溶液中单分子-双分子反应A+B⇌C的一般动力学规律。

General kinetic laws of monomolecular-bimolecular reaction A+B <= => C in solutions.

作者信息

Doktorov A B, Kadetov A A, Kipriyanov A A

机构信息

Institute of Chemical Kinetics and Combustion, SB RAS, 630090, Novosibirsk, Russia.

出版信息

J Chem Phys. 2004 May 8;120(18):8662-70. doi: 10.1063/1.1701842.

DOI:10.1063/1.1701842

PMID:15267795

Abstract

Non-Markovian kinetic equations of the reversible monomolecular-bimolecular reactions of the type A+B right arrow over left arrow C (at arbitrary ratio between A and B concentrations) derived earlier are used in the calculation of kinetics on macroscopic space-time scales. It is found that the kinetics of the systems with different structure of reactants is universal, and it is the direct generalization of the kinetic law of mass action of formal chemical kinetics. The analysis of the kinetics allows one to establish the time range of the applicability of the law of mass action. It is shown that beyond these limits the usual kinetic law of mass action becomes invalid, and correct description of the kinetics even in the most rough approximation calls for the non-Markovian corrections to usual kinetic laws.

摘要

先前推导的A + B ⇌ C型可逆单分子 - 双分子反应（A和B浓度比例任意）的非马尔可夫动力学方程被用于宏观时空尺度上的动力学计算。发现具有不同反应物结构的系统的动力学具有普遍性，并且它是形式化学动力学质量作用动力学定律的直接推广。对动力学的分析使人们能够确定质量作用定律的适用时间范围。结果表明，超出这些限制，通常的质量作用动力学定律变得无效，并且即使在最粗略的近似下，要正确描述动力学也需要对通常的动力学定律进行非马尔可夫修正。