Taft equation standard substituent

Taft [109] postulated that the rate of aliphatic ester hydrolysis is a function of substituent type. Using methyl as a standard substituent, he compared, for example, the effects of larger alkyls, and interpreted the results by means of two constants characterizing the steric and polar behaviour of the alkyls. In copolymerization theory, the Taft equation was used many times to describe the relative reactivities (See Chap. 5, Sect. 5.2) in homologous polymer series... 

In Taft s treatment the acid- and base-catalysed hydrolysis of substituted esters X-COOR are employed as combined reference reactions for defining polar and steric effects for the substituent X. Equation (5) governs the combined inductive, steric (5) and resonance (R) effects on the rate of a reaction.Equations (6) and (7) can be written for base-and acid-catalysed hydrolysis using methyl (Me) as the standard substituent. 

Equation (31) expresses the dependence of the relative rate (equilibrium) constant on the properties of the solvent characterized by the parameters Ap and Sp. The parameter Rp is proportional to the differences between the relative Gibbs free energies for the nth and sth solvent of the given and standard substrates. The parameter Sp characterizes the effect of a change of the substrate on the rate constant of the substrate with a standard substituent. In the Hammett equation this substituent is represented by hydrogen for which a was definitionally put equal to zero, while in the Taft and Taft-Pavelich equations methyl is used as the standard substituent [a = = 0). 

The alternative approach is the attempt to quantify substituent effects, and this has been most successfully done by the Hammett equation and its various extensions (Hammett, 1970). Here one set of free energy data is compared with another set. One set is taken as standard (originally the dissociation constants of benzoic acids) and other rate or equilibrium data are compared (by logarithmic plots). So much has been written about this treatment that discussion here is unnecessary. Absolute values of a (the substituent constant) are not to be expected, in fact one would expect a different a for every reaction (i.e. for every p). In the present context it is important to note that both the Hammett equation and the closely related Taft treatment are based on systems where solvation is known to be important and therefore the application of these treatments using parameters derived from solution phase studies to reactions in the gas phase may be of uncertain value. 

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