Field and Resonance Components of Substituent Effects in Relation to the Hammett Equation

Following Swain and Lupton's analysis of substituent effects, we have taken ΔG0 = aete + artr for a typical substituent effect reaction. In this equation ae and ar are substituent constants for electrostatic field and resonance effects while te and tr are corresponding transmission coefficients. Both substituent constants and tr are taken to be independent of solvent and temperature, while te is taken to depend on both solvent and temperature. General conclusions based on analysis of this model are the following. (i) A Hammett ρσ equation with constant σ values that are valid over a range of temperatures for a variety of reactions in several solvents can be obtained only when either the field or the resonance interaction is negligible compared with the other. (ii) A Hammett ρσ equation can be expected to hold for "similar" reaction series in a given solvent at one temperature even when both the field and resonance interactions are important, (iii) An isoequilibrium or isokinetic relationship can be expected only when the field interaction is dominant.The general equations leading to these and other conclusions are presented so that one can later insert appropriate mathematical descriptions of detailed models and thereby obtain information about specific reactions.