| Abstract: | The rate constants for the reactions of the OH radicals with a series of aldehydes have been measured in the temperature range 243–372 K, using the pulsed laser photolysis‐pulsed laser induced fluorescence method. The obtained data for propanaldehyde, iso‐butyraldehyde, tert‐butyraldehyde, and n‐pentaldehyde were as follows (in cm3 molecule?1 s?1): (a) in the Arrhenius form: (5.3 ± 0.5) × 10?12 exp(405 ± 30)/T], (7.3 ± 1.9) × 10?12 exp(390 ± 78)/T], (4.7 ± 0.8) × 10?12 exp(564 ± 52)/T], and (9.9 ± 1.9) × 10?12 exp(306 ± 56)/T]; (b) at 298 K: (2.0 ± 0.3) × 10?11, (2.6 ± 0.4) × 10?11, (2.7 ± 0.4) × 10?11, and (2.8 ± 0.2) × 10?11, respectively. In addition, using the relative rate method and alkanes as the reference compounds, the room‐temperature rate constants have been measured for the reactions of chlorine atoms with propanaldehyde, iso‐butyraldehyde, tert‐butyraldehyde, n‐pentaldehyde, acrolein, and crotonaldehyde. The obtained values were (in cm3 molecule?1 s?1): (1.4 ± 0.3) × 10?10, (1.7 ± 0.3)10?10, (1.6 ± 0.3) × 10?10, (2.6 ± 0.3) × 10?10, (2.2 ± 0.3) × 10?10, and (2.6 ± 0.3) × 10?10, respectively. The results are presented and discussed in terms of structure‐reactivity relationships and atmospheric importance. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 676–685, 2000 |
