HAMMETT PLOTS substituent effects => field, resonance, inductive, polarizability and steric effects ; the first 4 are

electronic effects; together, these are stereoelectronic effects steric effects are electronic in origin since they are repulsions brought about by atoms approaching within their respective van der Waals distances, where electron clouds of the groups repel each other Hammett plots are used to picture how reaction mechanisms change as a function of electronic changes induced by substituents ; it is defined using the dissociation of benzoic acid and the ability of meta or para substituents to influence its acidity ; ortho groups are excluded to eliminate steric effects

the substituent parameter x is defined using H=0

> 0 => the substituted benzoic acid is less acidic than benzoic acid => EWG < 0 => the substituted benzoic acid is more acidic than benzoic acid => EDG usually, p > m since para substituents can influence the charge at the ipso carbon via resonance

 -OH and OR groups are EW in the meta position (inductive effect) but are ED in the para position (resonance effect)

to determine if the reaction mechanism creates a positive or negative charge, the slope of the Hammett plot is defined:

describes the sensitivity of the new reaction to substituent effects relative to the influence of the substituent on the ionization of benzoic acid >1 => more sensitive to substituents than benzoic acid and negative charge is building up 0 < < 1 => less sensitive to substituents than benzoic acid but negative charge is building up ~0 => no substituent effects => no change occurs in the RDS < 0 => build up of positive charge