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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >The Energetics of the Hydrogenolysis,Dehydrohalogenation,and Hydrolysis of 4,4'-Dichloro-diphenyl-trichloroethane from ab Initio Electronic Structure Theory
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The Energetics of the Hydrogenolysis,Dehydrohalogenation,and Hydrolysis of 4,4'-Dichloro-diphenyl-trichloroethane from ab Initio Electronic Structure Theory

机译：从头算电子结构理论看4,4'-二氯-二苯基-三氯乙烷的氢解，脱氢卤化和水解能

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Electronic structure methods were used to calculate the aqueous reaction energies for hydrogenolysis,dehydrochlorination,and nucleophilic substitution by OH~- of 4,4'-DDT.Thermochemical properties DELTAH_f~o (298.15 K),S~° (298.15 K,1 bar),DELTAG_s (298.15 K,1 bar) were calculated by using ab initio electronic structure calculations,isodesmic reactions schemes,gas-phase entropy estimates,and continuum solvation models for a series of DDT type structures (p-C_6H_4Cl)_2-CH-CCl_3,(p-C_6H_4Cl)_2-CH-CCl_(2 centre dot),(p-C_6H_4Cl)_2-CH-CHC1_2,(p-C_6H_4Cl)_2-C=CCl_2,(p-C_6H_4Cl)_2-CH-CCl_2OH,(p-C_6H_4Cl)_2-CH-CCl(=O),and (p-C_6H_4-C1)_2-CH-COOH.On the basis of these thermochemical estimates,the overall aqueous reaction energetics of hydrogenolysis,dehydrochlorination,and hydrolysis of 4,4'-DDT were estimated.The results of this investigation showed that the dehydrochlorination and hydrolysis reactions have strongly favorable thermodynamics in the standard state,as well as under a wide range of pH conditions.For hydrogenolysis with the reductant aqueous Fe(II),the thermodynamics are strongly dependent on pH,and the stability region of the (p-C_6H_4C1)_2-CH-CCl_(2 centre dot)(aq)) species is a key to controlling the reactivity in hydrogenolysis.These results illustrate the use of ab initio electronic structure methods to identify the potentially important environmental degradation reactions by calculation of the reaction energetics of a potentially large number of organic compounds with aqueous species in natural waters.
机译：用电子结构方法计算了4,4'-DDT的氢解，脱氯化氢和OH〜-亲核取代的水反应能。热化学性质DELTAH_f〜o（298.15 K），S〜°（298.15 K，1 bar ），使用从头算电子结构计算，等渗反应方案，气相熵估计和一系列DDT型结构（p-C_6H_4Cl）_2-CH-的连续溶剂化模型，计算了DELTAG_s（298.15 K，1 bar） CCl_3，（p-C_6H_4Cl）_2-CH-CCl_（2个中心点），（p-C_6H_4Cl）_2-CH-CHC1_2，（p-C_6H_4Cl）_2-C = CCl_2，（p-C_6H_4Cl）_2-CH-CCl_2OH ，（p-C_6H_4Cl）_2-CH-CCl（= O）和（p-C_6H_4-C1）_2-CH-COOH。在这些热化学估算的基础上，氢解，脱氯化氢和水解的总水性反应能研究结果表明，脱氯化氢和水解反应在标准状态和宽范围内都具有非常有利的热力学。在还原性Fe（II）水溶液中进行氢解时，热力学强烈依赖于pH，并且（p-C_6H_4C1）_2-CH-CCl_（2中心点）（aq））物种的稳定性区域为这些结果说明了从头算电子结构方法的使用，该方法通过计算天然水中潜在的大量有机化合物与水性物质的反应能来确定潜在的重要环境降解反应。

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