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Rate constants for the reactions of HCCCO and NCCO radicals with molecular oxygen

✍ Scribed by Takashi Imamura; Nobuaki Washida

Publisher: John Wiley and Sons
Year: 2001
Tongue: English
Weight: 349 KB
Volume: 33
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.1040

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✦ Synopsis

Reactions of HCCCO and NCCO radicals with O 2 have been studied by a combination of pulsed laser photolysis and photoionization mass spectrometry. HCCCO was produced by 193-nm photolysis of methylpropiolate or 3-butyn-2-one, and NCCO was formed by 193-nm photolysis of acetylcyanide. The rate constants obtained at 298 Ϯ 3 K were (6.5 Ϯ 0.7) ϫ 10 Ϫ12 cm 3 molecule Ϫ1 s Ϫ1 for the HCCCO ϩ O 2 reaction, and no pressure dependence was observed between 1.5 and 16 Torr of N 2 as a bath gas. Because HCO and HCCO radicals were observed as reaction products, it was confirmed that the reaction proceeds by a two-body reaction. On the other hand, the rate constants of NCCO with O 2 depended on the total pressure and were (5.4-8.8) ϫ 10 Ϫ13 cm 3 molecule Ϫ1 s Ϫ1 for total pressures 2.0-15.5 Torr of N 2 , confirming that the reaction proceeds by a three-body process.

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