Abstract

A semi-empirical level-based model is developed that describes the detailed kinetics of the formation and decay of hydrogen atoms during relaxation of the vibrational energy of hydrogen molecules in the gas phase of a microwave discharge in liquid hydrocarbons in the range of the translational temperature from 600 to 3000 K at atmospheric pressure. It is shown that, depending on the conditions in the gas phase, the monomolecular decomposition of hydrogen can consist of two stages—the early and late stages. At the early stage, the dissociation of a hydrogen molecule occurs with a non-equilibrium energy distribution over the internal degrees of freedom of the molecule. At the late stage, chemical equilibrium in the concentration of hydrogen atoms is established. The specific energy stored in the vibrational degree of freedom of the hydrogen molecule decreases as a result of the dissociation of molecules during the equilibrium between the translational-rotational and vibrational degrees of freedom of the molecule. As a result, the relaxation time of the vibrational energy increases and becomes equal to the time at which the equilibrium of hydrogen atoms concentration is established.

中文翻译：

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液态烃中微波放电中分子氢解离的非平衡动力学

摘要

建立了基于半经验水平的模型，该模型描述了在平移温度范围内液态烃中微波放电的气相中氢分子的振动能在氢分子的振动能弛豫期间氢原子形成和衰变的详细动力学。在大气压下为600至3000K。结果表明，取决于气相的条件，氢的单分子分解可以包括两个阶段-早期和晚期。在早期阶段，氢分子的解离以分子内部自由度上的非平衡能量分布发生。在后期，建立氢原子浓度的化学平衡。由于在分子的平移-旋转和振动自由度之间的平衡期间分子解离的结果，存储在氢分子的振动自由度中的比能降低。结果，振动能量的弛豫时间增加并且变得等于建立氢原子浓度平衡的时间。