Composition Dependence of Nonequilibrium Effects in Gas‐Phase Reactions
Composition Dependence of Nonequilibrium Effects in Gas‐Phase Reactions
复制标题
气相反应中非平衡效应的组成依赖性
DOI：
10.1063/1.1725565
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发表时间：
1964
影响因子：
4.4
通讯作者：
J. Ross
中科院分区：
文献类型：
--
作者：
C. W. Pyun;J. Ross
化学反应的过程扰乱了反应物和生成物的平动分布和内部分布。通过对所有反应物和生成物的适当玻尔兹曼方程的一阶扰动解，推导出在稀相、均相和等温气相中发生的不同定义的反应速率系数的非平衡分布效应的组成和亲和依赖性。一般来说，正反速率系数的比值与平衡常数的差异程度取决于非平衡分布的影响程度；一个例外是在大量过量惰性气体中进行异构化或激发反应时，在各自无限亲和极限下的表观正反速率系数的比值。详细的计算给出了这种情况和其他一些简单的情况，包括硬球分子的双分子反应和只有两种内部状态的组分的反应。在极限下……
The process of a chemical reaction perturbs the translational and internal distributions of reactants and products. The composition and affinity dependences of the effects of the nonequilibrium distributions are derived for variously defined rate coefficients of reactions occurring in a dilute, homogeneous, and isothermal gas phase by a first‐order perturbation solution of appropriate Boltzmann equations for all reactants and products. In general, the ratio of forward‐to‐reverse rate coefficient differs from the equilibrium constant to the extent of the influence of the nonequilibrium distributions; one exception is the ratio of the apparent forward‐to‐reverse rate coefficient in the respective limits of infinite affinity for an isomerization or excitation reaction proceeding in large excess of inert gas. Detailed calculations are presented for this and some other simple cases including a bimolecular reaction of hard‐sphere molecules and a reaction with components in only two internal states. In the limit...