A chemical pathway perspective on the kinetics of low-temperature ignition of propane
A chemical pathway perspective on the kinetics of low-temperature ignition of propane
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DOI：
10.1016/j.combustflame.2019.01.006
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发表时间：
2019-04
影响因子：
4.4
通讯作者：
Shirong Bai;Michael J. Davis;R. Sivaramakrishnan;R. T. Skodje
中科院分区：
文献类型：
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作者：
Shirong Bai;Michael J. Davis;R. Sivaramakrishnan;R. T. Skodje
用最近发展起来的化学动力学路径表示法分析了丙烷/空气混合物的低温着火化学。“历史求和表示”允许使用在复杂反应网络中移动时跟随化学部分的全球化学路径上的展开来计算依赖于时间的动力学可观测值。这种方法指定了生成特定中间体或产品物种所通过的完整化学途径的概率。通过列举构成催化循环的化学路径，特别是高活性OH-自由基的催化生成，分析了点火过程中自由基池的增长。除了众所周知的碳氢化合物低温点火过程中涉及QOOH和酮氢过氧化氢物种的反应路线外，我们还明确确定了其他几个循环，这些循环负责剩余的大部分OH-的产生。
The chemistry of low-temperature ignition in propane/air mixtures is analyzed using a recently developed pathway representation of the chemical kinetics. The “Sum Over Histories Representation” allows time-dependent kinetic observables to be computed using an expansion over global chemical pathways that follow chemical moieties as they move through a complex reaction network. This methodology assigns probabilities to complete chemical pathways through which specific intermediate or product species are generated. The growth of the radical pool during the ignition process is analyzed by enumerating chemical pathways that constitute catalytic cycles, in particular the catalyzed production of the highly reactive OH-radical. In addition to the well-known reaction route followed in low-temperature ignition of hydrocarbons which involves the QOOH and keto-hydroperoxide species, we have explicitly identified several other cycles that are responsible for most of the remaining OH-production.