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Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase |
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| Authors: | Sarka Langer Evert Ljungstr m Thomas Ellermann Ole J Nielsen and Jens Sehested |
| Institution: | a Department of Inorganic Chemistry, University of Göteborg and Chalmers University of Technology, S-412 96, Göteborg, Sweden b National Environmental Research Institute, Frederiksborgvej 399, DK-4000, Roskilde, Denmark c Section for Chemical Reactivity, ES&T Department, Risø National Laboratory, DK-4000, Roskilde, Denmark |
| Abstract: | UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm. σR = (2.6 ± 0.4) × 10−18 cm2 molecule−1 and σRO2 = (4.1 ± 0.6) × 10−18 cm2 molecule−1 (base e). The rate constant for the self-reaction of the alkyl radicals is (2.5 ± 1.1) × 10−11 cm3 molecule−1 s−1. The rate constants for reaction of the alkyl radicals with molecular oxygen and the alkylperoxy radicals with NO and NO2 are (9.1 ± 1.5) × 10−13, (4.3 ± 1.6) × 10−12 and (1.2 ± 0.3) × 10−11 cm3 molecule−1 s−1, respectively. The rate constants given above refer to reaction at the tert-butyl side of the molecule. |
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