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|Title:||Experimental Confirmation of the Dicarbonyl Route in the Photo-oxidation of Toluene and Benzene|
|Authors:||GOMES ALVAREZ Elena; VIIDANOJA Jyrki; MUNOZ Amalie; WIRTZ Klaus; HJORTH JENS|
|Citation:||ENVIRONMENTAL SCIENCE & TECHNOLOGY vol. 41 no. 24 p. 8362-8369|
|Publisher:||AMER CHEMICAL SOC|
|Type:||Articles in Journals|
|Abstract:||The methodology of solid phase microextraction (SPME) with O-(2,3,4,5,6)-pentafluorobenzylhydroxylamine hydrochloride (PFBHA) on-fiber derivatization for the determination of carbonyls has been applied to the photo-oxidation of benzene and toluene carried out in the EUPHORE chambers. This work focuses on the results obtained for a number of highly reactive carbonyls, crucial in the determination of branching ratios and confirmation of the carbonylic route. The observed yields and kinetic behavior were compared to simulations with the Master Chemical Mechanism model, version 3.1 (MCMv3.1). The following yields were measured in the toluene system: glyoxal, (37 ± 2)%; methylglyoxal, (37 ± 2)%; 4-oxo-2-pentenal, >(13.8 ± 1.5)%; and total butenedial, (13 ± 7)% [cis-butenedial, (6 ± 3)%; trans-butenedial, (7 ± 4)%]. For benzene, the experimental glyoxal yields were (42 ± 3) and (36 ± 2)% for the two successive experiments (September 24 and 25, 2003), (17 ± 9)% for total butenedial [(8 ± 4)% cis-butenedial and (9 ± 5)% trans-butenedial (September 24, 2003)] and (15 ± 6)% total butenedial (September 25, 2003) [(7 ± 3) and (7 ± 3)% for the cis and trans isomers, respectively]. PTR-MS estimations for butenedial also allowed the two isomers of butenedial to be distinguished, but the measurements showed signs of interference from other products. The results presented confirm the fast ring cleavage and provide further experimental confirmation of the dicarbonylic route.|
|JRC Institute:||Institute for Environment and Sustainability|
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