Kate Coleen D.

Galera BS in Chemistry II April 17, 2107

Experiment 8
RELATIVE RATES OF ELECTROPHILIC AROMATIC SUBSTITUTION

I.Data and Results

A. Relative Rates of Bromination
Compound Time of Decolorization Observations
Benzene 1 minute From colorless solution, it
contained an immiscible layer
and turned pale yellow in color.
Chlorobenzene 1minute and 42 seconds The colorless solution produced
immiscible layer and turned
pale yellow in color.
Phenol 1.2 seconds The solution have an immiscible
layer and was transparent in
color.
Nitrophenol 7 seconds There was no color change.
Aniline 2 minutes and 18 seconds From colorless solution turned
pale yellow in color.
Acetanilide 9seconds From colorless solution turned
pale yellow in color.
The first one to become pale yellow is phenol followed by nitrophenol, acetanilide, benzene,
chlorobenzene and aniline.
B. Effects of Solvents on Reaction Rates
Compound Time of Decolorization Observations
Acetanilide + Bromine in 2minutes and 53 seconds From yellow color of solution
Cyclohexane turned pale yellow.
Acetanilide + Bromine in acetic 53 seconds From pale yellow color of
acid solution turned colorless.

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.

The general reaction is:

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

McMurry, John. Organic Chemistry. Thomson Publications. 2004

“Factors Affecting Relative Rates of Electrophilic Aromatic Subsitution”

https://www.scribd.com/document/292854915/Factors-Affecting-the-Relative-rates-of-Electrophilic-
Aromatic-Substitution-Reactions

“Affecting Relative Rates of Electrophilic Aromatic Subsitution”

“https://www.coursehero.com/file/7816626/Relative-Rates-of-Aromatics-Lab/

“Affecting Relative Rates of Electrophilic Aromatic Subsitution”

https://www.scribd.com/document/331627043/Experiment-9