Thermal decomposition of peroxyacetyl nitrate in the presence of nitric oxide
The thermal reactions occurring in mixtures containing peroxyacetyl nitrate and nitric oxide at part-per-million concentrations in synthetic air are investigated. In the presence of NO, peroxyacetylnitrate decomposes at a measurable rate at room temperature, with accompanying oxidation of NO to NO/sub 2/. The results can be explained by a mechanism involving the following reactions: CH/sub 3/COO/sub 2/NO/sub 2/ = CH/sub 3/COO/sub 2/ + NO/sub 2/ (1), CH/sub 3/COO/sub 2/ + NO/sub 2/ = CH/sub 2/COO/sub 2/NO/sub 2/ (2), and CH/sub 3/COO/sub 2/ + NO = CH/sub 3/CO/sub 2/ + NO/sub 2/ (3). The effect of variation of the NO/NO/sub 2/ ratio and the temperature on the rate of oxidation of NO to NO/sub 2/ allows evaluation of the rate constant ratio K2/k3 = 0.54 + or - 0.17 and the Arrhenius expression k1 = 10+(14.90 + or - 0.60) exp (-104.0 + or - 3.2 kj/rt)/s. Thermochemical kinetic considerations give an approximate value for the heat of formation of peroxyacetyl nitrate, (=-241 + or - 40 kj/mol) and for the absolute value of the rate constant k2 = 1.4 x 10-12 cm/sup 3//molecule/s at 300 K. The implications of these results for the behavior of peroxyacetyl nitrate in the laboratory and in the atmosphere are discussed.
- OSTI ID:
- 6541998
- Journal Information:
- Environ. Sci. Technol.; (United States), Journal Name: Environ. Sci. Technol.; (United States) Vol. 11:9; ISSN ESTHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
Atmospheric-- Chemicals Monitoring & Transport-- (-1989)
54 ENVIRONMENTAL SCIENCES
AIR POLLUTION
ATMOSPHERIC CHEMISTRY
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
ENTHALPY
ESTERS
FORMATION HEAT
KINETICS
NITRATES
NITRIC ACID ESTERS
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN DIOXIDE
NITROGEN OXIDES
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PEROXYACETYL NITRATE
PHYSICAL PROPERTIES
POLLUTION
PYROLYSIS
REACTION HEAT
REACTION KINETICS
THERMOCHEMICAL PROCESSES
THERMODYNAMIC PROPERTIES