Chen Yang, Jiang Haotian, Liu Siyue, Shi Jiayu, Jin Yuqi, Yang Xueming, Dong Wenrui
Key Laboratory of Chemical Lasers, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
J Phys Chem A. 2023 Mar 23;127(11):2432-2439. doi: 10.1021/acs.jpca.2c07854. Epub 2023 Mar 13.
The kinetics of the simplest Criegee intermediate (CHOO) reaction with -butylamine ((CH)CNH) was studied under pseudo-first-order conditions with the OH laser-induced fluorescence (LIF) method at the temperature range of 283-318 K and the pressure range of 5-75 Torr. Our pressure-dependent measurement showed that at 5 Torr─the lowest pressure measured in the current experiment─this reaction was under the high-pressure limit condition. At 298 K, the reaction rate coefficient was measured to be (4.95 ± 0.64) × 10 cm molecule s. The title reaction was observed to be negative temperature-dependent; the activation energy of (-2.82 ± 0.37) kcal mol and the pre-exponential factor of (4.21 ± 0.55) × 10 cm molecule s were derived from the Arrhenius equation. The rate coefficient of the title reaction is slightly larger than (4.3 ± 0.5) × 10 cm molecule s of the CHOO reaction with methylamine; the electron inductive effect and the steric hindrance effect might play a role in contributing to such difference.
在283 - 318 K的温度范围和5 - 75 Torr的压力范围内，采用OH激光诱导荧光（LIF）方法，在准一级条件下研究了最简单的克里吉中间体（CHOO）与丁胺（(CH₃)₂CHCNH₂）反应的动力学。我们的压力依赖性测量表明，在5 Torr（本实验中测量的最低压力）下，该反应处于高压极限条件。在298 K时，测得反应速率系数为(4.95 ± 0.64) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹。观察到标题反应具有负温度依赖性；由阿仑尼乌斯方程得出活化能为(-2.82 ± 0.37) kcal mol⁻¹，指前因子为(4.21 ± 0.55) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹。标题反应的速率系数略大于CHOO与甲胺反应的(4.3 ± 0.5) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹；电子诱导效应和空间位阻效应可能在造成这种差异中起作用。
