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Rate constants for the gas phase reaction of OH radicals with peroxyacetyl nitrate (PAN) at 273 and 297 K
Author(s) -
Wallington Timothy J.,
Atkinson Roger,
Winer Arthur M.
Publication year - 1984
Publication title -
geophysical research letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.007
H-Index - 273
eISSN - 1944-8007
pISSN - 0094-8276
DOI - 10.1029/gl011i009p00861
Subject(s) - peroxyacetyl nitrate , radical , reaction rate constant , chemistry , torr , troposphere , photochemistry , nitrate , flash photolysis , gas phase , photodissociation , analytical chemistry (journal) , thermodynamics , combustion , organic chemistry , meteorology , physics , kinetics , nox , quantum mechanics
Recently, peroxyacetyl nitrate (PAN) has been postulated to be a potential tropospheric reservoir of oxides of nitrogen, and to be important in their long‐range transport. To better assess its atmospheric chemistry, absolute rate constants for the reaction of OH radicals with peroxyacetyl nitrate (PAN) have been determined using a flash photolysis resonance fluorescence technique. Rate constants of (1.13 ± 0.06) × 10 −13 cm³ molecule −1 s −1 and (1.37 ± 0.05) × 10 −13 cm³ molecule −1 s −1 , independent of total pressure over the range 25‐100 torr of argon, were determined at 273 ± 2 and 297 ± 2 K, respectively. (The errors limits represent two standard deviations; systematic errors could contribute an additional ∼10% uncertainty.) These rate constants imply that reaction with the OH radical is the most important removal process for PAN in the upper troposphere.