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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Understanding the Atmospheric Oxidation of HFE-7500 (C3F7CF(OC2H5)CF(CF3)(2)) Initiated by CI Atom and NO3 Radical from Theory
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Understanding the Atmospheric Oxidation of HFE-7500 (C3F7CF(OC2H5)CF(CF3)(2)) Initiated by CI Atom and NO3 Radical from Theory

机译：了解由CI原子和No3从理论引发的HFE-7500（C3F7CF（OC2H5）CF（CF3）（2））的大气氧化

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摘要

Kinetics and mechanistic pathways for atmospheric oxidation of HFE-7500 (n-C3F7CF(OCH2CH3)CF(CF3)(2)) initiated by Cl atom and NO3 radical have been studied using density functional theory. Oxidative degradation pathways facilitated by H-abstraction from the -OCH2 or -CH3 groups in HFE-7500 have been considered. It has been shown that H-abstraction from the alpha-site (-OCH2) is favored over other reaction pathways. The rate constants were computed employing transition-state theory and canonical variation transition-state theory incorporating small curvature tunnelling correction, over the temperature range of 250-450 K at atmospheric pressure. Calculated rate constants at 298 K and 1 atm compare well with earlier experiments. Temperature dependence of the rate constants and branching ratios for these pathways contributing to overall reaction are described. It has been shown that the rate constants over the studied temperature range was found to fit well to the modified Arrhenius equation (in cm(3) molecule(-1) s(-1)) k(Cl) = 1.10 x 10(-14) T-0.04 exp(-69.87 +/- 1.41/T) and k(NO3) = 7.66 x 10(-26) T-3.30 exp(596.40 +/- 1.22/T). Standard enthalpies of formation for the reactant (C3F7CF(OCH2CH3)CF(CF3)(2)) and the products [C3F7CF((OCHCH3)-H-center dot)CF(CF3)(2) and C3F7CF((OCH2CH2)-H-center dot)CF(CF3)(2)] during H-abstraction are derived using the isodesmic approach. Atmospheric implications of the titled molecule are presented.
机译：使用密度函数理论研究了由CL原子和NO3自由基引发的HFE-7500（N-C3F7CF（OCH2CH3）CF（CF3）（2））的大气氧化的动力学和机械途径。考虑了通过HFE-7500中的HFE-7500中的H-Abstach促进的氧化降解途径。已经证明，来自α-位点（-OCH2）的H-抽象在其他反应途径上受到青睐。计算使用过渡状态理论和规范变化转换状态理论的速率常数，其含有小曲率隧道校正，在大气压下250-450k的温度范围内。计算出的速率常数在298 k和1个ATM中与早期的实验相比很好。描述了对这些途径的速率常数和支化比的温度依赖性。已经表明，发现所研究的温度范围内的速率常数适合于改性的Arhenius方程（以cm（3）分子（-1）s（-1））k（cl）= 1.10 x 10（ - 14）T-0.04 exp（-69.87 +/- 1.41 / t）和K（NO3）= 7.66 x 10（-26）T-3.30 exp（596.40 +/- 1.22 / t）。反应物形成标准焓（C3F7CF（OCH2CH3）CF（CF 3）（2））和产物[C3F7CF（（OCHCH3）-H中心点）CF（CF3）（2）和C3F7CF（（OCH2CH2）-H -Center点）使用ISODSMIC方法导出H-Abstraction期间的CF（CF3）（2）]。提出了标题分子的大气意义。

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