Nonequilibrium Effects in the Kinetics of Isomerization Reactions and in the Kinetics of Dissociation and Recombination of Diatomic Molecules
Nonequilibrium Effects in the Kinetics of Isomerization Reactions and in the Kinetics of Dissociation and Recombination of Diatomic Molecules
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异构化反应动力学和双原子分子解离重组动力学中的非平衡效应
DOI：
10.1063/1.1695971
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发表时间：
1965
影响因子：
4.4
通讯作者：
N. Snider
中科院分区：
文献类型：
--
作者：
N. Snider
研究了经历解离和重组的双原子分子系统以及经历异构化的分子系统的时间演化。每种情况的起点都是主方程。该研究的具体目的是确定在什么条件下时间演化可以用适当的唯象方程[方程1]来描述。 (1) 或 (2)] 并确定唯象方程在远非平衡条件下是否成立，其中正向和反向速率常数的比率不是平衡常数。在异构化中，发现适当的唯象方程 [Eq. (2)]在足够长的时间后总是成立。在解离重组中存在系统，其中适当的现象学方程[方程。 (1)] 永远不成立。为了使该方程成立，必须满足涉及基本过程的速率常数和原子浓度的某些必要条件...
A study was made of the time evolution of a system of diatomic molecules undergoing dissociation and recombination and of a system of molecules undergoing isomerization. The starting point in each case was a master equation. The particular aims of the study were to determine the conditions under which the time evolution is describable by the appropriate phenomenological equation [Eq. (1) or (2)] and also to determine whether or not the phenomenological equations can hold under far from equilibrium conditions with forward and reverse rate constants whose ratio is not the equilibrium constant. In the isomerization it was found that the appropriate phenomenological equation [Eq. (2)] always holds after a sufficiently long time. In dissociation—recombination there exist systems in which the appropriate phenomenological equation [Eq. (1)] never holds. Certain necessary conditions involving rate constants for the elementary processes and the atom concentration must be fulfilled in order for this equation to eve...