Kinetic consequences of the principle of microscopic reversibility
Kinetic consequences of the principle of microscopic reversibility
复制标题
微观可逆性原理的动力学后果
DOI：
10.1039/tf9666202754
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发表时间：
1966
影响因子：
--
通讯作者：
K. Laidler
中科院分区：
文献类型：
--
作者：
R. M. Krupka;H. Kaplan;K. Laidler
对平衡状态下的基本反应，提出了微观可逆性原理。根据这一原理，对于任何处于平衡状态的体系，对于任何处于平衡状态的基本反应，无论是否处于平衡状态，在一个方向上有利的反应路径必须与在相反方向上有利的反应路径相反，并且速率常数之比就是平衡常数。在稳态条件下发生的非链式反应也是如此，只要备选路径就动力学顺序而言是等效的。对于在非稳态条件下发生的反应，对于稳态链式反应，以及对于可选路径不具有动力学等效的非链式反应，一个方向上的首选反应路径可能与另一个方向上的不同；在这种情况下，总速率常数的比值不等于平衡常数。当微观可逆性原理已经建立时，就永远不能用它来证明一个反应的机理；它只能用来消除动力学等效机制，而不是完全相反方向的反应。
The principle of microscopic reversibility was formulated for elementary reactions at equilibrium. It follows from the principle that for any system at equilibrium, and for any elementary reaction whether at equilibrium or not, the favoured reaction path in one direction must be the reverse of that in the opposite direction, and that the ratio of rate constants is the equilibrium constant. The same is true for non-chain reactions occurring under steady-state conditions provided that the alternative paths are equivalent as far as kinetic order is concerned. For reactions occurring under non-steady-state conditions, for chain reactions even in the steady state, and for non-chain reactions in which the alternative paths are not kinetically equivalent, the preferred reaction path in one direction may be different from that in the other; in such cases the ratio of the overall rate constants is not equal to the equilibrium constant. The principle of microscopic reversibility can never be used to prove the mechanism of a reaction when that for the reverse reaction has been established; it can only be used to eliminate kinetically equivalent mechanisms which are not the exact reverse of that for the reaction in the opposite direction.