模拟大气条件下由 OH 引发的乙二胺(NH2CH2CH2NH2)降解的实验和理论研究。第 1 部分:乙二胺 + OH 气相反应动力学

IF 2.9 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Tomas Mikoviny, Claus J. Nielsen*, Armin Wisthaler and Liang Zhu, 
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引用次数: 0

摘要

基于CCSD(T*)-F12a/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ量子化学结果,在室外大型大气模拟室内研究了自然光照条件下乙二胺(NH2CH2CH2NH2)与OH自由基的反应。在308±3 K和1013±3 hPa条件下,采用在线PTR-ToF-MS检测相对速率实验确定OH速率系数为kOH =(2.8±0.8)× 10-10 cm3 - 1 s-1。理论研究包括乙二胺的构象图,显示了反应动力学建模中要考虑的9种构象,CCSD(T*)-F12a/aug-cc-pVTZ优化的几何形状,以及所有构象的振动非调和性计算结果。通过主方程计算得到了OH自由基与9种乙二胺构象的反应速率系数,表明反应动力学受反应前加合物的形成和紧密过渡态的控制,得到了玻尔兹曼构象加权速率系数kOH = 2.9 × 10-10 cm3分子- 1 s-1,并且在298 K和1013 hPa时h -从NH2和CH2基团中抽离的分支为1:1。在大气条件下,计算出的速率系数与温度呈负相关,与压力的变化可以忽略不计。理论动力学数据与实验结果一致,200-400 K区域的速率系数可近似为修正的Arrhenius表达式K (T) = 1.23 × 10-10 × (T/298)0.6 × exp(249 K/T) cm3分子- 1 s-1。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Experimental and Theoretical Study of the OH-Initiated Degradation of Ethylenediamine (NH2CH2CH2NH2) under Simulated Atmospheric Conditions. Part 1: Kinetics of the Ethylenediamine + OH Gas Phase Reaction

The ethylenediamine (NH2CH2CH2NH2) reaction with OH radicals was studied under natural sunlight conditions in a large outdoor atmospheric simulation chamber and in theoretical calculations based on CCSD(T*)-F12a/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ quantum chemistry results. The OH rate coefficient was determined in relative rate experiments employing online PTR-ToF-MS detection to be kOH = (2.8 ± 0.8) × 10–10 cm3 molecule–1 s–1 at 308 ± 3 K and 1013 ± 3 hPa. The theoretical study includes a conformational mapping of ethylenediamine showing nine conformers to be considered in reaction kinetics modeling, CCSD(T*)-F12a/aug-cc-pVTZ optimized geometries, and results from vibrational anharmonicity calculations for all conformers. The rate coefficients for the OH radical reaction with each of the nine ethylenediamine conformers were obtained in master equation calculations showing the kinetics being governed by both the formation of prereaction adducts and by tight transition states giving a Boltzmann conformer weighted rate coefficient kOH = 2.9 × 10–10 cm3 molecule–1 s–1, and a 1:1 branching between H-abstraction from the NH2 and CH2 groups at 298 K and 1013 hPa. The calculated rate coefficient shows a negative temperature dependence and a negligible variation with pressure under atmospheric conditions. The theoretical kinetics data were aligned to the experimental result, and the rate coefficient in the 200–400 K region can be approximated by a modified Arrhenius expression k(T) = 1.23 × 10–10 × (T/298)0.6 × exp(249 K/T) cm3 molecule–1 s–1.

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来源期刊
ACS Earth and Space Chemistry
ACS Earth and Space Chemistry Earth and Planetary Sciences-Geochemistry and Petrology
CiteScore
5.30
自引率
11.80%
发文量
249
期刊介绍: The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.
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