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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Investigation on the Mechanism and Kinetics of Atmospheric Reaction of Methyldichloroacetate with Hydroxyl Radical
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Theoretical Investigation on the Mechanism and Kinetics of Atmospheric Reaction of Methyldichloroacetate with Hydroxyl Radical

机译：甲基二氯乙酸羟基乙酸乙酯大气反应机理和动力学的理论研究

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The atmospheric reaction of methyldichlor-oacetate (MDCA) with OH radical is studied using electronic structure calculations. Five different pathways were considered for the initial reactions, which results in the formation of alkyl radical of MDCA along with H2O, HOCl, and CH3O circle. Among the five pathways studied, the alpha-carbon atom (-CHCl(2)site) H atom abstraction reaction, which leads to the formation of the alkyl radical intermediate (CCl2C)-C-circle(O)- OCH3 (I1) is found to be more favorable with an energy barrier of 7.3 kcal/mol, and Cl-atom abstraction reaction is having high energy barrier of 21.3 kcal/mol at M06-2X/6-311++G(2df,2p) level. The calculated thermochemical parameters show that except Cl-atom abstraction channel the other initial reaction channels are highly exothermic. The rate constant is calculated for the initial H atom abstraction reactions using canonical variational transition state theory over the temperature range of 278 to 350 K. The Arrhenius plot shows positive temperature dependence for both the reactions. The results from the calculated thermochemical parameters and rate constants show that the formation of the alkyl radical intermediate (I1) is more favorable with the rate constant of 2.07 X 10(-13) cm(3) molecule(-1) s(-1) at 298 K. The calculated atmospheric lifetime of MDCA is 28 days at normal atmospheric OH concentration. The results obtained from secondary reactions show that the major product formed from the oxidation chemistry of MDCA is methyl-2-chloro-2-oxoacetate (or) methyl oxalyl chloride.
机译：使用电子结构计算研究了甲基二氯丙酯（MDCA）与OH基团的大气反应。考虑了初始反应的五种不同的途径，这导致MDCA的烷基与H2O，HOCl和CH 3 O圈形成。在研究的五种途径中，α-碳原子（-CHCl（2）位点）H原子抽取反应，这导致形成烷基的中间体（CCL2C）-C圆圈（O） - OCH3（I1）是发现对7.3kcal / mol的能量屏障更有利，CL-原子抽象反应在M06-2X / 6-311 ++ g（2dF，2p）水平下具有21.3kcal / mol的高能量屏障。计算出的热化学参数表明除了CL-Atom抽象信道之外，其他初始反应通道是高度放热的。在278至350k的温度范围内使用规范变差转换状态理论计算初始H原子抽象反应的速率常数。Arhenius图显示了对反应的正温度依赖性。计算出的热化学参数和速率常数的结果表明，烷基基团中间体（I1）的形成更有利于2.07×10（-13）cm（3）分子（-1）分子（-1）（-1） ）298 K. MDCA的计算出的大气寿命在正常大气oh浓度下28天。从二次反应获得的结果表明，由MDCA的氧化化学形成的主要产物是甲基-2-氯-2-氧乙酸甲酯（或）甲氧基氯。

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