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• W2067465718 abstract "The rate constant of the reaction of Cl atoms with methacrolein (k1) has been measured relative to that of Cl with propane (k2) or cyclohexane (k6) at ambient temperature and pressures varying from 1−950 Torr. The experiments were carried out by irradiation (350 nm) of Cl2/methacrolein/propane or cyclohexane mixtures in N2 or N2/O2 diluent at ambient temperature in a spherical (500 cm3) Pyrex reactor (GC/FID analyses) or a 140 L FTIR smog chamber. The measured relative rate constant ratios in the GC/FID experiments were k1/k2 = 1.464 ± 0.015(2σ) in N2 and k1/k2 = 1.68 ± 0.03(2σ) in N2/O2 diluent (O2 > 20 000 ppm). No pressure dependence was observed over the range studied in N2 (120−950 Torr) using the GC/FID. In the FTIR/smog chamber experiments values of k1/k6 = 0.645 ± 0.032, 0.626 ± 0.037, 0.586 ± 0.026, and 0.479 ± 0.024 were measured in 700, 100, 10, and 1 Torr, respectively, of N2 diluent. Using k2 = (1.4 ± 0.2) × 10−10 and k6 = (3.3 ± 0.5) × 10−10 high pressure limiting rate constants of k1 = (2.05 ± 0.3) × 10−10 [GC/FID] and (2.13 ± 0.34) × 10−10 [FTIR] cm3 molecule−1 s−1 were determined. In experiments using the GC/FID reactor with N2 diluent the following products (molar yields) were observed: 2,3-dichloro-2-methylpropanal [(47.2 ± 8)% excluding error in calibration]; methacryloyl chloride [(22.9 ± 2)%]; and 2-chloromethylacrolein [(2.3 ± 0.8)%]. Addition of 200 ppm O2 (with Cl2 = 5000 ppm) resulted in a sharp reduction of the 2,3-dichloro-2-methylpropanal yield (to ∼2%) with an accompanying appearance of chloroacetone [yield = (55 ± 7)% decreasing to (44 ± 7)% in air diluent]. The methacryloyl chloride yield was 23% for [O2]/[Cl2] ratios from 0 to 0.2 but decreased to near zero as the O2/Cl2 ratio was increased to ∼400. The variation in methacryloyl chloride yield with the O2/Cl2 ratio in the initial mixture allowed an approximate measurement of the rate constant for the reaction of the methacryloyl radical with O2 relative to that with Cl2 (kO2/kCl2 = 0.066 ± 0.02). In experiments using the FTIR reactor in 700 Torr of N2 diluent, methacryloyl chloride [(26 ± 3)%] and HCl [(27 ± 3)%] were observed as products. In 700 Torr of air diluent, the observed products were: chloroacetone [(44 ± 5)%], CO2 [(27 ± 3)%], HCl [(21 ± 3)%], and HCHO [(14 ± 2)%], and CH3C(O)CH2OH (3−4%). The observation of CH3C(O)CH2OH indicates the presence of OH radicals in the system. At atmospheric pressure and 297 K, the title reaction proceeds [(24.5 ± 5)%] via abstraction of the aldehydic hydrogen atom, [(2.3 ± 0.8)%] via abstraction from the −CH3 group, and approximately [(47 ± 8) %] via addition to the CH2═C< double bond with most of the addition occurring at the terminal carbon atom (uncertainties represent statistical 2σ). The results are discussed with respect to the literature data." @default.
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• W2067465718 date "2010-06-08" @default.
• W2067465718 modified "2023-10-11" @default.
• W2067465718 title "Kinetics and Mechanism of the Reaction of Methacrolein with Chlorine Atoms in 1−950 Torr of N₂ or N₂/O₂ Diluent at 297 K" @default.
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• W2067465718 doi "https://doi.org/10.1021/jp103317c" @default.
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