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If σp + values correlate better than σp values, then it can be implied that a carbocation conjugated with the benzene ring is being created in the transition state. A survey of Hammett substituent constants and resonance and field parameters - cr00002a004. 0." COI "1 . c.a 0.26 con {—055) cm . lea . 030 o,ss . 1.15 . -00 . "a 0.82 . .10 . 0.4* . -0.15 . laa. Hammett's correlation covers chemical reactivity, spectroscopy and other physical properties, and even the biological activity of drugs. Virtually all quantitative treatments of reactivity of organic. In our next post, we’ll explain the reasons for both ortho-, para- and meta- direction, and try to show why halogens fit in the former category but not the latter.

Atomic parameters (IE, EA, D, ...) While substituents on the meta and para positions exert only electronic effects on ionization, substituents on the ortho position cause steric effects as well. The Hammett constant σR for a. To derive the Hammett equation, we need to recall the quantitative relationship between the structure and reactivity first. To do so, we need to find some mathematical parameter that can. Direct application of the I-Iammett equation to ortho-substituted benzene derivatives is unsuccessful, due to steric effects. In this equation is the reference reaction rate of the unsubstituted reactant, and k that of a substituted reactant. A plot of for a given equilibrium versus for a given reaction rate with many.