Pathological detonations are detonations with a propagation velocity higher than the classical Chapman–Jouguet velocity and which depends on the wave structure. Such a behavior has been experimentally observed in low-pressure hydrogen-chlorine mixtures and important discrepancies were reported between the experimental and the theoretical velocities. Using the steady planar detonation model, along with a state-of-the-art chemical mechanism this work aims at investigating two aspects potentially responsible for these discrepancies: (i) the impacts of uncertainties in chemical kinetics mechanisms, and (ii) thermal non-equilibrium effects. The uncertainties in the rate constants of reactions R2: 2Cl+M=Cl+M and R3: Cl+H=HCl+Cl are found to be the dominant sources of uncertainty for the steady propagation velocity and the induction length of the pathological detonations. The multi-temperature, thermal non-equilibrium model is found to provide generally higher detonation velocity than the experimental value and the eigenvalue solutions obtained under thermal equilibrium. Nevertheless, for specific values of the initial vibrational temperature of HCl, the results can be closer to the experimental values. This latter aspect provides the motivation for future work that relies on more comprehensive thermal non-equilibrium modeling.

中文翻译：

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H[式略]-Cl[式略]混合物中的病理爆炸：不确定性量化和热非平衡效应

病态爆炸是传播速度高于经典查普曼-茹格速度的爆炸，并且取决于波结构。这种行为已在低压氢氯混合物中通过实验观察到，并且实验速度与理论速度之间存在重要差异。使用稳定平面爆轰模型以及最先进的化学机制，这项工作旨在研究可能导致这些差异的两个方面：（i）化学动力学机制中的不确定性的影响，以及（ii）热非- 平衡效应。反应 R2: 2Cl+M=Cl+M 和 R3: Cl+H=HCl+Cl 的速率常数的不确定性被发现是病理爆炸的稳定传播速度和诱导长度不确定性的主要来源。发现多温度热非平衡模型通常提供比实验值和热平衡下获得的特征值解更高的爆速。然而，对于HCl初始振动温度的特定值，结果可以更接近实验值。后一个方面为未来依赖于更全面的热非平衡模型的工作提供了动力。