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N-nitration of secondary aliphatic amines in the particle phase
Tianzeng Chen1, Yanli Ge2, Yongchun Liu3
1State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China.
Abstract:
Amines are frequently detected in atmospheric particles and are internally mixed with other particle-phase components. However, research on the further reactions of amine with reactive species after entering the particle phase is still limited. This study investigated the nitration reaction process of particulate dimethylamine (DMA), formed via a substitution reaction between DMA and (NH4)2SO4, with NOx. In situ attenuated total reflectance-infrared Fourier transform spectroscopy (in situ ATR-FTIR) and proton transfer reaction mass spectroscopy (PTR-MS), as well as DFT methods at the B3LYP level using the 6-311++G (d, p) basis set, were mainly used to confirm the formation of nitramine and nitrosamine in the nitration/nitrosation process of DMA. A hydrogen-bonding intermediate ([(CH3)2N⋯HONO]) is initially formed when particulate DMA reacts with NO2 followed by aminyl radical formation, and then nitr- and nitros-amine form through addition reactions with NO2 and NO, respectively. The dimer of NO2 (i.e., N2O4) and the product of NO and NO2 (i.e., N2O3) can also react with DMA to attack the lone pair electrons on the central N atom of DMA to finally form nitr- and nitros-amine. This study helps reveal the nitration reaction mechanism of organic amines in the particle phase. It also aids in understanding the process of nitrogen cycling in the atmosphere.
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