Measuring hydroperoxide chain-branching agents during n-pentane low-temperature oxidation
Measuring hydroperoxide chain-branching agents during n-pentane low-temperature oxidation
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DOI：
10.1016/j.proci.2016.05.044
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发表时间：
2017
期刊：
影响因子：
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通讯作者：
Anne Rodriguez;O. Herbinet;Zhandong Wang;F. Qi;C. Fittschen;P. R. Westmoreland;F. Battin‐Leclerc
中科院分区：
文献类型：
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作者：
Anne Rodriguez;O. Herbinet;Zhandong Wang;F. Qi;C. Fittschen;P. R. Westmoreland;F. Battin‐Leclerc
H2 O2和过氧化氢等链支化剂的反应对自燃的发生起决定性作用。这些代理人的形成已在大气压喷射搅拌反应器中进行了研究，在低温氧化的正戊烷（初始燃料摩尔分数为0.01，停留时间为2秒）使用三种不同的诊断：飞行时间质谱结合可调谐同步辐射光电离，飞行时间质谱结合激光光电离，和CW腔衰荡光谱。这三种诊断使得能够组合分析H2 O2、C1-C2和C5烷基氢过氧化物、C3-C5烯基氢过氧化物和包括羰基官能团的C5烷基氢过氧化物（酮基氢过氧化物）。使用这两种类型的质谱的结果进行比较的化学计量的混合物。形成的数据是在当量比从0.5到2，这些过氧化物和两个氧化的产品，乙烯酮和戊二酮，这通常是不分析在喷射搅拌反应器氧化。链烯基氢过氧化物的形成在烷烃氧化是第一次。最近开发的模型ofn-pentane氧化艾滋病的动力学讨论这些产品和C3-C5烯基氢过氧化物和戊二酮的建议途径。
The reactions of chain-branching agents, such as H2O2and hydroperoxides, have a decisive role in the occurrence of autoignition. The formation of these agents has been investigated in an atmospheric-pressure jet-stirred reactor during the low-temperature oxidation ofn-pentane (initial fuel mole fraction of 0.01, residence time of 2 s) using three different diagnostics: time-of-flight mass spectrometry combined with tunable synchrotron photoionization, time-of-flight mass spectrometry combined with laser photoionization, andcw-cavity ring-down spectroscopy. These three diagnostics enable a combined analysis of H2O2, C1–C2, and C5alkylhydroperoxides, C3–C5alkenylhydroperoxides, and C5alkylhydroperoxides including a carbonyl function (ketohydroperoxides). Results using both types of mass spectrometry are compared for the stoichiometric mixture. Formation data are presented at equivalence ratios from 0.5 to 2 for these peroxides and of two oxygenated products, ketene and pentanediones, which are not usually analyzed during jet-stirred reactor oxidation. The formation of alkenylhydroperoxides during alkane oxidation is followed for the first time. A recently developed model ofn-pentane oxidation aids discussion of the kinetics of these products and of proposed pathways for C3–C5alkenylhydroperoxides and the pentanediones.