Rate constant and products for the reaction of Cl atom with n-butyraldehyde

✍ Scribed by Hai Wu; Yujing Mu

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 168 KB
• Volume: 39
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.20228

✦ Synopsis

Abstract

The photooxidations of n‐butyraldehyde initiated by Cl atom were carried out at room temperature (298 ± 2K) and 1 atm pressure. The rate coefficient for the reactions of Cl atom with n‐butyraldehyde was determined as k = (2.04 ± 0.36) × 10^−10^ cm^3^ molecule^−1^ s^−1^ by using relative rate techniques. The photooxidation products of n‐butyraldehyde reaction with Cl atom were also studied by using both gas chromatography‐mass spectrometry (GC‐MS) and gas chromatography techniques. C~2~H~5~CHO, CH~3~CHO, CO and CO~2~ were the major products observed. In the absence of NO, the observed yields of C~2~H~5~CHO, CH~3~CHO, and CO were 60%, 3%, and 9%, respectively. However, when NO was introduced into the reaction chamber and the initial ratios of [NO]~0~/[n‐butyraldehyde]~0~ were between 1 and 8, the yield of C~2~H~5~CHO decreased to 33%, whereas that of CH~3~CHO and CO rose up to 21% and 25%, respectively. On the basis of mechanism data deduced in this study and the fraction molar yields, the approximate branching ratios for Cl atom attack at C(O)H, α‐, β‐, and γ‐positions in n‐butyraldehyde could be derived as ⩾42%, <25%, 21%, and ⩽12%, respectively. © 2007 Wiley Periodicals, Inc. 39: 168–174, 2007