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

Physical Chemistry Chemical Physics Pub Date: 2007-02-14 DOI: 10.1039/B700235A

Abstract

Rate coefficients for the gas-phase reaction of the OH radical with (E)-2-pentenal (CH3CH2CH[double bond, length as m-dash]CHCHO), (E)-2-hexenal (CH3(CH2)2CH[double bond, length as m-dash]CHCHO), and (E)-2-heptenal (CH3(CH2)3CH[double bond, length as m-dash]CHCHO), a series of unsaturated aldehydes, over the temperature range 244–374 K at pressures between 23 and 150 Torr (He, N2) 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 (cm3 molecule?1 s?1 units): k1(297 K) = (4.3 ± 0.6) × 10?11, k1(T) = (7.9 ± 1.2) × 10?12 exp[(510 ± 20)/T]; k2(297 K) = (4.4 ± 0.5) × 10?11, k2(T) = (7.5 ± 1.1) × 10?12 exp[(520 ± 30)/T]; and k3(297 K) = (4.4 ± 0.7) × 10?11, k3(T) = (9.7 ± 1.5) × 10?12 exp[(450 ± 20)/T] for (E)-2-pentenal, (E)-2-hexenal and (E)-2-heptenal, respectively. The quoted uncertainties are 2σ (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.

Graphical abstract: Rate coefficients for the reaction of OH with (E)-2-pentenal, (E)-2-hexenal, and (E)-2-heptenal
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