Maguta Mihayo Musabila, Aursnes Marius, Bunkan Arne Joakim Coldevin, Edelen Katie, Mikoviny Tomáš, Nielsen Claus Jørgen, Stenstrøm Yngve, Tang Yizhen, Wisthaler Armin
Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo , P. O. Box 1033, Blindern, 0315 Oslo, Norway.
J Phys Chem A. 2014 May 15;118(19):3450-62. doi: 10.1021/jp500305w. Epub 2014 May 6.
The rates of CH3NHNO2 and (CH3)2NNO2 reaction with OH radicals were determined relative to CH3OCH3 and CH3OH at 298 ± 2 K and 1013 ± 10 hPa in purified air by long path FTIR spectroscopy, and the rate coefficients were determined to be k(OH+CH3NHNO2) = (9.5 ± 1.9) × 10(-13) and k(OH+(CH3)2NNO2) = (3.5 ± 0.7) × 10(-12) (2σ) cm(3) molecule(-1) s(-1). Ozone was found to react very slowly with the two nitramines, k(O3+nitramine) < 10(-21) cm(3) molecule(-1) s(-1). Product formation in the photo-oxidation of CH3NHNO2 and (CH3)2NNO2 was studied by FTIR, PTR-ToF-MS, and quantum chemistry calculations; the major products in the OH-initiated degradation are the corresponding imines, CH2═NH and CH3N═CH2, and N-nitro amides, CHONHNO2 and CHON(CH3)NO2. Atmospheric degradation mechanisms are presented.
在298±2 K和1013±10 hPa的纯净空气中，通过长程傅里叶变换红外光谱法，相对于甲醚和甲醇测定了CH3NHNO2和(CH3)2NNO2与OH自由基的反应速率，确定速率系数为k(OH + CH3NHNO2) = (9.5±1.9)×10(-13)和k(OH + (CH3)2NNO2) = (3.5±0.7)×10(-12)(2σ) cm(3) molecule(-1) s(-1)。发现臭氧与这两种硝胺反应非常缓慢，k(O3 + 硝胺) < 10(-21) cm(3) molecule(-1) s(-1)。通过傅里叶变换红外光谱、质子转移反应飞行时间质谱和量子化学计算研究了CH3NHNO2和(CH3)2NNO2光氧化过程中的产物形成；OH引发降解的主要产物是相应的亚胺，CH2═NH和CH3N═CH2，以及N-硝基酰胺，CHONHNO2和CHON(CH3)NO2。给出了大气降解机制。
