These relations can be exploited to elucidate the mechanism of a reaction. As the value of ρ is related to the charge during the rate determining step, mechanisms can be devised based on this information. If the mechanism for the reaction of an aromatic compound is thought to occur through one of two mechanisms, the compound can be modified with substituents with different σ values and kinetic measurements taken. Once these measurements have been made, a Hammett plot can be constructed to determine the value of ρ. If one of these mechanisms involves the formation of charge, this can be verified based on the ρ value. Conversely, if the Hammett plot shows that no charge is developed, i.e. a zero slope, the mechanism involving the building of charge can be discarded. Hammett plots may not always be perfectly linear. For instance, a curve may show a sudden change in slope, or ρ value. In such a case, it is likely that the mechanism of the reaction changes upon adding a different substituent. Other deviations from linearity may be due to a change in the position of the transition state. In such a situation, certain substituents may cause the transition state to appear earlier (or later) in the reaction mechanism. Dominating electronic effects 3 kinds of ground state or static electrical influences predominate: Resonance (mesomeric) effect Inductive effect: electrical influence of a group which is transmitted primarily by polarization of the bonding electrons from one atom to the next Direct electrostatic (field) effect: electrical influence of a polar or dipolar substituent which is transmitted primarily to the reactive group through space (including solvent, if any) according to the laws of classical electrostatics The latter two influences are often treated together as a composite effect, but are treated here separately. Westheimer demonstrated that the electrical effects of π-substituted dipolar groups on the acidities of benzoic and phenylacetic acids can be quantitatively correlated, by assuming only direct electrostatic action of the substituent on the ionizable proton of the carboxyl group. Westheimer's treatment worked well except for those acids with substituents that have unshared electron pairs such as –OH and –OCH3, as these substituents interact strongly with the benzene ring. Roberts and Moreland studied the reactivities of 4-substituted bicyclo[2.2.2]octane-1-carboxylic acids and esters. In such a molecule, transmission of electrical effects of substituents through the ring by resonance is not possible. Hence, this hints on