Taatjes Craig A, Hansen Nils, McIlroy Andrew, Miller James A, Senosiain Juan P, Klippenstein Stephen J, Qi Fei, Sheng Liusi, Zhang Yunwu, Cool Terrill A, Wang Juan, Westmoreland Phillip R, Law Matthew E, Kasper Tina, Kohse-Höinghaus Katharina
Combustion Research Facility, Mail Stop 9055, Sandia National Laboratories, Livermore, CA 94551-0969, USA.
Science. 2005 Jun 24;308(5730):1887-9. doi: 10.1126/science.1112532. Epub 2005 May 12.
Models for chemical mechanisms of hydrocarbon oxidation rely on spectrometric identification of molecular structures in flames. Carbonyl (keto) compounds are well-established combustion intermediates. However, their less-stable enol tautomers, bearing OH groups adjacent to carbon-carbon double bonds, are not included in standard models. We observed substantial quantities of two-, three-, and four-carbon enols by photoionization mass spectrometry of flames burning representative compounds from modern fuel blends. Concentration profiles demonstrate that enol flame chemistry cannot be accounted for purely by keto-enol tautomerization. Currently accepted hydrocarbon oxidation mechanisms will likely require revision to explain the formation and reactivity of these unexpected compounds.
碳氢化合物氧化化学机理模型依赖于火焰中分子结构的光谱鉴定。羰基（酮）化合物是公认的燃烧中间体。然而，它们不太稳定的烯醇互变异构体，在碳 - 碳双键相邻位置带有羟基，并未包含在标准模型中。通过对燃烧现代燃料混合物中代表性化合物的火焰进行光电离质谱分析，我们观测到了大量的二碳、三碳和四碳烯醇。浓度分布表明，烯醇火焰化学不能单纯用酮 - 烯醇互变异构来解释。目前被认可的碳氢化合物氧化机理可能需要修正，以解释这些意外化合物的形成和反应活性。
