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Kinetics and mechanisms for the reaction of hydroxyl radicals with trifluoroacetic acid under atmospheric conditions

✍ Scribed by Sinéad Carr; Jack J. Treacy; Howard W. Sidebottom; Richenda K. Connell; Carlos E. Canosa-Mas; Richard P. Wayne; James Franklin

Publisher
Elsevier Science
Year
1994
Tongue
English
Weight
619 KB
Volume
227
Category
Article
ISSN
0009-2614

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✦ Synopsis

The rate constant for the gas-phase reaction of the hydroxyl radical with trifluoroacetic acid has been determined over the temperature range 283-323 K using a relative rate technique. The results provide a value of k( OH+CF,C(O)OH) = 2.O~lO-*~exp(-l46~500/T)cm~molecule~'s-'basedonk(OH+C~H,)=7.8~lO~'~exp(-l020fl00/T)cm~molecule~' s-l for the rate constant of the reference reaction. The OH-radical initiated oxidation of CF,C(O)OH was investigated at 298 K in oxygen at 1 atm total pressure using Fourier-transform infrared spectroscopy. The major carbon-containing products were C(O)F,, CF303CF3 and CO*, suggesting that the dominant reaction channel for loss of the CF3C(0)0 radical, formed by hydrogen atom abstraction, is carbon-carbon bond cleavage. The results indicate that the gas-phase reaction of OH radicals with trifluoroacetic acid may provide a sink for this compound in the troposphere that cannot be neglected.

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