Atmospheric Chemistry of n-Butanol: Kinetics, Mechanisms, and Products of Cl Atom and OH Radical Initiated Oxidation in the Presence and Absence of NOx
Hurley, MD; Wallington, TJ; Laursen, L; Javadi, MS; Nielsen, OJ; Yamanaka, T; Kawasaki, M
| HERO ID | 608522 |
|---|---|
| In Press | No |
| Year | 2009 |
| Title | Atmospheric Chemistry of n-Butanol: Kinetics, Mechanisms, and Products of Cl Atom and OH Radical Initiated Oxidation in the Presence and Absence of NOx |
| Authors | Hurley, MD; Wallington, TJ; Laursen, L; Javadi, MS; Nielsen, OJ; Yamanaka, T; Kawasaki, M |
| Journal | Journal of Physical Chemistry A |
| Volume | 113 |
| Issue | 25 |
| Page Numbers | 7011-7020 |
| Abstract | Smog chamber/FTIR techniques were used to determine rate constants of k(Cl+n-butanol) = (2.21 ± 0.38) × 10−10and k(OH+n-butanol) = (8.86 ± 0.85) × 10−12cm3molecule−1s−1in 700 Torr of N2/O2diluent 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 CH3CH2CH(O)CH2OH and CH3CH(O)CH2CH2OH 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 α-position to give an α-hydroxy alkyl radical which reacts with O2to give butyraldehyde. The results are discussed with respect to the atmospheric chemistry of n-butanol. [ABSTRACT FROM AUTHOR] Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) |
| Doi | 10.1021/jp810585c |
| Pmid | 19462959 |
| Wosid | WOS:000267205500022 |
| Url | http://dx.doi.org/10.1021/jp810585c |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |
| Keyword | ATMOSPHERIC chemistry; BUTANOL; CHEMICAL kinetics; CHLORINE; HYDROXYL group; OXIDATION; FOURIER transform infrared spectroscopy; NITROGEN oxides; REACTION mechanisms (Chemistry) |
| Is Qa | No |