Use of cw-CRDS for studying the atmospheric oxidation of acetic acid in a simulation chamber

The coupling between cavity ring-down spectroscopy (CRDS) and an environmental chamber in the investigation of photo-induced reaction mechanisms is demonstrated for the first time.The development of the CRDS device and the corresponding analytical performances are presented. The first application is devoted to the investigation of the branching ratio of the •OH radical reaction of CH3C(O)OH and CH3C(O)OD under tropospheric conditions. An environmental chamber coupled to two complementary detection systems is used: gas chromatography with FTIR spectroscopy for quantitative detection of acetic acid; CRDS for quantitative detection of CO2. Investigation of the reaction kinetics of •OH+CH3C(O)OH gives a rate constant of (6.5±0.5)×10-13 cm3 molecule-1 s-1 (296 K) and shows good agreement with literature data. The product study indicates that the H-abstraction channel from the acid group is the dominant pathway with a branching ratio of (78±13)%, whereas the corresponding D-abstraction channel in the •OH+CH3C(O)OD reaction represents only (36±7)%. This result could be attributed to a strong kinetic isotope effect. Glyoxylic acid has also been detected for the first time as by-product.These results illustrate the high interest of the CRDS technique in the investigation of atmospheric relevant problems.

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