Single pulse shock tube study of allyl radical recombination.
Single pulse shock tube study of allyl radical recombination.
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DOI：
10.1021/jp402391n
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发表时间：
2013-06
期刊：
影响因子：
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通讯作者：
A. Fridlyand;P. Lynch;R. Tranter;K. Brezinsky
中科院分区：
文献类型：
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作者：
A. Fridlyand;P. Lynch;R. Tranter;K. Brezinsky
在单脉冲激波管中研究了烯丙基自由基的重组和歧化，并在 1-10 bar、650-1300 K 和 1.4-2 ms 反应时间下进行气相色谱测量。 1,5-己二烯和烯丙基碘用作前体。使用来自补充无隔膜激波管/激光纹影密度测定研究的导出速率表达式对结果进行模拟，提供了与前体消耗和所有主要稳定中间体的形成的极好的一致性。在目前的条件下没有观察到明显的压力依赖性。结果发现，在这些实验条件下，必须考虑冷却波中烯丙基自由基的反应才能准确模拟实验结果，并对这种不寻常的情况进行了讨论。在烯丙基碘实验中，在比预期更低的温度下发现了更高含量的丙二烯、丙烯和苯。讨论了可能的机制，并表明含碘物质是丙二烯、丙烯和苯的低温形成的原因。
The recombination and disproportionation of allyl radicals has been studied in a single pulse shock tube with gas chromatographic measurements at 1-10 bar, 650-1300 K, and 1.4-2 ms reaction times. 1,5-Hexadiene and allyl iodide were used as precursors. Simulation of the results using derived rate expressions from a complementary diaphragmless shock tube/laser schlieren densitometry study provided excellent agreement with precursor consumption and formation of all major stable intermediates. No significant pressure dependence was observed at the present conditions. It was found that under the conditions of these experiments, reactions of allyl radicals in the cooling wave had to be accounted for to accurately simulate the experimental results, and this unusual situation is discussed. In the allyl iodide experiments, higher amounts of allene, propene, and benzene were found at lower temperatures than expected. Possible mechanisms are discussed and suggest that iodine containing species are responsible for the low temperature formation of allene, propene, and benzene.