To understand the effects of the chemical structure of two C₅ alkene isomers on their combustion properties, and to highlight the major chemical reactions occurring during their high‐temperature oxidation, water time histories were measured behind reflected shock waves for the oxidation of 1‐pentene (C₅H₁₀‐1) and 3‐methyl‐1‐butene (3M1B) in 99.5% Ar. The experiments were carried out at three different equivalence ratios (φ = 0.5, 1.0, and 2.0) at pressures and temperatures ranging from 1.29 to 1.47 atm and 1 331 to 1 877 K, respectively. The H₂O quantification extends the database for 1‐pentene and provides new insights for 3M1B. These unique results were used to validate and to develop a new detailed kinetics model. Numerical predictions are presented, and the new model was able to capture the results with suitable accuracy, with 3M1B being notably more reactive than C₅H₁₀‐1. Sensitivity and rate‐of‐production analyses were performed to help explain the results. Under the present conditions, the reactivity is rapidly initiated by molecular dissociation of a fraction of the pentene isomers. The initiation phase then induces H‐atom abstraction by active radicals (H, OH, O, HO₂, and CH₃) to first produce alkenyl C₅H₉ radicals (or an alkyl radical and an alkenyl radical by breaking a C─C bond) and subsequent, smaller fragments. The difference in terms of reactivity between the isomers is essentially due to the fact that 3M1B has one particularly weak tertiary allylic C─H bond, which allows for fast H‐atom abstraction compared with 1‐pentene.

中文翻译：

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冲击管光谱水测量和1-戊烯和3-甲基-1-丁烯的详细动力学模型

为了了解两种C ₅烯烃异构体的化学结构对其燃烧特性的影响，并突出其高温氧化过程中发生的主要化学反应，在反射冲击波后测量了水的时间历史，以反映1-戊烯的氧化（C ₅ H ₁₀ -1）和3-甲基-1-丁烯（3M1B）在99.5％Ar中的含量。实验分别在 1.29至1.47 atm和1 331至1 877 K的压力和温度下以三种不同的当量比（φ = 0.5、1.0和2.0）进行。H ₂O量化扩展了1-戊烯的数据库，并为3M1B提供了新的见解。这些独特的结果用于验证和开发新的详细动力学模型。提出了数值预测，并且新模型能够以适当的精度捕获结果，其中3M1B的反应性明显高于C ₅ H ₁₀ -1。进行了敏感性和生产率分析以帮助解释结果。在当前条件下，一部分戊烯异构体通过分子离解而迅速引发反应。然后，引发阶段通过活性自由基（H，OH，O，HO ₂和CH ₃）诱导H原子抽象，首先生成烯基C ₅ H ₉自由基（或通过破坏C–C键的烷基或烯基）和随后的较小片段。异构体之间在反应性方面的差异主要是由于3M1B具有一个特别弱的叔烯丙基C-H键，与1-戊烯相比，该键可实现快速的H原子抽象。