standard enthalpy of formation (Δ_fH~(⊙)),standard free energy of formation (Δ_fG~(⊙)) and N_(PCS).The stability of PCDBTOs congeners was obtained theoretically based on the relative magnitude of their Δ_fG~(⊙).The values of c_(p,m) were calculated by using statistical thermodynamic calculation program in the temperature range from 200 K to 1000 K based on Gaussian 03 output files.The relative equation between c_(p,m) and temperature was obtained by the least square method.It is found that c_(p,m) and T,T~(-1) and T~(-2) have a very good relationship (R~2=1.000).Furthermore,based on the relationship of molecular volume and toxicity,it is predicted that the TCDBTO isomers may be the most toxic among the PCDBTOs compounds.
