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Kinetic and Mechanistic Investigation for the Gas-Phase Tropospheric Photo-oxidation Reactions of 2,2,2-Trifluoroethyl Acrylate with OH Radicals and Cl Atoms
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-03-18 , DOI: 10.1021/acs.jpca.9b10009 Avinash Kumar 1 , Balla Rajakumar 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-03-18 , DOI: 10.1021/acs.jpca.9b10009 Avinash Kumar 1 , Balla Rajakumar 1
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The photo-oxidation of 2,2,2-trifluoroethyl acrylate (TFEA) (CH2CHC(O)OCH2CF3) initiated by OH radicals and Cl atoms was investigated in tropospheric conditions using both experimental and computational methods. The kinetic measurements were carried out in the temperature range of 268–363 K using the relative rate method. The rate coefficients for the reaction of OH radicals with TFEA were measured relative to diethyl ether, ethylene, and acetaldehyde. The rate coefficients for the reaction of Cl atoms with TFEA were measured relative to propylene and ethylene. The rate coefficients for the reaction of TFEA with OH radicals and Cl atoms at 298 K were experimentally measured to be kR1exp – 298 K = (1.41 ± 0.31) × 10–11 cm3 molecule–1 s–1 and kR2exp – 298 K = (2.37 ± 0.50) × 10–10 cm3 molecule–1 s–1, respectively. The deduced temperature-dependent Arrhenius expressions for the reactions of OH radicals and Cl atoms with TFEA are kR1exp – (268 – 363 K) = (9.82 ± 1.37) × 10–12 exp. [(812 ± 152)/T] cm3 molecule–1 s–1 and kR2exp – (268 – 363 K) = (1.25 ± 0.17) × 10–11 exp. [(862 ± 85)/T] cm3 molecule–1 s–1, respectively. To complement our experimental results, computational calculations were performed at CCSD(T)/cc-pVDZ//M062X/6-31+G(d,p) and CCSD(T)/cc-pVDZ//MP2/6-311+G(d,p) levels of theory, respectively, in combination with canonical variational transition-state theory (CVT) with small curvature tunneling (SCT) over the temperature range of 200–400 K. Furthermore, the degradation mechanisms initiated by OH radicals and Cl atoms were proposed for the titled reactions based on the qualitative analysis of the products in gas chromatography–mass spectrometry (GC–MS) and gas chromatography–infrared spectroscopy (GC–IR). Atmospheric implications, thermochemistry, and branching ratios for the titled reactions are discussed in detail in the paper.
中文翻译：
2,2,2-三氟乙基丙烯酸酯与OH自由基和Cl原子气相对流层光氧化反应的动力学和机理研究
在对流层条件下，使用实验和计算方法研究了由OH自由基和Cl原子引发的丙烯酸2,2,2-三氟乙基丙烯酸酯（TFEA）（CH 2 CHC（O）OCH 2 CF 3）的光氧化。使用相对速率法在268–363 K的温度范围内进行了动力学测量。相对于乙醚，乙烯和乙醛，测量了OH自由基与TFEA反应的速率系数。相对于丙烯和乙烯，测量了Cl原子与TFEA反应的速率系数。实验测得TFEA与OH自由基和Cl原子在298 K下反应的速率系数为k R1 exp – 298 K=（1.41±0.31）×10 –11 cm 3分子–1 s –1，k R2 exp – 298 K =（2.37±0.50）×10 –10 cm 3分子–1 s –1。推导的OH自由基和Cl原子与TFEA反应的温度依赖性Arrhenius表达式为k R1 exp –（268 – 363 K） =（9.82±1.37）×10 –12 exp。[（812±152）/ T ] cm 3分子–1 s –1和k R2 exp –（268 – 363 K）=（1.25±0.17）×10 –11 exp [（862±85）/ T ] cm 3分子–1 s –1， 分别。为了补充我们的实验结果，对CCSD（T）/ cc-pVDZ // M062X / 6-31 + G（d，p）和CCSD（T）/ cc-pVDZ // MP2 / 6-311 +进行了计算G（d，p）的理论水平，分别结合在200–400 K的温度范围内具有小曲率隧穿（SCT）的规范变分过渡态理论（CVT）。此外，OH自由基引发的降解机理根据气相色谱-质谱（GC-MS）和气相色谱-红外光谱（GC-IR）中产物的定性分析，提出了C和Cl原子用于标题反应。本文详细讨论了标题反应的大气影响，热化学和支化比。
更新日期：2020-03-19
中文翻译：
2,2,2-三氟乙基丙烯酸酯与OH自由基和Cl原子气相对流层光氧化反应的动力学和机理研究
在对流层条件下，使用实验和计算方法研究了由OH自由基和Cl原子引发的丙烯酸2,2,2-三氟乙基丙烯酸酯（TFEA）（CH 2 CHC（O）OCH 2 CF 3）的光氧化。使用相对速率法在268–363 K的温度范围内进行了动力学测量。相对于乙醚，乙烯和乙醛，测量了OH自由基与TFEA反应的速率系数。相对于丙烯和乙烯，测量了Cl原子与TFEA反应的速率系数。实验测得TFEA与OH自由基和Cl原子在298 K下反应的速率系数为k R1 exp – 298 K=（1.41±0.31）×10 –11 cm 3分子–1 s –1，k R2 exp – 298 K =（2.37±0.50）×10 –10 cm 3分子–1 s –1。推导的OH自由基和Cl原子与TFEA反应的温度依赖性Arrhenius表达式为k R1 exp –（268 – 363 K） =（9.82±1.37）×10 –12 exp。[（812±152）/ T ] cm 3分子–1 s –1和k R2 exp –（268 – 363 K）=（1.25±0.17）×10 –11 exp [（862±85）/ T ] cm 3分子–1 s –1， 分别。为了补充我们的实验结果，对CCSD（T）/ cc-pVDZ // M062X / 6-31 + G（d，p）和CCSD（T）/ cc-pVDZ // MP2 / 6-311 +进行了计算G（d，p）的理论水平，分别结合在200–400 K的温度范围内具有小曲率隧穿（SCT）的规范变分过渡态理论（CVT）。此外，OH自由基引发的降解机理根据气相色谱-质谱（GC-MS）和气相色谱-红外光谱（GC-IR）中产物的定性分析，提出了C和Cl原子用于标题反应。本文详细讨论了标题反应的大气影响，热化学和支化比。
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