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Experiment 8
RELATIVE RATES OF ELECTROPHILIC AROMATIC SUBSTITUTION
II.Discussion
The rate-determining step of electrophilic aromatic substitution is the first step in which the
aromatic ring attacks an electrophile. This breaks the aromaticity of the formally aromatic ring. Then, in a
subsequent faster step, a hydrogen is lost to restore aromaticity of the aromatic ring. This aromaticity
causes the product to become more stable, which is also favored. Normally in substitution across a double
bond, the nucleophile then attacks the carbocation. In the case of Arenes however, this mechanism is
carried out differently. In aromatic compounds, the aromaticity of the compound would be lost, and the
activation energy for the reaction is too high. Instead the nucleophile acts as a base to remove the proton.
The net result is that one of the hydrogens is substituted for the electrophile. The electrophile is created
by breaking apart bromine via a heterolytic cleavage that produces a Br- and a Br+. The bromine cation
acts as the electrophile and is created in the presence of acetic acid. The electrophile then reacts with a
double bond in the arene (the nucleophile), making a bond and forming an arene cation. This arene cation
is then deprotonated, forming the product.
The main purpose of this experiment is to examine the effect of substituents present on the ring
on the rate of electrophilic aromatic substitution. Also, to examine the effect of solvent on the rate of
electrophilic aromatic substitution. The related structures chosen for this experiment are benzene,
chlorobenzene, phenol, nitrophenol, aniline, and acetanilide.
Usually, halogenations of an aromatic ring are performed using an iron catalyst; however, if a
catalyst were used, the reaction would happen too fast to follow using a spectrophotometer. In order to
monitor the reaction using a spectrophotometer, it is assumed that the measured absorbance is directly
proportional to the current concentration of bromine {Beer’s Law: Absorbance = molar absorptivity (L
mol-1 cm-1) * cell path length (cm) * concentration (M)}. All solutions used in this experiment, except the
bromine solution, are clear and colorless, so they should not have much (if any) effect on the total
absorbance measured.
III.Conclusion
In doing this experiment, it is important to determine the effects of the substituents, solvent, and
temperature. The presence of a substituent affects the reactivity and orientation of the ring, whereas, a
substituent more reactive than benzene is termed as an activator and are classified as ortho- para-
directors, while a substituent less reactive than benzene is termed as deactivators and are classified as
meta-directors. In terms of solvents, the more polar the solvents, the faster rates of reaction would occur,
the same goes for temperature, whereas, the higher the temperature, the rates of electrophilic aromatic
substitution reaction would react faster.
IV.References