Rate coeffcients for the reaction of OH with (E)-2-pentenal, (E)-2-hexenal, and (E)-2-heptenal

被引:32
作者
Davis, M. E.
Gilles, M. K.
Ravishankara, A. R.
Burkholder, James B.
机构
[1] NOAA, Earth Syst Res Lab, Div Chem Sci, Boulder, CO 80305 USA
[2] Univ Colorado, Cooperat Inst Res Environm Sci, Boulder, CO 80309 USA
[3] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA
关键词
D O I
10.1039/b700235a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Rate coefficients for the gas-phase reaction of the OH radical with (E)-2-pentenal (CH3CH2CH=CHCHO), (E)-2-hexenal (CH3(CH2) 2CH=CHCHO), and (E)-2-heptenal (CH3(CH2)(3)CH=CHCHO), a series of unsaturated aldehydes, over the temperature range 244-374 K at pressures between 23 and 150 Torr (He, N-2) are reported. Rate coefficients were measured under pseudo-first-order conditions in OH with OH radicals produced via pulsed laser photolysis of HNO3 or H2O2 at 248 nm and detected by pulsed laser-induced fluorescence. The rate coefficients were independent of pressure and the room temperature rate coefficients and Arrhenius expressions obtained are (cm(3) molecule(-1) s(-1) units): k(1)(297 K) = (4.3 +/- 0.6) x 10(-11), k(1)(T) = (7.9 +/- 1.2) x 10(-12) exp[(510 +/- 20)/T]; k(2)(297 K) = (4.4 +/- 0.5) x 10(-11), k(2)(T) = (7.5 +/- 1.1) x 10(- 12) exp[(520 +/- 30)/T]; and k(3)(297 K) = (4.4 +/- 0.7) x 10(- 11), k3(T) (9.7 +/- 1.5) x 10(-12) exp[(450 +/- 20)/T] for (E)-2-pentenal, (E)-2-hexenal and ( E)-2-heptenal, respectively. The quoted uncertainties are 2 sigma (95% confidence level) and include estimated systematic errors. Rate coefficients are compared with previously published room temperature values and the discrepancies are discussed. The atmospheric degradation of unsaturated aldehydes is also discussed.
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页码:2240 / 2248
页数:9
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