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Mechanistic and kinetics study on the reaction of CF3CBrCH2 with OH: A theoretical study
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2020-07-09 , DOI: 10.1002/poc.4079
Yunju Zhang 1 , Yuxi Sun 1
Affiliation  

Quantum chemical method (CCSD(T)/cc‐pVTZ//M06‐2X/6‐311++G(d,p)) is employed to research the CF3CBrCH2 + OH reaction. The results indicate that the reaction takes place through the interaction of the oxygen atom of the OH radical with the middle C and terminal C atom of CF3CBrCH2 generating adduct IM1 (CF3CBrCH2OH) and IM2 (CF3CBrOHCH2), respectively, and then further dissociation or rearrangement to many products. The rate constants have been computed at 10−10 to 1010 Torr and 200–3000 K by RRKM theory for various product pathways. The results show that at 200–800 K, the rate constant for the production of IM1 (CF3CBrCH2OH) by collisional deactivation is dominant; at high temperatures, the production of P1 (CF3CBrCHOH + H) becomes predominate. The predicted data for CF3CBrCH2 + OH agree closely with available experimental value. The total rate constants are independent on pressure and dependent on temperature. The rate equation can be fitted as k(T) = 1.77 × 10 −7T−0.65exp(−4518.77/T) at 200–300 K, 30 Torr of Ar. The atmospheric lifetime of CF3CBrCH2 in OH is around 2.77 days. TD‐DFT computations imply that IM1, IM2, IM3, IM4, IM5, and IM6 will photolyze under the sunlight.

中文翻译:

CF3CBrCH2与OH反应的机理和动力学研究:理论研究

量子化学方法(CCSD(T)/ CC-pVTZ // M06-2X / 6-311 ++ G(d,ρ))被用来研究对CF 3 CBrCH 2 + OH反应。结果表明,反应发生通过自由基与CF的中央C和终端C原子的OH的氧原子的相互作用3 CBrCH 2生成加合物IM1(CF 3 CBrCH 2 OH)和IM2(CF 3 CBrOHCH 2),然后进一步分解或重排为许多产品。速率常数已计算为10 -10至10 10根据RRKM理论,Torr和200–3000 K适用于各种产品路径。结果表明,在200–800 K时,碰撞失活产生IM1(CF 3 CBrCH 2 OH)的速率常数占优势;在高温下,P1(CF 3 CBrCHOH + H)的产生占主导地位。对于CF预测数据3 CBrCH 2 + OH与实验值紧密一致。总速率常数与压力无关,与温度无关。速率方程可以拟合为kT)= 1.77×10 -7 T -0.65 exp(-4518.77 / T)在200–300 K,30 Torr的Ar。CF的大气寿命3 CBrCH 2中OH是围绕2.77天。TD-DFT计算表明IM1,IM2,IM3,IM4,IM5和IM6将在阳光下发生光解。
更新日期:2020-09-11
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