Hubei Collaborative Innovation Center for Rare Metal Chemistry, Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Cihu Road 11, Huangshi, 435002, Hubei, People's Republic of China.
College of Foreign Languages, Hubei Normal University, Cihu Road 11, Huangshi, 435002, Hubei, People's Republic of China.
Environ Sci Pollut Res Int. 2020 May;27(13):15772-15784. doi: 10.1007/s11356-020-08100-z. Epub 2020 Feb 22.
Chlorine atoms initiated oxidation reactions are significant for the removal of typical volatile organic compounds (VOCs) in the atmosphere. The intrinsic mechanisms of CH=CHCOOH + Cl reaction have been carried out at the CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) level. There are hydrogen abstraction and C-addition pathways on potential energy surfaces. By analyses, the addition intermediates of IM1(ClCHCHCOOH) and IM2(CHCHClCOOH) are found to be dominant. The secondary reactions of IM1 and IM2 have been discussed in the presence of O, O, NO, and NO. And we have also investigated the degradation mechanisms of ClCHCHOCOOH with NO, NO, and self-reaction. Moreover, the atmospheric kinetics has been calculated by the variable reaction coordinate transition-state theory (VRC-TST). As a result, the rate constants show negative temperature and positive pressure dependence. The atmospheric lifetime and global warming potentials of acrylic acid have been calculated. Overall, the current study elucidates a new mechanism for the atmospheric reaction of chlorine atoms with acrylic acid.
氯原子引发的氧化反应对于去除大气中典型的挥发性有机化合物（VOCs）非常重要。在 CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) 水平上，对 CH=CHCOOH + Cl 反应的内在机制进行了研究。在势能表面上存在氢提取和 C-加成途径。通过分析，发现加成中间体 IM1(ClCHCHCOOH) 和 IM2(CHCHClCOOH) 占主导地位。在存在 O、O、NO 和 NO 的情况下，讨论了 IM1 和 IM2 的次级反应。我们还研究了 ClCHCHOCOOH 与 NO、NO 和自反应的降解机制。此外，还通过可变反应坐标过渡态理论（VRC-TST）计算了大气动力学。结果表明，速率常数表现出负温度和正压力依赖性。计算了丙烯酸的大气寿命和全球变暖潜能值。总的来说，本研究阐明了氯原子与丙烯酸在大气中的反应的新机制。
