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CHM143L Organic Chemistry 2 Laboratory

4th Quarter SY 2013-2014

Factors Affecting the Relative Rates of Electrophilic Aromatic Substitution


Miranda, Marilyn1, Decena, Patricia Mae, T.2
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapa Institute of Technology; 2Student, CHM143L/A41, School of Chemical Engineering,
Chemistry and Biotechnology, Mapa Institute of Technology
1

ABSTRACT
This experiment mainly focuses on the electrophilic aromatic substitution reactions and the factors which affect the relative
rates for the said reactions. For the first part of this experiment, reaction of benzene, chlorobenzene, aspirin, acetanilide, pnitrophenol, anisole, and phenol with bromine solution were observed. It shows that the compounds react faster than benzene
are most likely to have an activator substituent, and those that are slower have a deactivator substituent. For the second part
of the experiment, the solvent effect, using cyclohexane and acetic acid as reagents on the bromination of anisole was also
observed. The reaction favors using the more polar solvent was favored. And for the third part, the relative rate of reaction of
acetanilide in ethyl acetate is determined based on varying temperature. By plotting the results, it can be easily observed that
temperature is directly proportional to reactivity.
Keywords: electrophilic aromatic substitution, substituent effect, temperature effect, solvent effect, bromination of aromatic compounds

INTRODUCTION
Aromatic compounds are compounds that contain a
benzene ring, a six-membered ring with conjugated double
and single bonds. These compounds do not undergo
electrophilic addition reactions although they have multiple
double bonds, but undergoes electrophiilic aromatic
substitutions, where electrophilic substitutions replaces a
certain proton on benzene with another elecrtrophile. The
weak reactivity of the compound towards addition reaction
is due to complete pi () electron delocalization or simply
termed as resonance. Such reactions in the electrophilic
aromatic substitution reaction are halogenation, nitration,
sulfonation, Friedel-Crafts alkylation and acylation. For that
substitution, the reaction consists of an electrophile (E+) and
an electron-rich aromatic ring called nucleophile. The
electrophile would then be substituted to one of the H +
attached to the benzene ring.
This experiment was all about the reaction of aromatic
compounds with bromine. In each mechanism, the rate of
formation of electrophilic bromine was first determined.
One of the double bond of the aromatic ring attacked the
electrophilic bromine. A carbocation containing a bromine
substituent then formed. To be stable again, the hydrogen
sharing the carbon bond with bromine was removed.
Electrophiles can also be attacked by substituted aromatic
compounds or with functional groups. However, there is a

Experiment 01 Group No. 3 May 8, 2014

concern with this reaction regarding regioselectivity. For a


monosubstituted benzene, there are three different reactive
positions existing, position 2 for ortho, position 3 and 5 for
meta, position 4 and 6 for para. Substituents can be
generally divided into two classes: activating and
deactivating towards the aromatic ring.
Activating groups stabilize the cationic intermediate formed
through donating electron into the ring system. These
electron density is not equally distributed into the entire
ring, but intense on ortho-para positions (2,4,6). These
positions would be the most reactive points of the
compounds towards electrophile. Examples of activated
aromatic rings are aniline, phenol, and toluene.
Unlike the deactivating substituents where they destabilizes
by withdrawing electron density from the ring particularly
again on the ortho-para positions. Thus, most unreactive
position are the meta positions (3,5). This makes the
reaction rate to slow down unlike what activating groups do.
Examples of deactivated aromatic rings are benzaldehyde
nitrobenzene and trifluoromethylbenzene.
Other factors aside from the substituents that were used in
this experiment are effect of solvent used in the reaction,
and varying temperature are also taken into consideration.

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The reactivity of a paticular substance can also be


measured through its rate. One attribute of rate is time,
which is measured as reaction takes place. For electrophilic
aromatic substitution, the factors which affect the reactivity
of the aromatic compounds can be determined through the
reaction rate. In this experiment, bromination is the reaction
that has taken place. The core aim of this experiment is to
be able to observe the factors that affect the rate of
bromination through electrophilic aromatic substitution. In
addition to that, other factors such as the effect of solvent
used and the effect of temperature were also examined.
MATERIALS AND METHODS
The experiment was performed last Thursday, 8th of May
2014. Micro test tubes, cork stoppers, test tube rack, 2-mL
pipettes, suction bulbs, thermometer, hot plate and hot
water bath are the materials and apparatuses that were
used in performing the experiments. The first part of this
experiment is all about the Substituent Effect. The test
compounds that were used here are as follows: 0.2 M in
ethyl acetate of benzene, chlorobenzene, aspirin,
acetanilide, p-nitrophenol, anisole and phenol. To start with,
0.20 mL of each test compounds was transferred into
separate micro test tubes.Then, 0.20 mL of bromine
solution was added into the micro test tubes, one at a time.
This was done for all of the test compounds. The time of
decolorization was noted once the reaction took into
completion.
For the second part of the experiment, Solvent Effect, 0.2M
anisole solutions in ethyl acetate were prepared. 0.20 mL of
it was transferred into a test tube and 0.05 M bromine in
cyclohexane was added to it. The time elapsed for the
reaction was recorded. In another micro test tube, 0.20 mL
of the anisole solution was transferred and 0.20 mL of
bromine in acetic acid was added into it. The reaction was
observed and the time elapsed was recorded.
0.2 M acetanilide in ethyl acetate was prepared for the third
part of the experiment which is the Temperature Effect. 0.20
mL of it was transferred into a micro test tube. 0.20 mL of
bromine in acetic acid was added into it. The test tube was
heated in a 50C water bath. The steps were repeated for
70C and 90C water bath.
DISCUSSION OF RESULTS
I. Substituent Effect

Experiment 01 Group No. 3 May 8, 2014

Benzene, chlorobenzene, aspirin, acetanilide, pnitrophenol, anisole and phenol were subsequently reacted
with bromine. Because of the stabilizing property of
aromatic compounds, a catalyst is really needed in order to
complete a bromination reaction. However, the bromination
of aromatic compounds is not accompanied by a catalyst,
FeBr3. Thats why the reaction is not as fast as expected.
The time of reaction for each corresponding aromatic
compounds is tabulated below.
Table 1. Aromatic Compounds Structures
and Their Time of Reaction
Compound
Time of
Structure
Decolorizati
w/
on
classificati
on
Benzene

14 minutes

Chlorobenze
ne

16 minutes

Aspirin

22 minutes

Deactivator
ortho and
para

(-COOH)
Deactivator
meta

Acetanilide

17 minutes

pnitrophenol

15 minutes
(no reaction)

Activator ortho and


para

(-NO2)
Deactivator
Meta

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Anisole

15 minutes
Activator ortho and
para

Phenol

4 seconds

Aspirin
Activator ortho and
para

All of the six compounds were reacted with bromine and


went under electrophilic aromatic substitution. When
decolorization takes places, we knew a there is a reaction
between the substances.
Substituents can affect the reactivity of aromatic
compounds. Chlorobenzene, which contains a Clsubstituent a deactivator, has the slowest rate. It is
suggested to have deactivating substituent because it
reacted slower than benzene. Benzene served as our
reference compounds since it contains no substituent. The
rest of the compounds have activating substituents. Phenol
which ideally reacted fastest has a hydroxyl substituent. It is
then followed by an anisole, aspirin, acetanilide and lastly,
p-nitrophenol.
These activating substituents are electron donating groups
which stabilizes the ring. It directs the electrophile on orthopara positions which are the most reactive points of the
ring. On the other hand, a deactivating substituent instead
of donating, tend to withdraw electrons. This substituent will
direct the electrophile to meta positions which are the less
reactive points of the ring. With this, it will make the ring
less reactive. The resonance structures can also explain
how substituents are classified. The position of carbocation
on the ring determines the orientation of where should the
electrophile would be attached, which are ortho, para or
meta positions. Resonances of each aromatic compound
are shown at the following table.

p-nitrophenol

Anisole

Phenol

Phenol reacts fastest since the atom, O, which is directly


attached to the ring is highly electronegative compared to
the atom attached to the oxygen which is H.
Table 2. Reaction of phenol with Br2

Figure 1. Resonance Structure of


Aromatic Compounds Examined
Chlorobenzene

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Most stable:
Ortho
Para
Meta

50%
50%
0%

II. Solvent Effects


The second part of the experiment examined the effect of
solvent on the reaction rates of the aromatic substitution
reaction, using bromination reaction. Anisole was
brominated in two different solvents, cyclohexane and
acetic acid. At the end of experiment, bromination of anisole
in acetic acid occured faster than that of in cyclohexane.
Taking a look on the nature of these two solvents, acetic
acid is known to be a polar substance, and cyclohexane is
an alkane which is non-polar in nature. Their structures are
shown below:
Figure 2. Structure of Solvents Used

Table 3. Frequency vs. Temperature Graph

For a certain reaction, there is a corresponding energy


barrier. In order to overcome that easily without the use of
energy, we are using a catalyst. Since catalyst is not
present in the experiment, reaction rate is observable as
temperature changes. As we increase the temperature, we
are overcoming the energy barrier faster. Thus, by
increasing the temperature, reaction will be faster.
CONCLUSIONS AND RECOMMENDATIONS

Polar solvents are capable of stabilizing the intermediate


carbocation. Because of this, the halogen, bromine, can be
easily attacked by the carbocation which stabilizes faster.
III. Temperature Effects
The last part of the experiment examined the effect of
temperature on such reaction. Bromination of acetanilide in
ethyl acetate were tested on 90C, 70C and 50C water
bath. Bromination in 90C temperature took place in just 35
seeconds while at 70C, the reaction happened after 720
seconds. At 50C temperature, it occurred for about 932
seconds. Plotting the data, it can be observed that there is
a great exponential increase of the reaction rate as the
temperature increases.

With this experiment properly executed, the experimenters


found out that due to stability, aromatic compounds undergo
electrophilic substitution rather than addition.
Substituent that is present on an aromatic ring may fasten
or slow down the relative rates of electrophilic aromatic
substitution. Substituent which makes an aromatic ring
more reactive than benzene is classified as activator. And
the one that makes an aromatic ring less reactive are called
deactivators. Activator always directs an electrophile, E+, to
ortho-para positions. Deactivators, on the other hand, may
direct an electrophile to ortho-para positions (halogen
substituent) or to meta position (carbonyl group or CN
group).
The results also conclude that solvent and temperature has
significant effects on the rates of such reaction. Electrophilic
substitution reaction in polar solvent reacts faster than that
of less polar or non-polar solvent. It is due to polar solvents
are capable of stabilizing the carbocation. Relative rates of
such reaction are directly proportional to the temperature,
making it faster as temperature increases.
Hence, the experiment proves that factors: substituents,
solvent and temperature have significant effects on the
relative rates of electrophilic aromatic substitution reaction.

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REFERENCES
1. Baluyut John Y. G., De Castro Kathlia A.,
Organic Chemistry Laboratory for Chemical Engineering
Students Part 2, 2004
2. http://ebookhome.org/home/fundamentals-oforganic-chemistry-6th-edition-157410.html
3. Solomon and Fryhle. Organic Chemistry. 8th
Edition. Prentice hall.
4. Klein, David. Organic Chemistry. John Wiley &
Sons, Inc., 111 River Street, Hoboken, NJ.

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