3‐Carene is an important potential biofuel with properties similar to the jet‐propellant JP‐10. Its thermal decomposition and combustion behavior is to date unknown, which is essential to assess its quality as a fuel. A combined experimental and kinetic modeling study has been conducted to understand the initial decomposition of 3‐carene. The pyrolysis of 3‐carene was investigated in a jet‐stirred quartz reactor at atmospheric pressure, at temperatures varying from 650 to 1050 K, covering the complete conversion range. The decomposition of 3‐carene was observed to start around 800 K, and it is almost complete at 970 K. Online gas chromatography shows that primarily aromatics are generated which suggests that 3‐carene is not a good fuel candidate. The potential energy surface for the initial decomposition pathways determined by KinBot shows that a hydrogen elimination reaction dominates, giving primarily cara‐2,4‐diene. Next to this molecular pathway, radical pathways lead to aromatics via ring opening. The kinetic model was automatically generated with Genesys and consists of 2565 species and 9331 reactions. New quantum chemical calculations at the CBS‐QB3 level of theory were needed to calculate rate coefficients and thermodynamic properties relevant for the primary decomposition of 3‐carene. Both the conversion of 3‐carene and the yields of the primary products (ie, benzene and hydrogen gas) are well predicted with this kinetic model. Rate of production analyses shows that the dominant pathways to convert 3‐carene are hydrogen elimination reaction and radical chemistry.

中文翻译：

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3-烯热解的详细实验和动力学建模研究

3-Carene是一种重要的潜在生物燃料，其性质类似于喷气推进剂JP-10。迄今为止，其热分解和燃烧行为尚不清楚，这对于评估其作为燃料的质量至关重要。进行了组合的实验和动力学建模研究，以了解3-烯的初始分解。在大气压下，在650至1050 K的温度范围内，在射流搅拌的石英反应器中研究了3-烯的热解，涵盖了整个转化范围。观察到3-烯的分解在800 K附近开始，并且在970 K时几乎完全分解。在线气相色谱显示主要生成芳烃，这表明3-烯不是很好的燃料候选物。KinBot确定的初始分解途径的势能面表明，氢消除反应占主导地位，主要生成cara-2,4-diene。在此分子途径旁边，自由基途径通过开环导致芳族化合物。动力学模型由Genesys自动生成，由2565种和9331个反应组成。需要在CBS-QB3理论水平上进行新的量子化学计算，以计算与3-烯的一次分解有关的速率系数和热力学性质。用该动力学模型可以很好地预测3-烯的转化率和初级产物（即苯和氢气）的产率。产率分析表明，转化3-烯的主要途径是氢消除反应和自由基化学。