Journal
ATMOSPHERIC ENVIRONMENT
Volume 55, Issue -, Pages 185-189Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.atmosenv.2012.02.094
Keywords
Nitroamines; Imines; Photolysis; Atmospheric reaction
Funding
- The Research Council of Norway
- VISTA-programme [6157]
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The atmospheric reactions of alkylamino radicals, R1R2N, with O-2 and NO2 were studied by theoretical methods to elucidate the possible pathways to imine formation at the atmospheric conditions. The calculations show that all relevant routes proceed via initial additions to the nitrogen atom of the amino radical, R1R2N-NO2, R1R2N-ONO and R1R2N-OO that then may undergo dissociation via five-center-ring transition states resulting in imines and HONO or HO2. The rate coefficient for amino radical reaction with O-2 is shown to be several orders of magnitude smaller than the corresponding reaction with NO2 center dot N-nitro amines are the major product in secondary amino radical reactions with NO2. For primary amino radical reactions with NO2 the amounts of N-nitro amines and imines will depend upon pressure and chain length. Results from TDDFr studies of N-nitro and N-nitrooxy amine photo stability indicate fast photolysis of N-nitrooxy amines at atmospheric conditions. (C) 2012 Elsevier Ltd. All rights reserved.
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