CHM145L Organic Chemistry 1 Laboratory

2nd Quarter SY 2014-2015

Factors Affecting the Relative rates of Electrophilic Aromatic Substitution Reactions

Miranda, Marilyn1, Monta, Xyrell Claude D.2
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology; 2Student , CHM145L/A21, School of Chemical Engineering,
Chemistry and Biotechnology, Mapua Institute of Technology
1

ABSTRACT
Aromatic Compounds are those organic compounds which have a benzene ring. These compounds always follows the
substitution reaction due to the stability of the benzene ring, thus it will not process the elimination, addition or the
rearrangement reaction. One of its common reactions is the electrophilic aromatic substitution, wherein, an electrophile reacts
with an aromatic ring and substitutes a hydrogen atom. The experiment was done in three parts that determined the factors of
electrophilic substitution on different aromatic rings, that involved the comparison of different reaction rates and structure of
the compounds. The purpose of this experiment is to visualize the effects of the substituents in the relative rates of
electrophilic aromatic substitution; to know the effect of solvent on reaction rates of reaction; and to know the effect of
temperature on relative rates of reaction. The difference between the reaction rates and identifying and understanding the
structure of the said compounds leads to the conclusions that a substituent that is more reactive than bezene is termed as an
activator and are classified as ortho- para- directors, while a substituent that is less reactive than benzene is termed as
deactivator and are classified as meta- directors. In terms of the solvent, the more polar the solvent is, the faster the rate of
reaction would likely occur, whereas, this goes the same for temperature, the higher the temperature means the faster the rate
of electrophilic aromatic substitution reaction. In doing this experiment, students are advised to be strict in observing the
decolorization reaction of each compounds to avoid errors in gathering the data.
Keywords: : aromatic compounds, substituents, solvents, orho- para- directors, meta- directors

INTRODUCTION

Electrophilic Aromatic Substitution Reactions are one

of the significant processes in synthesizing a certain
organic compound. For this reaction allows the
introduction of many different functional groups onto
an aromatic ring system, wherein, the overall reaction
involves the substitution of a hydrogen on the aromatic
ring system by an electrophile.
The said reaction then, most commonly occur in
aromatic compounds. In the electrophilic substitution,
there are several factors that affect its relative rates,
such as the substituent, solvent and temperature. The
presence of a substituent on the aromatic ring affects
its reactivity, wherein, it could either activate or

Experiment 09 Group No. 03 11 25 14

deactivate the ring, this can make the ring to be more

or less reactive than benzene, respectively. In
addition, the presence of a substituent does also affect
the orientation of a particular reaction. It is said that
these substituents can be divided into three groups,
namely, the ortho- and para- directing activators; and
deactivators, and meta-directing deactivators. It should
be noted though, that there are no meta-directing
activators.

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CHM145L Organic Chemistry 1 Laboratory

2nd Quarter SY 2014-2015

0.05M bromine in cyclohexane

Bromine in acetic acid
Apparatus:
Micro test tubes
Test tube rack
2 milliliter pipet

Fig. 1 otho- para- directing activators; and deactivators metadirecting activators

As stated earlier, the presence of the substituents

affects the reactivity and orientation of the ring, these
two factors are said to be controlled by the inductive
and resonance effects. By definition, inductive effect is
the withdrawal or donation of electrons through a
sigma bond due to electronegativity and the polarity of
bonds in functional groups, the resonance functions
the same as the inductive effect, yet this time the
donation of electrons occurs in a pi bond reaction for
the reason that, the p orbital overlaps the substituent
on the aromatic ring. The purpose of this experiment is
to visualize the effects of the substituents in the
relative rates of electrophilic aromatic substitution; to
know the effect of solvent on reaction rates of reaction;
and to know the effect of temperature on relative rates
of reaction.
MATERIALS AND METHODS

Reagents:
0.2 M solutions in ethyl acetate of the ff:
Benzene
Acetanilide
Phenol
Chlorobenzene
P-nitrophenol
Aspirin
Anisole
Bromine Solution

Experiment 09 Group No. 03 11 25 14

As stated earlier, this experiment aims to determine

the effects of the substituents, solvent and
temperature on the relative rates of the electrophilic
aromatic substitution, hence, this experiment was
done in three parts. At the first part, in determining the
substituent effect, a 0.20 milliliter of each solutions
were transferred into separated test tubes. This was
then followed by the addition of a 0.20 milliliter of
bromine solution to each tube that contains the
benzene, chlorobenzene, and aspirin. Afterwards the
tubes were set aside and observed until decolorization
occurs, the process was then repeated to the phenol
and anisole. This was then followed by the addition of
the bromine solution to the tubes that contains the
acetanilide and p-nitrophenol, decolorization was then
observed. At the second part, in determining the
solvent effect, a 0.20 milliliter of the anisole solution
was first transferred in a test tube, which was then
followed by the addition of the 0.20 milliliter of freshly
prepared 0.05M bromine in cyclohexane. On another
test tube, a 0.20 milliliter of anisole solution was mixed
with 0.20 milliliter bromine in acetic acid. The reactivity
between the two solvents were then compared after its
completion for two hours. At the last part, in
determining the temperature effect, a 0.20 milliliter of
0.2 M in ethyl acetate was first transferred into as test
tube, this was then followed by the addition of the 0.20
milliliter of bromine in acetic acid. A water bath was
then prepared, wherein, a 300 milliliter of water in a
400 milliliter beaker was preheated, whereas, the
water bath was heated 1 degree Celsius above the
desired temperature. The test tube was then heated in
a 50oC water bath. The same procedure was done in a
70oC and 90oC water bath, the gathered results were
then plotted with 1/t sec as the ordinate and the
absolute temperature as the abscissa.

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RESULTS

layer and was

transparent in
color.

l. Substituent Effect
Table 2.1

COMPOUND

Benzene

Chlorobenzene

Aspirin

Acetanilide

p-nitrophenol

Anisole

Phenol

TIME OF
DECOLORIZ
ATION

REMARKS

25 mins.
32 sec.

From red orange

color, the solution
contained an
immiscible layer
and turned yellow
in color.

II. Solvent Effect

Compound

45 mins.
13 sec.

The red orange

color remained the
same and
produced an
immiscible layer.

Anisole +
bromine in
cyclohexane

32 sec

The color changed

from orange to
yellow and
contained an
immiscible layer.

Anisole +
bromine in
acetic acid

22 sec

The color of the

solution became
transparent with
an immiscible
layer

28 sec

There was no
color change

13 sec

The solution
became
transparent and
contained an
immiscible layer.

11 sec

Remarks

2 hrs. and 15
mins.

From the red

orange color,
the solution
tuned into pale
yellow .

1 hr. and 35
mins

The orange
color of the
solution turned
pale yellow.

Table 2.2

III. Temperature Effect

Compound

90 C

70 C

Time of
decolorization

Remarks

170 sec

The time of
decolorization
was fast.

192 sec

The time of
decolorization
was faster

215 sec

The time of
decolorization
of 5
was the3 fastest

The solution have

an immiscible
o

50 C
Experiment 09 Group No. 03 11 25 14

Time of
Decolorization

CHM145L Organic Chemistry 1 Laboratory

2nd Quarter SY 2014-2015

Table 2.3

Fig. 2

DISCUSSION

Based on the gathered data, as observed from the first

part, the time of the decolorization of cholorobenzene
is much slower than that of benzene, due to the fact
that chlorine is less reactive than benzene. This then
makes the chlorine act as a deactivator for the
aromatic ring, thus, making them ortho-para directors.
Again, as seen on table 2.1, the time of decolorization
of aspirin is much faster than the benzene and
chlorobezene, this then makes the aromatic ring less
reactive than benzene, which makes aspirin a metadirecting deactivator. This means that, the
destabilization of ortho- and para- intermediates is
caused by the formation of resonance at the positive
charges of the carbocation intermediate directly on the
ring carbon atom that contains the deactivating group,

Experiment 09 Group No. 03 11 25 14

whereas, simultaneously, the resonance of the

withdrawal of the electrons is felt at the ortho- and
para- postion. Hence, the reaction in aspirin along with
an electrophile occurs at the meta position. Moving
down the table, the time of decolorization of
acetanilide is 22 seconds which is faster, when
compared to aspirin and p-nitrophenol. However, in
beteween the acetanilide and the p-nitrphenol, the
acetanilide must have a faster time of decolorization,
due to the fact that acetanilide has strong, electron
donating resonance effect that is most likely observed
at the ortho- and para- positions. In the case of pnitrophenol, despite of the fact that it has a more
reactive activator compared to acetanilide, this
compound will still react slower because of its
deactivator, particularly is the NH2. As we move down
further, the decolorization time of phenol, basing on
the gathered results, is much faster when compared to
the time of decolorization of anisole, for the reason
that the phenol has an OH substituent which then,
makes it more reactive than benzene, and since they
are more reactive than benzene, we could say that
phenols can be classified as ortho- para- directing
activators. Anisole on the other hand, do also have a
substituent that makes the aromatic ring more reactive
than benzene, this substituent is the OCH 3 and is as
well classifeid as an ortho- para- directing activators,
Yet OH is more reactive than OCH 3, which will then
make the phenol react faster than the anisole.
At the second part of the experiment, the effect of
solvent on the reaction rates of the aromatic
substitution reaction via bromination was exhibited,
whereas, the anisole was brominated in two different
solvent, particularly the cycloexane and acetic acid. In
the end of the experiment it was observed that the
bromination of anisole in acetic acid transpired faster
than that of cylcohexane.
The last part of the experiment involves the
bromination of acetanilide in ethyl acetate, which was
tested on a 90C , 70C, and 50C temperature.
Table 2.3 clearly suggests that as the temperature is
increased the rate of reaction is also increased, this
then corresponds to the plotted graph, wherein, an

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exponential increase in the reaction rate was observed

as the temperature increases. Moreover, we can then
say that the graph is linear with respect to the two
variables, which is the temperature and the rate of
reaction, which is identified as 1/t. This then suggests
that the involved reaction is in a first order reaction.
CONCLUSIONS AND RECOMMENDATIONS

Upon this experiment, firstly, I would like to

recommend the students who will perform this
experiment, should be strict in observing the time of
decolorization of a certain compound in order to avoid
errors in recording and gathering data. In doing this
experiment, it is important to determine the effects of
the substituents, solvent, and temperature, whereas, it
has come to my conclusion, that 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 woukd react faster.
REFERENCES :
1. Klein, David (2012). Organic Chemistry. Danvers. John
Wiley & Sons, Inc.,
2. Mendoza, Estrella (1990). Chemistry. Quezon City,
Phoenix Press, Inc.,
3. Wilbraham, Anthony (1997).Chemistry (4th Ed.). San
Juan, Addison - Wesley Publishing Company, Inc.,
4. Masterton, William (2009). Chemistry (Principles and
Reactions).Belmont, Brooks/Cole Cengage Learning.,
5. McMurry, John.
Publications. 2004

Organic

Chemistry.

Experiment 09 Group No. 03 11 25 14

Thomson

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