CHOO与CHCHCHO反应的温度和压力依赖速率系数测量
Temperature- and pressure-dependent rate coefficient measurement for the reaction of CHOO with CHCHCHO.
作者信息
Liu Yiqiang, Zhou Xiaohu, Chen Yang, Chen Maodu, Xiao Chunlei, Dong Wenrui, Yang Xueming
机构信息
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Ministry of Education), School of Physics, Dalian University of Technology, Dalian, 116024, China.
出版信息
Phys Chem Chem Phys. 2020 Nov 18;22(44):25869-25875. doi: 10.1039/d0cp04316h.
Propionaldehyde is one of the most abundant aldehydes, which are an important class of volatile organic compounds. In this work, the rate coefficient of the reaction of the simplest Criegee intermediate CH2OO with propionaldehyde (CH3CH2CHO) was measured for the first time in a flash photolysis reaction tube by using the OH laser-induced fluorescence (LIF) method at temperature and pressure in the range of 283 to 318 K and 5 to 200 Torr. This reaction is observed to be pressure- and temperature-dependent. The measured rate coefficient at 50 Torr is in the vicinity of the high-pressure limit value of (3.23 ± 0.49) × 10-12 cm3 s-1 at 298 K, which is in agreement with a previously reported theoretical result of 2.44 × 10-12 cm3 s-1. The Arrhenius plot of the temperature-dependent rate coefficients yields an activation energy of (-1.99 ± 0.23) kcal mol-1.
丙醛是含量最为丰富的醛类之一，醛类是一类重要的挥发性有机化合物。在本研究中，首次在闪光光解反应管中，于283至318 K的温度范围以及5至200托的压力条件下，采用OH激光诱导荧光（LIF）方法，测定了最简单的克里奇中间体CH₂OO与丙醛（CH₃CH₂CHO）反应的速率系数。观察到该反应与压力和温度相关。在50托下测得的速率系数，在298 K时接近高压极限值(3.23 ± 0.49) × 10⁻¹² cm³ s⁻¹，这与先前报道的理论结果2.44 × 10⁻¹² cm³ s⁻¹相符。温度相关速率系数的阿仑尼乌斯图给出的活化能为(-1.99 ± 0.23) kcal mol⁻¹。
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