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Rate constant and products for the reaction of Cl atom with n‐butyraldehyde
Authors:Hai Wu  Yujing Mu
Institution:1. National Institute of Metrology of China, Beijing 100013, P.R. China;2. Research Center for Eco‐Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, P.R. China;3. Research Center for Eco‐Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, P.R. ChinaResearch Center for Eco‐Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, P.R. China
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 cm3 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. C2H5CHO, CH3CHO, CO and CO2 were the major products observed. In the absence of NO, the observed yields of C2H5CHO, CH3CHO, 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 C2H5CHO decreased to 33%, whereas that of CH3CHO 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
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