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Kinetic study of reaction C2H5 + HO2 in a photolysis reactor with time-resolved faraday rotation spectroscopy
Proceedings of the Combustion Institute ( IF 5.3 ) Pub Date : 2020-10-14 , DOI: 10.1016/j.proci.2020.07.095
Hongtao Zhong , Chao Yan , Chu C. Teng , Guoming Ma , Gerard Wysocki , Yiguang Ju

The rate constant and branching ratios of ethyl reaction with hydroperoxyl radical, C2H5 + HO2 (1), a key radical-radical reaction for intermediate temperature combustion chemistry, were measured in situ for the first time in a photolysis Herriott cell by using mid-IR Faraday rotation spectroscopy (FRS) and UV-IR direct absorption spectroscopy (DAS). The microsecond time-resolved diagnostic technique in this work enabled the direct rate measurements of the target reaction at 40 and 80 mbar and reduced the experimental uncertainty considerably. C2H5 and HO2 radicals were generated by the photolysis of (COCl)2/C2H5I/CH3OH/O2/He mixture at 266 nm. By direct measurements of the transient profiles of C2H5, HO2 and OH concentrations, the overall rate constant for this reaction at 297 K was determined as k1(40 mbar) = (3.8 ± 0.8) × 1011 cm3 molecule1 s1 and k1(80 mbar) = (4.1 ± 1.0) × 1011 cm3 molecule1 s1. The direct observation of hydroxyl radical (OH) indicated that OH formation channel was the major channel with a branching ratio of 0.8 ± 0.1.



中文翻译:

时间分辨法拉第旋转光谱法研究光解反应器中反应C 2 H 5 + HO 2的动力学

首次在光解Herriott电池中原位测量与氢过氧自由基C 2 H 5 + HO 2(1)的乙基反应的速率常数和支化比,C 2 H 5 + HO 2是中温燃烧化学的关键自由基自由基反应。使用中红外法拉第旋转光谱(FRS)和紫外红外直接吸收光谱(DAS)。这项工作中的微秒时间分辨诊断技术可以在40和80 mbar下对目标反应进行直接速率测量,并大大降低了实验不确定性。(COCl)2 / C 2的光解产生C 2 H 5和HO 2自由基在266 nm下的H 5 I / CH 3 OH / O 2 / He混合物。通过直接测量C 2 H 5,HO 2和OH浓度的瞬态曲线,可以确定该反应在297 K时的总速率常数为k 1(40 mbar)=(3.8±0.8)×10-11cm 3分子-1个 s-1个和k 1(80 mbar)=(4.1±1.0)×10-11cm 3分子-1个 s-1个。羟基自由基(OH)的直接观察表明,OH形成通道是主要通道,支化比为0.8±0.1。

更新日期:2020-10-15
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