Linear Free Energy Relationships
Linear Free Energy Relationships
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线性自由能关系
DOI：
10.1021/cr60222a005
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发表时间：
1968
期刊：
影响因子：
--
通讯作者：
P. R. Wells
中科院分区：
文献类型：
--
作者：
P. R. Wells
了解反应性对许多反应变量的依赖性，特别是底物结构、试剂结构和反应介质，是化学的主要目标之一。从定性的角度来看，主要反应类型的更重要特征已经被认识，并且许多单个反应的更详细的细节已经得到澄清。然而，根据理论对即使是最简单的过程的结果、速度和范围进行定量预测仍然是未来的目标。带着这个目标，当前的研究试图在定量的基础上建立完善的定性概念，作为更精确理论的必要垫脚石。在过去的三十年中，利率和均衡数据的稳步积累导致了许多经验相关性的形成。这些有望简化理论问题，使注意力集中在一个或两个反应变量上，而其他变量基本保持不变。这些相关性的一般形式是一个反应 (A) 的速率或平衡常数的对数与经历相同反应物结构或反应条件变化的第二个反应 (B) 的速率或平衡常数的对数之间的线性关系。（每组速率或平衡常数称为反应级数。）该关系可以用方程表示1
An understanding ofthe dependence of reactivity upon the many reaction variables, particularly sub-strate structure, reagent structure and reaction me-dium, is one of the primary aims of chemistry. In qualitative terms the more important features of the main reaction types have been recognized, and thefiner details of many individual reactions havebeen clarified. The quantitative prediction from theory ofthe result, velocity and extent of even the simplest processes is, however, still an objective for the future. With this aim in view current investigations seek to place on a quantitative basis well-established qualitative concepts as a necessary stepping stone to more precise theories. During the past three decades the steady accumula-tion of rate and equilibrium data has led to the formulation of a number of empirical correlations. These promise to simplify the theoretical problem by per-mitting attention to be focused on only one or two of the reaction variables, while the others are held es-sentially constant.The general form of these correlations is a linear relationship between the logarithms of the rate or equilibrium constants for one reaction (A) and those for a second reaction (B) subjected to the same variations of reactant structure or reaction conditions.(Each set of rate or equilibrium constants is termed a reaction series.) The relationship may be expressed by equation 1