Atmospheric fate of nitramines: an experimental and theoretical study of the OH reactions with CH3NHNO2 and (CH3)2NNO2.
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.
Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo , P. O. Box 1033, Blindern, 0315 Oslo, Norway.
Mihayo Musabila
MM
Maguta
Marius
M
Aursnes
Arne Joakim Coldevin
AJ
Bunkan
Katie
K
Edelen
Tomáš
T
Mikoviny
Claus Jørgen
CJ
Nielsen
Yngve
Y
Stenstrøm
Yizhen
Y
Tang
Armin
A
Wisthaler
D000814:Aniline Compounds / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry*; D004123:Dimethylamines / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D008744:Methylamines / Q000737:chemistry*; D009578:Nitrobenzenes / Q000737:chemistry*; D010126:Ozone / Q000737:chemistry; D011789:Quantum Theory
D000814:Aniline Compounds; D004123:Dimethylamines; D008744:Methylamines; D009578:Nitrobenzenes; D017665:Hydroxyl Radical; C061688:N-nitromethylamine; D010126:Ozone; C015384:nitramine; C013962:dimethylnitramine