Institute of Functional Material Chemistry, National &Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, 130024 Changchun, People's Republic of China.
School of Life Science, Northeast Normal University, 130024 Changchun, People's Republic of China.
Sci Rep. 2017 Jan 9;7:40264. doi: 10.1038/srep40264.
In this study, the mechanistic and kinetic analysis for reactions of CFOCH(CF) and CFOCFCFH with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CFOCH(CF)/CFOCD(CF) and CFOCFCFH/CFOCFCFD with OH and Cl were estimated so as to provide the theoretical estimation for future laboratory investigation. All rate constants, computed by canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT), are in reasonable agreement with the limited experimental data. Standard enthalpies of formation for the species were also calculated. Atmospheric lifetime and global warming potentials (GWPs) of the reaction species were estimated, the large lifetimes and GWPs show that the environmental impact of them cannot be ignored. The organic nitrates can be produced by the further oxidation of CFOC(•)(CF) and CFOCFCF• in the presence of O and NO. The subsequent decomposition pathways of CFOC(O•)(CF) and CFOCFCFO• radicals were studied in detail. The derived Arrhenius expressions for the rate coefficients over 230-350 K are: k = 5.00 × 10T exp(-849.73/T), k = 1.79 × 10T exp(-4262.65/T), k= 1.94 × 10 T exp(-884.26/T), and k = 9.44 × 10T exp(-913.45/T) cm molecule s.
在这项研究中，我们在 CCSD(T)//B3LYP/6-311++G(d,p)水平上对 CFOCH(CF)(CFOCH(CF))和 CFOCFCFH 与 OH 自由基和 Cl 原子的反应进行了机理和动力学分析。我们还估算了反应 CFOCH(CF)/CFOCD(CF)和 CFOCFCFH/CFOCFCFD 与 OH 和 Cl 的动力学同位素效应，为未来的实验室研究提供理论估计。通过正则变分过渡态理论 (CVT) 与小曲率隧道修正 (SCT) 计算的所有速率常数与有限的实验数据吻合良好。我们还计算了这些物种的标准生成焓。估算了反应物种的大气寿命和全球升温潜能值 (GWP)，大的寿命和 GWP 表明它们对环境的影响不容忽视。在 O 和 NO 的存在下，CFOC(•)(CF)和 CFOCFCF•可以进一步氧化生成有机硝酸盐。我们详细研究了 CFOC(O•)(CF)和 CFOCFCFO•自由基的后续分解途径。在 230-350 K 范围内得到的速率系数的 Arrhenius 表达式为：k=5.00×10T exp(-849.73/T)，k=1.79×10T exp(-4262.65/T)，k=1.94×10T exp(-884.26/T)，k=9.44×10T exp(-913.45/T)cm 分子 s。
