Abstract
Experiments have been conducted in the laboratory and in the outdoor smog chamber (EUPHORE) to study the photolysis and the OH-initiated oxidation of (1) acrolein (CH2CHCHO) and (2) trans-crotonaldehyde (CH3CHCHCHO). In addition, the UV−visible absorption spectra for these two unsaturated aldehydes have been determined at (298 ± 2) K, and the rate constants for OH reactions have been measured using PLP-LIF technique as function of pressure (20−300) Torr in the temperature range (243−372) K. The obtained rate constant values are k1 = (6.55 ± 1.22) · 10-12 exp[(333 ± 54)/T] and k2 = (5.77 ± 1.14) · 10-12 exp[(533 ± 58)/T] cm3 molecule-1 s-1. From both midday photolysis rates J1 ≤ 2 · 10-6 s-1 for acrolein and J2 ≤ 1.2 · 10-5 s-1 for trans-crotonaldehyde, measured at EUPHORE during summer, and UV−visible absorption cross sections, very low effective quantum yields were derived: Φeff ≤ 0.005 for acrolein, and Φeff ≤ (0.030 ± 0.006) for trans-crotonaldehyde. The major primary products of the OH-initiated oxid...
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