Organic Chemistry Laboratory Manual 1

EXPERIMENT 9. RELATIVE RATES OF ELECTROPHILIC AROMATIC SUBSTITUTION

Electrophilic aromatic substitution (EAS) is an organic reaction in which a hydrogen atom

attached to the aromatic ring is replaced by an electrophile (E+). The mechanism of an EAS
reactions involves two steps, 1) the rate-determining step which is the generation of a positively-
charged intermediate when an E+ forms a sigma bond to the aromatic ring, and 2) the fast step
which is the abstraction of a proton from the intermediate to yield a substituted aromatic ring.

H H H
E E E E
slow
E H+

The rate of EAS depends on the stability of the intermediate. The lower the activation
energy needed for the formation of the intermediate, the more stable the intermediate; thus, the
more readily the product is formed.

The presence of substituents in an aromatic ring affects the rate of EAS. An electron-
donating substituent activates the ring towards EAS by increasing the electron density on the
aromatic ring making it more electron-rich and more reactive to an electrophile. Electron-
donating substituents also stabilize the positively charged intermediates by resonance or
inductive effects. An electron-withdrawing group, on the other hand, withdraws electron density
from the ring making it less reactive towards an electrophile. It deactivates the ring towards EAS
by destabilizing the resulting intermediate formed.

One example of EAS is halogenation of aromatic compounds using elemental bromine

or chlorine. It is normally carried out in the presence of a Lewis acid that acts as a catalyst.
Unlike alkenes, the more tightly held p electrons of aromatic compounds could not polarize the
halogen molecule to such extent that can cause the weak halogen-halogen bond to break.
FeBr3 for instance, is commonly used as Lewis acid in an EAS reaction. It polarizes the halogen
molecule and helps further weaken the halogen-halogen bond by forming a complex as shown
below. The p-electron system of the benzene ring attacks the Br+ ion that is generated.

Br Br -
Br
δ+ δ-
Br Br Fe Br Br Br Fe Br Br Fe Br + Br+
Br Br Br

A polar solvent can also assume the role of a Lewis acid. It stabilizes the positively-
charged intermediate generated in the rate-determining step and it influences the rate at which
the intermediate loses H+.

In this experiment, the relative reactivity of various substituted benzene towards

bromination will be determined and compared.

Organic Chemistry Group ● Institute of Chemistry ● University of the Philippines Diliman

Organic Chemistry Laboratory Manual 2

MATERIALS AND APPARATUS

Test solutions: 0.2 M solutions in ethyl acetate:

chlorobenzene, phenol, nitrophenol, benzaldehyde, toluene

measuring pipettes (5 mL) test tubes

0.05 M Br2 in 90% CH3COOH Pasteur pipettes
0.05 M Br2 in cyclohexane

PROCEDURE

A. Relative Rates of Bromination

Add 2 drops each of the test solutions in separate 4” test tubes (Note 1). To each of the
test solutions, add 2 drops of 0.05 M Br2 in 90% CH3COOH. Note the time of addition. Shake
and store them away from light (Notes 2 and 3). Record the time it takes for decolorization to
take place. Theoretically, the observed color change should be from yellow to pale yellow or
colorless. If there is no color change observed within 30 minutes, warm the solution mixture in a
hot water bath. Record your observations.

B. Effects of Solvents on Reaction Rates

Place 5 drops of toluene solution in two test tubes. Add 5 drops of 0.05 M Br2 in
cyclohexane to one test tube, and 5 drops of 0.05 M Br2 in 90% CH3COOH to another test tube.
Note the time of addition and observe for any sign of a reaction. Record the time of the
decolorization. Compare the results.

NOTES

1. Use test tubes of the same diameter and size.

2. Perform the whole experiment in dark conditions.

3. Make sure to prepare a control solution for comparison.

WASTE DISPOSAL

Dispose all solvents in “halogenated organic waste” jar.

REFERENCES

Helmkamp GK and Johnson HW Jr. 1983. Selected Experiments in Organic

Chemistry. W.H Freeman and Co., New York

Knipe AC and Watts WE. 1993-1994. Organic Reaction Mechanisms: Annual Survey.

McKenzie C. 1967. Experimental Organic Chemistry. Prentice Hall, New Jersey

Organic Chemistry Group ● Institute of Chemistry ● University of the Philippines Diliman