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Atmospheric chemistry of FCO x radicals: Kinetic and mechanistic study of the FC(O)O 2 + NO 2 reaction
Author(s) -
Wallington Timothy J.,
Schneider William F.,
Møgelberg Trine E.,
Nielsen Ole J.,
Sehested Jens
Publication year - 1995
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550270410
Subject(s) - chemistry , radical , diluent , radiolysis , reaction rate constant , thermal decomposition , analytical chemistry (journal) , torr , decomposition , kinetics , atmospheric pressure , fourier transform infrared spectroscopy , context (archaeology) , atmospheric chemistry , atmospheric temperature range , chemical kinetics , ozone , nuclear chemistry , thermodynamics , organic chemistry , paleontology , physics , oceanography , quantum mechanics , geology , biology
A pulse radiolysis system was used to study the kinetics of the reaction of FC(O)O 2 radicals with NO 2 . By monitoring the rate of the decay of NO 2 using its absorption at 400 nm the reaction rate constant was determined to be (5.5 ± 0.6) × 10 −12 cm 3 molecule −1 s −1 at 296 K and 500–1000 mbar pressure of SF 6 diluent. A long path length Fourier transform infrared spectrometer was used to investigate the thermal stability of the product FC(O)O 2 NO 2 . The rate of thermal decomposition of FC(O)O 2 NO 2 was independent of the total pressure of N 2 diluent over the range 100–700 torr and was fit by the expression k −3 = 6.0 × 10 16 exp(−14150/ T ) s −1 . The results are discussed in the context of the atmospheric chemistry of FCO x radicals. © 1995 John Wiley & Sons, Inc.