正丁醛与氯原子反应的动力学和机理研究

Kinetics and mechanism of the reaction for n-butyraldehyde with Cl atoms

在室温和一个大气压下,利用气相色谱和气质联用研究了氯原子与正丁醛的光化学反应,获得了该反应的反应速率常数k2=(1 19±0 10)×108m3·mol-1·s-1;该反应的主要产物是:丙醛、乙醛、CO和CO2.结合这些主要产物以及它们的产率对氯原子与正丁醛反应的机理进行了探讨,获得了氯原子在正丁醛的—CHO、α位、β位和γ位摘氢份额分别为44%,25%,20%和11%.

The photooxidation of n-butyraldehyde initiated by Cl atoms was studied at room temperature and 1 atm. by using GC-FID and GC-MS. The rate constant for the reaction of n-butyraldehyde with Cl atoms which was obtained by relative method was (1.19±0.10)×10^(8) m^3·mol^(-1)·s^(-1). The major products of the reaction were propionaldehyde, acetaldehyde, CO and CO_2. Being considered these major products and their formation yields, the branching ratios of Cl attacking at the —CHO, α、β and γ positions in n-butyradehyde were 44%, 25%, 20% and 11%, respectively. The mechanism of the reaction was also discussed in detail.