Atmospheric chemistry of acetone: Kinetic study of the CH3C(O)CH2O2+NO/NO2 reactions and decomposition of CH3C(O)CH2O2NO2

✍ Scribed by Jens Sehested; Lene K. Christensen; Ole J. Nielsen; Merete Bilde; Timothy J. Wallington; William F. Schneider; John J. Orlando; Geoffrey S. Tyndall

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 290 KB
• Volume: 30
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/(sici)1097-4601(1998)30:7<475::aid-kin4>3.0.co;2-p

✦ Synopsis

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 By monitoring the rate of formation and decay of NO 2 295 K. using its absorption at the rate constants 400 and 450 nm k(CH C(O)CH O ϩ NO) ϭ (8 Ϯ 3 2 2 and were de-Ϫ12 Ϫ12 3 Ϫ1 Ϫ1 2) ϫ 10 k(CH C(O)CH O ϩ NO ) ϭ (6.4 Ϯ 0.6) ϫ 10 cm molecule s 3 2 2 2 termined. 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 was determined for the rate of thermal decomposition of CH 3 C(O)CH 2 O 2 NO 2 in Ϫ1 k Ϸ 3 s Ϫ6 700 torr total pressure of O 2 diluent at When combined with lower temperature studies 295 K. a decomposition rate of is determined. Den-16 Ϫ1 (250-275 K) k ϭ 1.9 ϫ 10 exp (Ϫ10830/T) s Ϫ6 sity 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 and Ϫ11

The results are discussed in the context of the atmospheric chem-Ϫ11 3 Ϫ1 Ϫ1 10 cm molecule s . istry of acetone and the long range atmospheric transport of ᭧ John Wiley & Sons, Inc. Int NO .

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