Theoretical and Experimental Study on the Reaction of tert-Butylamine with OH Radicals in the Atmosphere.
Theoretical and Experimental Study on the Reaction of tert-Butylamine with OH Radicals in the Atmosphere.
复制标题
DOI：
10.1021/acs.jpca.8b01862
复制
发表时间：
2018-04
期刊：
影响因子：
--
通讯作者：
Wen Tan;Liang Zhu;T. Mikoviny;C. Nielsen;A. Wisthaler;Philipp Eichler;M. Müller;B. d'Anna;Naomi J. Farren;J. Hamilton;J. Pettersson;M. Hallquist;S. Antonsen;Y. Stenstrøm
中科院分区：
文献类型：
--
作者：
Wen Tan;Liang Zhu;T. Mikoviny;C. Nielsen;A. Wisthaler;Philipp Eichler;M. Müller;B. d'Anna;Naomi J. Farren;J. Hamilton;J. Pettersson;M. Hallquist;S. Antonsen;Y. Stenstrøm
通过详细的量子化学研究和西班牙欧洲光反应器 (EUPHORE) 的实验室实验，对 OH 引发的叔丁胺 (tBA)、(CH3)3CNH2 的大气降解进行了研究。研究发现该反应主要通过氨基脱氢进行，在氮氧化物（NO x ）存在下，生成叔丁基硝胺、(CH3)3CNHNO2 和丙酮作为主要反应产物。丙酮是通过叔丁基亚硝胺 (CH3)3CNHNO 和/或其异构体叔丁基羟基二氮烯 (CH3)3CN=NOH 与 OH 自由基反应生成一氧化二氮 (N2O) 和 (CH3)3Ċ 自由基。后者转化为丙酮和甲醛。预测和观察到的少量反应产物包括甲醛、2-甲基丙烯、乙酰胺和丙-2-亚胺。 EUPHORE 室中的反应伴随着强烈的颗粒形成，这是由光化学形成的硝酸和试剂胺之间的酸碱反应引起的。硝酸叔丁胺盐具有低挥发性，298 K 时的蒸气压为 5.1 × 10-6 Pa。在 305 ± 2 K 和 1015 ± 1 hPa 下，测得叔丁胺与 OH 自由基之间的反应速率为 8.4 (±1.7) × 10-12 cm3 molecular-1 s-1。
The OH-initiated atmospheric degradation of tert-butylamine (tBA), (CH3)3CNH2, was investigated in a detailed quantum chemistry study and in laboratory experiments at the European Photoreactor (EUPHORE) in Spain. The reaction was found to mainly proceed via hydrogen abstraction from the amino group, which in the presence of nitrogen oxides (NO x), generates tert-butylnitramine, (CH3)3CNHNO2, and acetone as the main reaction products. Acetone is formed via the reaction of tert-butylnitrosamine, (CH3)3CNHNO, and/or its isomer tert-butylhydroxydiazene, (CH3)3CN═NOH, with OH radicals, which yield nitrous oxide (N2O) and the (CH3)3Ċ radical. The latter is converted to acetone and formaldehyde. Minor predicted and observed reaction products include formaldehyde, 2-methylpropene, acetamide and propan-2-imine. The reaction in the EUPHORE chamber was accompanied by strong particle formation which was induced by an acid-base reaction between photochemically formed nitric acid and the reagent amine. The tert-butylaminium nitrate salt was found to be of low volatility, with a vapor pressure of 5.1 × 10-6 Pa at 298 K. The rate of reaction between tert-butylamine and OH radicals was measured to be 8.4 (±1.7) × 10-12 cm3 molecule-1 s-1 at 305 ± 2 K and 1015 ± 1 hPa.