Research Institute for Sustainable Humanosphere and Pioneering Research Unit, Kyoto University, Gokasho, Uji, 611-0011 Japan.
J Phys Chem A. 2010 Apr 1;114(12):4224-31. doi: 10.1021/jp908104r.
The gas-phase reactions of Cl atoms with allyl alcohol (k(1)), 3-buten-2-ol (k(2)), and 2-methyl-3-buten-2-ol (k(3)) at 296 +/- 2 K have been investigated using absolute and relative rate methods in 1-700 Torr of N(2) diluent. Absolute rate studies were performed using pulsed laser photolysis/vacuum ultraviolet laser-induced fluorescence spectroscopy techniques. Relative rate studies were performed using smog chamber/Fourier transform infrared spectroscopy techniques. The absolute and relative rate studies gave consistent results. The kinetics of the reactions are dependent on pressure over the range studied. Molar yields for HCl production in 700 Torr of N(2) for reactions of chlorine atoms with allyl alcohol, 3-buten-2-ol, and 2-methyl-3-buten-2-ol were measured to be 0.26 +/- 0.03, 0.23 +/- 0.03, and 0.12 +/- 0.02, respectively. The chlorine-atom-initiated oxidation of 2-methyl-3-buten-2-ol in 700 Torr of air gave the following products (molar yields): acetone (47 +/- 4%), chloroacetaldehyde (47 +/- 5%), and HCHO (7.2 +/- 0.6%). The observation of substantial and indistinguishable yields of acetone and chloroacetaldehyde products indicates that a major fraction of the reaction proceeds via addition of chlorine atoms to the terminal carbon atom. The results are discussed with respect to the literature data.
Cl 原子与烯丙醇（k(1)）、3-丁烯-2-醇（k(2)）和 2-甲基-3-丁烯-2-醇（k(3)）在 296 ± 2 K 的气相反应在 1-700 Torr 的 N(2)稀释剂中通过绝对和相对速率方法进行了研究。绝对速率研究使用脉冲激光光解/真空紫外激光诱导荧光光谱技术进行。相对速率研究使用烟雾箱/傅里叶变换红外光谱技术进行。绝对和相对速率研究给出了一致的结果。反应动力学在研究范围内随压力而变化。在 700 Torr 的 N(2)中，Cl 原子与烯丙醇、3-丁烯-2-醇和 2-甲基-3-丁烯-2-醇反应生成 HCl 的摩尔产率分别测量为 0.26 ± 0.03、0.23 ± 0.03 和 0.12 ± 0.02。在 700 Torr 的空气中，Cl 原子引发的 2-甲基-3-丁烯-2-醇氧化生成下列产物（摩尔产率）：丙酮（47 ± 4%）、氯乙醛（47 ± 5%）和 HCHO（7.2 ± 0.6%）。观察到丙酮和氯乙醛产物的大量且无明显差异的产率表明，反应的主要部分通过 Cl 原子加成到末端碳原子上进行。结果与文献数据进行了讨论。
