Gallis Michael A, Bond Ryan B, Torczynski John R
Department of Microscale Science and Technology, Sandia National Laboratories, P.O. Box 5800, Albuquerque, New Mexico 87185-0346, USA.
J Chem Phys. 2009 Sep 28;131(12):124311. doi: 10.1063/1.3241133.
Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.
最近提出的分子水平化学模型仅使用动力学理论和基本分子性质(即无宏观反应速率信息)来预测平衡和非平衡反应速率,本文针对高层大气高超声速流动中发生的化学反应对这些模型进行了研究。对于近平衡条件下的情况,新模型与测得的阿仑尼乌斯速率吻合良好;对于远离平衡条件的情况,新模型与测得的速率以及其他理论模型均吻合良好。此外,新模型被应用于典型的燃烧和电离反应,与现有测量结果和理论模型吻合良好。因此,分子水平化学建模为预测气体中的平衡和非平衡化学反应速率提供了一种准确的方法。