Atmospheric fate of nitramines: an experimental and theoretical study of the OH reactions with CH3NHNO2 and (CH3)2NNO2

J Phys Chem A. 2014 May 15;118(19):3450-62. doi: 10.1021/jp500305w. Epub 2014 May 6.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aniline Compounds / chemistry*
  • Atmosphere / chemistry*
  • Dimethylamines / chemistry*
  • Hydroxyl Radical / chemistry*
  • Methylamines / chemistry*
  • Nitrobenzenes / chemistry*
  • Ozone / chemistry
  • Quantum Theory*

Substances

  • Aniline Compounds
  • Dimethylamines
  • Methylamines
  • Nitrobenzenes
  • Hydroxyl Radical
  • N-nitromethylamine
  • Ozone
  • nitramine
  • dimethylnitramine