CHM142L Organic Chemistry 1 Laboratory

3rd Quarter SY 2014-2015

Factors Affecting the Relative Rates of Nucleophilic Substitution

Miranda, Marilyn1, Ayson, Jose Paolo, L2
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology; 2Student (s),CH142L/A31, School of Chemical Engineering,
Chemistry and Biotechnology, Mapua Institute of Technology
1

ABSTRACT
The objectives of this experiment are are to identify the factors affecting the relative rates of S N2 reactions, to identify the
factors affecting the relative rates of S N1 reactions and to compare S N1 reactions from SN2 reactions. Nucleophilic substitution
is the reaction of the nucleophile (electron rich atom) with an electrophile (electron deficient atom). There are two main types
of nucleophilic substitution that can occur: SN2 (bimolecular) and SN1 (unimolecular) reactions. The S and N letters represent
nucleophilic substitution, but the different numbers tells how many steps at a time. We performed experiments to identify the
factors affecting the rate of reaction of the two mechanisms. For S N2, the factors are structure of the substrate, steric effect,
leaving group effect and the concentration of nucleophile. For S N1, the factors are structure of the substrate, leaving group
effect, solvent polarity, and concentration of nucleophile and the alkyl halide. S N2 substitution reaction favours methyl and
primary substrate while SN1 substitution reaction favours tertiary substrate. Benzyl bromide undergoes both S N2 and SN1
reactions readily because benzyl bromide as a primary alkyl halide, this substrate is a good substrate for S N2. It also ionizes
readily because the carbocation so formed (the benzyl cation) is stabilized by resonance. Steric hindrance makes backside
attack difficult because the high the steric hindrance the more the number of alkyl groups. A good leaving group increases the
rate of reaction by both mechanisms. Polar protic solvents increase the rate of reaction for unimolecular substitution while in
bimolecular favours polar aprotic solvents. The theories and relationships of substitution reaction mechanisms were learned
and observe in this experiment
Keywords: substitution reaction, bimolecular, unimolecular, substrate, steric effect, leaving group, polar protic, polar aprotic, nucleophile

INTRODUCTION
The purposes of this experiment are to identify the factors
affecting the relative rates of SN2 reactions, to identify the
factors affecting the relative rates of SN1 reactions and to
compare SN1 reactions from SN2 reactions. Nucleophilic
substitution is the reaction of the nucleophile (electron
rich atom) with an electrophile (electron deficient atom).
According to our manual, nucleophilic substitution
reactions are great interest to chemists because of their
great utility in transforming functional groups in organic
compounds. it is important to consider the factors that
affect the rates of these reactions so that the conditions
may be controlled to influence the direction of
nucleophilic substitution reaction. There are two main
types of nucleophilic substitution that can occur: SN2
(bimolecular) and SN1 (unimolecular) reactions. The S
and N letters represent nucleophilic substitution, but the
different numbers tells how many steps at a time. For S N2
reactions, bond is broken and a new bond is formed in
one step. The departure of the leaving group occurs
simultaneously with the backside attack by the

Experiment 06 Group No. 5 3/19/2015

nucleophile. The SN2 reaction thus leads to a predictable

configuration of the stereocenter - it proceeds with
inversion (reversal of the configuration). While in SN1
reactions happen with one step occurring at a time. A
planar carbenium ion is formed first, which then reacts
further with the nucleophile. Since the nucleophile is free
to attack from either side, this reaction is associated with
racemization. In both reactions, the nucleophile competes
with the leaving group. Because of this, one must realize
what properties a leaving group should have, and what
constitutes a good nucleophile. For this reason, it is
worthwhile to know which factors will determine whether
a reaction follows an SN1 or SN2 pathway. To predict
whether a reaction will be unimolecular or bimolecular is
to think about the reaction rate equation. For SN1
reactions only the substrate will increase the reaction rate
while in SN2 reactions both the substrate and the
nucleophile affect the rate of the reaction.
Which mechanism occurs under a certain set of
conditions and how fast it occurs depend on a variety of
factors. The structure of the organic halide, the leaving
group, the nucleophile, and the solvent can all play a role.

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CHM142L Organic Chemistry 1 Laboratory

3rd Quarter SY 2014-2015

MATERIALS AND METHODS

In the experiment, we first performed the experiment in
determining the factors affecting the rate of nucleophilic
bimolecular substitution reaction in the structure of the
substrate effect. The test compounds we used are 1bromobutane, 2-bromobutane, 2-bromo-2-methylpropane
and benzyl bromide. 0.50 ml of 15% of sodium iodide in
acetone was transferred in the four micro test tubes. In
each of the four test tubes, a drop of the test compounds
was added. The test tubes was stop up using small
corks. With the use of timer, the reaction was timed and
recorded the time of the reaction when the formation of
cloudiness or precipitation was observed. The reaction
for each test tube was observed for about 5 to 15
minutes. The next effect was the steric effect; the test
compounds used are 1-bromobutane, and 1-bromo-2, 2dimethylpropane. In two micro test tubes, 0.50 ml of 15%
in acetone was transferred. In one of the test tubes, a
drop of 1-bromobutane was added and 1-bromo-2, 2dimethylpropane to the other. The test tube stop up using
small cork and was shake. Using the timer, the reaction
was timed and recorded the time when a formation of
cloudiness or precipitate was observed. It was observed
for 5 to 10 minutes. The third effect was the leaving group
effect with the test compounds namely 1-bromobutane,
and 1-chlorobutane. In two micro test tubes with the 0.5
ml of 15% sodium iodide in acetone, 1-bromobutane was
added to the first one and 1-chlorobutane to the other.
The test tubes were corked and shake. For 5 to 15
minutes the reaction was observed with the timer. When
cloudiness or precipitate was observe the time of reaction
was recorded. The last effect for bimolecular substitution
reaction was the concentration nucleophile effect. In two
micro test tubes with the 0.5 ml of 15% sodium iodide in
acetone, a drop 1.0 M 1-bromobutane was added in one
test tube and a drop of 2.0 M 1-bromobutane to the other.
The test tubes were corked and shake. The time of the
reaction where cloudiness or precipitation was observed
was recorded. Another two test tubes was used to place
1.0 M 1-bromobutane solution. A drop 7.5 % of sodium
iodide in acetone was added to one of the micro test
tubes and a drop of 15% sodium iodide to the other. The
time of reaction where cloudiness or precipitation was
observed was recorded.
The second part of the experiment was factors affecting
the rate of nucleophilic unimolecular substitution reaction.
The first part was the structure of the substrate effect.
The procedures and the test compounds for bimolecular
are the same as for this experiment having the 0.50 ml of
Experiment 06 Group No. 5 3/19/2015

0.1 M silver nitrate in absolute ethanol solution as the

reacting substance. The rate of the reaction where
precipitation or cloudiness was observed was recorded.
The second part was the leaving group effect, the
procedures for the leaving group effect in bimolecular
substitution is the same for this part having tert-butyl
bromide and tert-butyl chloride as the test compounds
and 0.50 ml of 0.1 M silver nitrate in absolute ethanol as
the reacting substance. The time for the reaction for
cloudiness or precipitation to form was recorded. The
third part was the solvent polarity effect. 0.5 ml of 0.1 M
of silver nitrate in absolute ethanol solution was
transferred in a micro test tube. A drop of tert-butyl
bromide was added. The reaction time was recoded
when cloudiness or precipitation was observed. 0.50 ml
of silver nitrate in 5% ethanol/95% acetone solution and a
drop of tert-butyl bromide were added. The rate of
reaction was recorded when a precipitate or cloudiness
was observed. The last part for the factors of
unimolecular substitution reaction was the effect of
concentrations of nucleophile and the alkyle halide. 0.50
ml of 0.1 M of silver nitrate solution was transferred in two
micro test tubes. A drop of 0.1 tert-butyl bromide was
added to one test tube and 0.2 M of tert-butyl bromide
was added to the other. The time of reaction where
cloudiness or precipitation occurred was noted. The
procedure the same for 0.25 ml of 0.1 ml of silver nitrate
in ethanol and 0.25 ml of absolute ethanol adding 0.5 ml
of 0.1 M tert-butyl bromide in ethanol. The reaction time
was recorded.
DISCUSSIONS AND RESULTS
I.Factors Affecting the Rate of Nucleophilic Bimolecular
Substitution Reaction.
A. Structure of the Substance (Alkyl Halide) Effect

COMPOUND

Time of
Reaction

Observations

1bromobutane

1.05,
3:24

Cloudy
at
first,
then
there's
a
formation of
particles.

2bromobutane

4:10

Cloudy

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CHM142L Organic Chemistry 1 Laboratory

3rd Quarter SY 2014-2015

2-bromo-22:4
methylpropane

Benzyl
bromide

5:24

Its a bit
cloudy at first
and become
cloudier.
2 layers were
formed, the
upper
is
slightly clear
while
the
bottom was
white in color

Based on the results, 1-bromobutane reacted fastest with

sodium iodide in acetone. The alkyl halide that reacted
slowest based on the results was benzyl bromide but in
the actual the slowest must be 2-bromo-2methylpropane. Since SN2 favours methyl and primary
substrate, hence tert-butyl bromide is the slowest
because it is a tertiary substrate. 1-bromobutane is more
reactive than benzyl bromide because benzyl bromide is
more stable than 1-bromobutane even though it is a
primary substrate.
B. Steric Effect

COMPOUND
1-bromobutane

1-bromo-2, 2dimethylpropane

Time of
Reaction
6.49s

1:57

Observations
Theres a
formation of
white
precipitate.
Layers which
are cloudy are
formed.

1-bromobutane reacted faster than neopentyl bromide

because neopentyl bromide is more strerically hindered
that 1-bromobutane. As steric hindrance increases, the
number of alkyl groups increases making backside attack
more difficult.
C. Leaving Group Effect

Experiment 06 Group No. 5 3/19/2015

COMPOUND

Time of
Reaction

Observations

1-bromobutane

11.01s ; 1.0s

There was a
change in
colour and
formation of ppt.

1-chlorobutane

8:04

The solution
becomes a little
cloudy.

1-bromobutane has the faster the reaction rate than 1chlorobutane because bromine ion is a better leaving
group than chlorine ion. Whichever process is taking
place in the rate determining step, substitution or
heterolysis (bond cleavage), the bond from the alkyl
group to the leaving group is broken. The better the
leaving group, the easier it is to break this bond, and the
faster the reaction occurs. The better leaving group
speeds up the reaction by both mechanisms, and to
about the same degree. A better leaving group thus
increases the rate of reaction by both mechanisms.
D. Concentration of Nucleophile Effect

COMPOUND

Time for
Reaction

Observations

15% NaI in
acetone+1M
bromobutane

7.3 s

Turned
yellow

to

15% NaI in
acetone + 2 M
bromobutane

4.8 s

It became light
yellow

7.5% NaI in
acetone +1M
bromobutane

9.2 s

After 9.2 s, in
turned
into
yellow

15% NaI in
acetone+1M

9.5 s

it turned into
dark yellow

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bromobutane
Rate
Law Rate = k[I--][bromobutane]
Expression
Based on the results, the 2 M bromobutane reacts faster
than the 1 M bromobutane. The higher the molarity of the
substrate the faster it reacts. The second part, the 1M
bromobutane in 15% concentration of NaI in acetone
should have the faster reaction time because the higher
the concentration the stronger the nucleophile, since SN2
substitution reaction favours strong nucleophile.
II. Factors Affecting the Rate of Unimlecular Substitution
Reaction.
A. Structure of the substrate (Alkyl Halide) Effect

COMPOUND

Time of
Reaction

Observations

1-bromobutane

10.3 s

Formation of
white
precipitates

2-bromobutane

7.2 s ; 1.03

A change in
colour
happens, and
theres
a
formation
of
yellow green
ppt.

2-bromo-2methylpropane

immediately

Yellow green
precipitates
formed.

Benzyl bromide

immediately

Yellow green
precipitates
formed.

Based on the data, tert-butyl bromide reacts immediately,

since SN1 favours tertiary substrate. Therefore, 1-

Experiment 06 Group No. 5 3/19/2015

bromobutane react the slowest since it is a primary

substrate. Benzyl bromide undergoes both SN2 and SN1
reactions readily. For SN1 reactions, an intermediate
carbocation must form before the nucleophile can react.
The allyl cation and benzyl cation are both extremely
stable due to multiple resonance forms for each one.
Therefore, since benzyl bromide form stable cations, it
will be reactive with SN1 also.
B. Leaving Group Effect

COMPOUND

Time for
Reaction

Observations

2-Bromo-2methylpropane

5.12 s

Cloudy
dirty
white ppt.

2-Chloro-2methylpropane

4.32 s

Theres
like ppt.

chalk

Tert-butyl bromide should have the faster reaction time

since SN1 substitution reaction also favours good leaving
group. As stated earlier, the better the leaving group, the
easier it is to break this bond, and the faster the reaction
occurs. The better leaving group speeds up the reaction
by both mechanisms, and to about the same degree. A
better leaving group thus increases the rate of reaction by
both mechanisms.
C. Solvent Polarity Effect

COMPOUND

Time
of
Reaction

Observations

2-Bromo-2methylpropane+silver
nitrate in absolute
ethanol

Immediately

Yellow green
precipitate
formed
instantly.

2-Bromo-2methylpropane+silver
nitrate solution in 5%
ethanol/95% acetone

3.46 s

Bigger yellow
green
precipitates
fromed.

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CHM142L Organic Chemistry 1 Laboratory

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The tert-butyl bromide having the solvent silver nitrate in

absolute ethanol has faster reaction time than with the
solvent 5% ethanol and 95% acetone. Since SN1
substitution reaction favours polar protic solvents than
polar aprotic solvents. Therefore, solvents that can form
hydrogen bond or having hydrogen will increase the rate
of reaction.
D. Effect of Concentration of Nucleophile and the Alkyl
Halide

COMPOUND

Time of
Reaction

Observations

0.1 M tert-butyl
bromide
in
ethanol + 0.1 M
silver
nitrate
solution
in
ethanol

5.23 s

White
precipitate
layers were
formed.

0.2 M tert-butyl
bromide + 0.1
M silver nitrate
solution
in
ethanol.

3.63 s

More precipitate
and
layers
formed.

0.1 M silver
nitrate
in
ethanol + 0.1 M
tert-butyl
bromide
in
ethanol

3.15

Yellowish
precipitate and
layers
were
formed.

0.1 M silver
nitrate solution
in
absolute
ethanol and 1
ml
absolute
ethanol + 0.1M
tert-butyl
bromide
in
ethanol

5.4 s

There was more

yellowish
precipitate
formed as well
as layers.

Rate

Law

Expression

methylpropane]

The strength of the nucleophile does not affect the

reaction rate of SN1 because the nucleophile is not
involved in the rate-determining step. However, if more
than one nucleophile competing to bond to the
carbocation, the strengths and concentrations of those
nucleophiles affects the distribution of products that you
will get. Since the rate is dependent on the concentration
of the substrate rather than the nucleophile.
CONCLUSION
The objectives of this experiment are are to identify the
factors affecting the relative rates of SN2 reactions, to
identify the factors affecting the relative rates of S N1
reactions and to compare SN1 reactions from SN2
reactions. These objectives were achieved during the
experiment since we have identified the factors affecting
the relative rates of bimolecular and unimolecular
substitution reaction. Also, we differentiate the difference
between the bimolecular and unimolecular factors of
affecting their rates of reaction. I learned that S N2
substitution reaction favours methyl and primary
substrate while SN1 substitution reaction favours tertiary
substrate. Benzyl bromide undergoes both SN2 and SN1
reactions readily because benzyl bromide as a primary
alkyl halide, this substrate is a good substrate for SN2. It
also ionizes readily because the carbocation so formed
(the benzyl cation) is stabilized by resonance. Steric
hindrance makes backside attack difficult because the
high the steric hindrance the more the number of alkyl
groups. I also realized that a better leaving group
increases the rate of reaction by both mechanisms. Polar
protic solvents increase the rate of reaction for
unimolecular substitution while in bimolecular favours
polar aprotic solvents. I have learned so many things
regarding substitution reaction especially in the two
mechanisms and how they differ with each other. These
concepts can be helpful in the future for us chemical
engineering students.
REFERENCES

Rate = k[2-bromo-2-

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Baluyot, J. Y., & De Castro, K. A. (n.d.).

Organic Chemistry Laboratory Manual
for Chemical Engineering Students.
Klein, D. (2012). Organic Chemsitry.
Massachusetts: John Wiley & Sons, Inc.
Knipe, A. (2010). Organic Reactions
Mechanisms 2010. John Wiley and
Sons, Ltd.

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