Correlation Methods for Kinetic Data Linear Free Energy Relations

4 CORRELATION METHODS FOR KINETIC DATA LINEAR FREE ENERGY RELATIONS 

It is instructive to consider the rationale nnderlying the various linear free energy correlations and to indicate in qualitative fashion how substituents may inflnence reaction 

Since the transition state formnlation of a reaction rate expression treats the activated complex as being in equilibrium with the reactants, the resnlting expression for the reaction rate constant depends similarly on the free-energy difference between reactants and the activated complex. In this case equation (4.3.34) can be rewritten as 

Consider two molecnlar processes involving the reaction of structurally similar reactants with a common reagent. For example, 

When one looks at the general reaction systems from Ihe standpoint of the kineticist, species YNXjA would represent the transition state configuration. In this case, equation (7.4.2) indicates that 

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CORRELATION METHODS FOR KINETIC DATA—LINEAR FREE ENERGY RELATIONS... 

Correlation Methods for Kinetic Data Linear Free Energy Relations 203... 

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