Kinetics of OH and Cl reactions with a series of aldehydes

✍ Scribed by R. Thévenet; A. Mellouki; G. Le Bras

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 240 KB
• Volume: 32
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/1097-4601(2000)32:11<676::aid-kin3>3.0.co;2-v

✦ Synopsis

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 photolysispulsed laser induced fluorescence method. The obtained data for propanaldehyde, iso-butyraldehyde, tert-butyraldehyde, and n-pentaldehyde were as follows (in cm 3 molecule Ϫ1 s Ϫ1 ): (a) in the Arrhenius form: (5.3 Ϯ 0.5) ϫ 10 Ϫ12 exp[(405 Ϯ 30)/T], (7.3 Ϯ 1.9) ϫ 10 Ϫ12 exp[(390 Ϯ 78)/T], (4.7 Ϯ 0.8) ϫ 10 Ϫ12 exp[(564 Ϯ 52)/T], and (9.9 Ϯ 1.9) ϫ 10 Ϫ12 exp[(306 Ϯ 56)/T]; (b) at 298 K: (2.0 Ϯ 0.3) ϫ 10 Ϫ11 , (2.6 Ϯ 0.4) ϫ 10 Ϫ11 , (2.7 Ϯ 0.4) ϫ 10 Ϫ11 , and (2.8 Ϯ 0.2) ϫ 10 Ϫ11 , 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 cm 3 molecule Ϫ1 s Ϫ1 ): (1.4 Ϯ 0.3) ϫ 10 Ϫ10 , (1.7 Ϯ 0.3)10 Ϫ10 , (1.6 Ϯ 0.3) ϫ 10 Ϫ10 , (2.6 Ϯ 0.3) ϫ 10 Ϫ10 , (2.2 Ϯ 0.3) ϫ 10 Ϫ10 , and (2.6 Ϯ 0.3) ϫ 10 Ϫ10 , respectively. The results are presented and discussed in terms of structurereactivity relationships and atmospheric importance.