In this work, pyrolysis experiments of ethyl valerate were performed in a flow reactor over 705–1051 K at low and atmospheric pressures and in a jet-stirred reactor over 633–1013 K at near-atmospheric pressure. Products were measured with synchrotron vacuum ultraviolet photoionization mass spectrometry in the flow reactor pyrolysis and gas chromatography in the jet-stirred reactor pyrolysis. Valeric acid and ethylene were observed as the most abundant pyrolysis products in both experiments. Laminar burning velocities of ethyl valerate/air mixtures were also measured in a high-pressure constant-volume cylindrical combustion vessel at the initial temperature of 443 K and initial pressures of 1–10 atm. A kinetic model of ethyl valerate combustion incorporated with recent theoretical progress was developed to predict the new experimental data in this work, as well as the speciation data under flame conditions and laminar burning velocities at different initial temperatures and pressures in literature. Experimental observations and modeling analyses both confirm the significant role of the intramolecular elimination reaction of ethyl valerate producing valeric acid and ethylene. In particular, this reaction has exclusive significance in decomposition of ethyl valerate under pyrolysis conditions, indicating pyrolysis experiments can provide crucial constraints for its rate constant. Subsequent decomposition reactions of valeric acid at higher temperatures enrich the intermediate pool, especially radicals, and can continue producing ethylene to make its mole fraction keep growing under the investigated temperature ranges in the jet-stirred reactor pyrolysis. Under the flame propagation conditions, C₀C₁ reactions have the highest sensitivity coefficients to the flame propagation, while ethylene- and vinyl-involved reactions also play important roles due to the abundant production of ethylene.

在这项工作中，戊酸乙酯的热解实验在低压和大气压下于705–1051 K的流动反应器中和在接近大气压下于633–1313 K的喷射搅拌反应器中进行。在流动反应器热解中用同步加速器真空紫外光电离质谱法测量产物，在喷射搅拌反应器热解中用气相色谱法测量产物。在两个实验中均观察到戊酸和乙烯是最丰富的热解产物。戊酸乙酯/空气混合物的层流燃烧速度也在高压恒容圆筒形燃烧器中以443 K的初始温度和1-10 atm的初始压力进行了测量。建立了结合最新理论进展的戊酸乙酯燃烧动力学模型，以预测这项工作中的新实验数据，以及文献中不同初始温度和压力下火焰条件和层流燃烧速度下的形态数据。实验观察和模型分析均证实了戊酸乙酯产生戊酸和乙烯的分子内消除反应的重要作用。特别地，该反应在热解条件下对戊酸乙酯的分解具有独特的意义，这表明热解实验可以为其速率常数提供关键的约束条件。随后在较高温度下戊酸的分解反应会富集中间库，尤其是自由基 并可以继续生产乙烯，以使其摩尔分数在喷射搅拌的反应器热解过程中在研究的温度范围内保持增长。在火焰传播条件下，C₀ C ₁反应对火焰传播具有最高的敏感性系数，而参与乙烯和乙烯基的反应由于乙烯的大量生产也起着重要作用。