当前位置：
X-MOL 学术
›
J. Phys. Chem. A
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Cl Atom-Initiated Photo-Oxidation Reactions of Vinyl Trifluoroacetate and Allyl Trifluoroacetate in Tropospheric Conditions
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-03-10 , DOI: 10.1021/acs.jpca.9b11166 Revathy Kaipara 1 , B. Rajakumar 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-03-10 , DOI: 10.1021/acs.jpca.9b11166 Revathy Kaipara 1 , B. Rajakumar 1
Affiliation
|
Relative rate (RR) technique coupled with gas chromatography (GC) was used to investigate the kinetics of the reactions of two hydrofluoroesters (allyl trifluoroacetate (CF3C(O)OCH2CH═CH2, ATFA) and vinyl trifluoroacetate (CF3C(O)OCH═CH2, VTFA)) with Cl atoms between 268 and 363 K and at 760 Torr of N2 (or air). The temperature-dependent Arrhenius expressions for the title reactions were obtained to be k268–363KVTFA+Cl = [(7.83 ± 2.26) × 10–12 exp((974 ± 89)/T)] cm3 molecule–1 s–1 and k268–363KATFA+Cl = [(9.03 ± 1.92) × 10−12 exp((883 ± 65)/T)] cm3 molecule–1 s–1, respectively. A negative temperature dependency was observed for both the reactions. In addition to this, the kinetics of the studied reactions was evaluated computationally at the CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) level of theory in the temperature range of 200–400 K using canonical variational transition (CVT) state theory in conjunction with small curvature tunneling (SCT) corrections and interpolated single point energy (ISPE) methods. The product analysis of the reactions of VTFA and ATFA with Cl atoms in the presence of O2 was also investigated using gas chromatography–mass spectrometry (GC-MS) and gas chromatography–infrared spectroscopy (GC-IR). The plausible oxidation mechanism of the title reactions was proposed based on the product analyses. Further, to comprehend the impact of these molecules on the troposphere, atmospheric lifetimes, lifetime-corrected radiative forcing (RF), and global warming potential (GWP) were estimated and are presented in this manuscript.
中文翻译：
对流层中三氟乙酸乙烯酯和三氟乙酸烯丙酯的Cl原子引发的光氧化反应
相对速率（RR）技术与气相色谱法（GC）用于研究2个hydrofluoroesters（烯丙基三氟乙酸盐（CF的反应的动力学3）C（O OCH 2 CH = CH 2，ATFA）和乙烯基三氟乙酸盐（CF 3 C（O）OCH ＝ CH 2，VTFA）），其中Cl原子介于268和363 K之间，N 2（或空气）为760 Torr 。标题反应的温度依赖性阿伦尼乌斯表达式为k 268–363K VTFA + Cl = [（7.83±2.26）×10 –12 exp（（974±89）/ T）] cm 3分子–1 s – 1和k268–363K ATFA + Cl = [（9.03±1.92）×10 -12 exp（（883±65）/ T）] cm 3分子–1 s –1。两种反应均观察到负温度依赖性。除此之外，在200–400的温度范围内，以CCSD（T）/ cc-pVTZ // MP2 / 6-311 ++ G（d，p）的理论水平对所研究反应的动力学进行了计算评估。 K使用规范变分过渡（CVT）状态理论结合小曲率隧穿（SCT）校正和内插单点能量（ISPE）方法。O 2存在下VTFA和ATFA与Cl原子反应的产物分析还使用气相色谱-质谱（GC-MS）和气相色谱-红外光谱（GC-IR）进行了研究。在产物分析的基础上，提出了标题反应的合理氧化机理。此外，为了理解这些分子对流层的影响，估算了大气寿命，寿命校正的辐射强迫（RF）和全球变暖潜能（GWP），并在本手稿中进行了介绍。
更新日期：2020-03-10
中文翻译：
对流层中三氟乙酸乙烯酯和三氟乙酸烯丙酯的Cl原子引发的光氧化反应
相对速率（RR）技术与气相色谱法（GC）用于研究2个hydrofluoroesters（烯丙基三氟乙酸盐（CF的反应的动力学3）C（O OCH 2 CH = CH 2，ATFA）和乙烯基三氟乙酸盐（CF 3 C（O）OCH ＝ CH 2，VTFA）），其中Cl原子介于268和363 K之间，N 2（或空气）为760 Torr 。标题反应的温度依赖性阿伦尼乌斯表达式为k 268–363K VTFA + Cl = [（7.83±2.26）×10 –12 exp（（974±89）/ T）] cm 3分子–1 s – 1和k268–363K ATFA + Cl = [（9.03±1.92）×10 -12 exp（（883±65）/ T）] cm 3分子–1 s –1。两种反应均观察到负温度依赖性。除此之外，在200–400的温度范围内，以CCSD（T）/ cc-pVTZ // MP2 / 6-311 ++ G（d，p）的理论水平对所研究反应的动力学进行了计算评估。 K使用规范变分过渡（CVT）状态理论结合小曲率隧穿（SCT）校正和内插单点能量（ISPE）方法。O 2存在下VTFA和ATFA与Cl原子反应的产物分析还使用气相色谱-质谱（GC-MS）和气相色谱-红外光谱（GC-IR）进行了研究。在产物分析的基础上，提出了标题反应的合理氧化机理。此外，为了理解这些分子对流层的影响，估算了大气寿命，寿命校正的辐射强迫（RF）和全球变暖潜能（GWP），并在本手稿中进行了介绍。
京公网安备 11010802027423号