Rogeni Misaelle M.

Petinglay Date performed: March 30, 2017

B.S. in Chemistry II Date submitted: April 10, 2017

Experiment No. 8
RELATIVE RATES OF ELECTROPHILIC AROMATIC SUBSTITUTION

I. Summary of Results

Table 1. Relative Rates of Bromination

Test Physical Time of Appearance of
Solutions Properties Pale Yellow Solution
0.2 M solutions in ethyl
Colorless solution 4 minutes
acetate of benzene
0.2 M solutions in ethyl 1 minute and
Colorless solution
acetate of chlorobenzene 42 seconds
0.2 M solutions in ethyl
Colorless solution 1.2 seconds
acetate of phenol
0.2 M solutions in ethyl 4 minutes and 30
Very pale yellow solution
acetate of nitrophenol seconds
0.2 M solutions in ethyl
Very pale yellow solution 19 seconds
acetate of aniline
0.2 M solutions in ethyl
Colorless solution 9 seconds
acetate of acetanilide

Table 2. Effects of Solvents on Reaction Rates

Color of Time of
Solution Observations
0.05 M Br2 Decolorization
0.05 M Br2 in
Red orange (in 2 minutes and 53 Color change: Pale yellow to
cyclohexane +
cyclohexane) seconds colorless solution
acetanilide
0.05 M Br2 in
Orange (in Color change: Yellow to pale
CH3COOH + 53 seconds
CH3COOH) yellow solution
acetanilide

II. Discussion

Electrophilic aromatic substitution is the characteristic reaction of benzene where in a

hydrogen atom is replaced by an electrophile. Many substituted benzene rings undergo
electrophilic aromatic substitution. Halogens, OH, NH2, alkyl, and many functional groups that
contain a carbonyl are some common substituents. These substituents can affect the course of
electrophilic aromatic substitution and can either increase or decrease the electron density in the
bezene ring.
Relative Rates of Bromination

In this part of the experiment the effect of substituents present on the ring on the rate of
electrophilic aromatic substitution was examined. 0.2 M solutions in ethyl acetate of: benzene,
chlorobenzene, phenol, nitrophenol, aniline, and acetanilide were used as test solutions. Two
drops each of the test solutions was placed in separate test tubes and added with two drops of
0.05 M Br2 in 90% CH3COOH. The time where in the solutions became very pale yellow was
noted and compared to a control solution. A reaction has occurred if there is a change in color.

Substituents can generally be divided into two classes regarding electrophilic

substitution: activating and deactivating towards the aromatic ring. Activating groups stabilize
the cationic intermediate formed during the substitution by donating electrons into the ring
system, by either inductive effect or resonance effects. This makes the reaction faster. On the
other hand, deactivating substituents destabilize the intermediate cation and thus decrease
the reaction rate.

The results of the experiment show that nitrophenol and aniline turned very pale yellow
while the remaining test solutions were colorless and the arrangement of increasing rate of
reactivity is nitrophenol< benzene < chlorobenzene < aniline < acetanilide < phenol. However
these experimental results deviated from the theorectical data. Theoretically, in increasing
arrangement, it should be, nitrophenol < chlorobenzene < benzene < acetanilide < phenol <
aniline. Amine contains an amino group while acetanilide has acylamino group. Chlorobenzene
has a halogen group while phenol has a hydorxyl group. Benzene has only hydogens bonded on
it while nitrophenol has a nitro group.

Effects of Solvents on Reaction Rates

In this part of the experiment, the effect of solvent on the rate of electrophilic aromatic
substitution was examined. Acetanilide was used as the sample and two different solvents were
added in separate test tubes: 0.05 M Br2 in cyclohexane and 0.05 M Br2 in 90% CH3COOH. The
time of decolorization or occurrence of any reaction was noted and the two setups were
compared.

Acetic acid tends to donate electrons on the aromatic ring making acetanilide more
reactive towards bromination. On the other hand, cyclohexane withdraws electrons from the
group making the reaction slower. The results of the experiment show that 0.05 M Br2 in 90%
CH3COOH solvent reacted faster than 0.05 M Br2 in cyclohexane solvent. In cyclohexane the
color change was from pale yellow to colorless solution while in acetic acid it was from yellow
to pale yellow solution. As predicted, the reaction of bromine took about 2 minutes and 53
seconds while the reaction of acetic acid only took 53 seconds.

By donating electrons to the aromatic ring, the rate of reaction is increased while
withdrawal of electrons to the aromatic ring can decreased the rate of reaction.
 III. Conclusion

The presence of substituents on the ring and the solvent can affect the relative rates of
electrophilic aromatic substitution. Both factors have the same concept. If the substituent is more
electronegative than the other hydrogen atoms attached to the benzene ring, the substituent has a
greater electron withdrawing ability making a slower reaction. If electrons on the sigma-bond of
substituent move more readily towards the benzene ring, the substituent has a greater electron
donating ability making a faster reaction.

Due to some errors, the experimental results did not agree with the theoretical data in the
first part of the experiment. These errors may be due to contamination of chemical reagents,
inappropriate proportions, uncontrolled environmental factors such as light and temperature and
human errors

IV. References

Smith, J. G., 2009. Organic Chemistry (3rd ed.) 1221 Avenue of the Americas, New York, NY
10020: The McGraw-Hill Companies, Inc.

Electrophilic Aromatic Substitution Reactions. Retrieved A pril 7, 2017 from

http://web.chem.ucla.edu/~harding/notes/notes_14D_EAS02.pdf

Relative Rates of Electrphilic Aromatic Substitution. Retrieved April 7, 2017 from

https://www.scribd.com/doc/295972011/RELATIVE-RATES-OF-ELECTROPHILIC-
AROMATIC-SUBSTITUTION