In this work a comparison between redox potentials, obtained by constructing current-potential plots from chronoamperometric measurements, and the parameter sigma(x), as proposed by Zuman in terms of the Hammett substituent parameters, was performed for several quinone compounds. This study shows the limitations of this approach and proves that methods based on quantum chemistry can be used to study the substituent effect in quinone systems. By using the Density Functional Theory, in the Kohn-Sham context with three exchange-correlation functionals, BLYP, B3LYP, and BHLYP, it was found that the electron affinity is good enough to give a useful relationship with experimental redox potentials of quinone systems. This conclusion is reached when the basis set functions involve diffuse functions, and also when the Hartree-Fock exchange energy is included in the exchange-correlation functional. The Fukui function, to describe preferential sites involved at initial stages of a system that bind an electron, is analyzed when electron donor and electron acceptor groups are present as substituents in quinone systems. The methods applied in this work are valid for any kind of quinone compound and will be used in further analysis of the electron reorganization in semiquinone species.