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Atmospheric chemistry of acetone: Kinetic study of the CH 3 C(O)CH 2 O 2 +NO/NO 2 reactions and decomposition of CH 3 C(O)CH 2 O 2 NO 2
Author(s) -
Sehested Jens,
Christensen Lene K.,
Nielsen Ole J.,
Bilde Merete,
Wallington Timothy J.,
Schneider William F.,
Orlando John J.,
Tyndall Geoffrey S.
Publication year - 1998
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/(sici)1097-4601(1998)30:7<475::aid-kin4>3.0.co;2-p
Subject(s) - chemistry , reaction rate constant , radical , analytical chemistry (journal) , thermal decomposition , radiolysis , atmospheric temperature range , decomposition , acetone , context (archaeology) , diluent , infrared , kinetics , nuclear chemistry , organic chemistry , thermodynamics , paleontology , physics , quantum mechanics , biology , optics
Pulse radiolysis was used to study the kinetics of the reactions of CH 3 C(O)CH 2 O 2 radicals with NO and NO 2 at 295 K. By monitoring the rate of formation and decay of NO 2 using its absorption at 400 and 450 nm the rate constants k (CH 3 C(O)CH 2 O 2 +NO)=(8±2)×10 −12 and k (CH 3 C(O)CH 2 O 2 +NO 2 )=(6.4±0.6)×10 −12 cm 3 molecule −1 s −1 were determined. Long path length Fourier transform infrared spectrometers were used to investigate the IR spectrum and thermal stability of the peroxynitrate, CH 3 C(O)CH 2 O 2 NO 2 . A value of k −6 ≈3 s −1 was determined for the rate of thermal decomposition of CH 3 C(O)CH 2 O 2 NO 2 in 700 torr total pressure of O 2 diluent at 295 K. When combined with lower temperature studies (250–275 K) a decomposition rate of k −6 =1.9×10 16 exp (−10830/ T ) s −1 is determined. Density functional theory was used to calculate the IR spectrum of CH 3 C(O)CH 2 O 2 NO 2 . Finally, the rate constants for reactions of the CH 3 C(O)CH 2 radical with NO and NO 2 were determined to be k (CH 3 C(O)CH 2 +NO)=(2.6±0.3)×10 −11 and k (CH 3 C(O)CH 2 +NO 2 )=(1.6±0.4)×10 −11 cm 3 molecule −1 s −1 . The results are discussed in the context of the atmospheric chemistry of acetone and the long range atmospheric transport of NO x . © John Wiley & Sons, Inc. Int J Chem Kinet: 30: 475–489, 1998