Atmospheric Chemistry ofn-Butanol: Kinetics, Mechanisms, and Products of Cl Atom and OH Radical Initiated Oxidation in the Presence and Absence of NOx.

Abstract

Smog chamber/FTIR techniques were used to determine rate constants of k(Cl+n-butanol) = (2.21 +/- 0.38) x 10(-10) and k(OH+n-butanol) = (8.86 +/- 0.85) x 10(-12) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296 +/- 2K. The sole primary product identified from the Cl atom initiated oxidation of n-butanol in the absence of NO was butyraldehyde (38 +/- 2%, molar yield). The primary products of the Cl atom initiated oxidation of n-butanol in the presence of NO were (molar yield) butyraldehyde (38 +/- 2%), propionaldehyde (23 +/- 3%), acetaldehyde (12 +/- 4%), and formaldehyde (33 +/- 3%). The substantially lower yields of propionaldehyde, acetaldehyde, and formaldehyde as primary products in experiments conducted in the absence of NO suggests that chemical activation is important in the atmospheric chemistry of CH(3)CH(2)CH(O)CH(2)OH and CH(3)CH(O)CH(2)CH(2)OH alkoxy radicals. The primary products of the OH radical initiated oxidation of n-butanol in the presence of NO were (molar yields) butyraldehyde (44 +/- 4%), propionaldehyde (19 +/- 2%), and acetaldehyde (12 +/- 3%). In all cases, the product yields were independent of oxygen concentration over the partial pressure range of 10-600 Torr. The yields of propionaldehyde, acetaldehyde, and formaldehyde quoted above were not corrected for secondary formation via oxidation of higher aldehydes and should be treated as upper limits. The reactions of Cl atoms and OH radicals with n-butanol proceed 38 +/- 2 and 44 +/- 4%, respectively, via attack on the alpha-position to give an alpha-hydroxy alkyl radical which reacts with O(2) to give butyraldehyde. The results are discussed with respect to the atmospheric chemistry of n-butanol.