CHM142L Organic Chemistry 1 Laboratory

2nd Quarter SY 2014-2015

Factors Affecting the Relative Rates of Nucleophilic Substitution Reactions

Terrado, Rence Christian L.

Professor Marilyn Miranda, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology; Bote,Jairus Lemuel ; Brillas, Catherine Jill
CHM142L/B21, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology

ABSTRACT
Nucleophilic substitution is a reaction wherein a nucleophile attacks a partially positive charge or
an atom called the electrophile. After attacking the substrate, atoms called the leaving group
departs bringing with it an electron pair. There are two types of nucleophilic substitution. They are
the unimolecular and bimolecular. The SN2 and SN1 reactions. In the experiment, the group is to
determine which reactions yields faster and how are they react fast or slow. The objectives of the
experiment are: (1) to identify the factors affecting the relative rates of Sn2 reaction (2) to
identify the factors affecting the relative rates of Sn1 reactions and also (3) to differentiate Sn1
and Sn2 reactions. Data were gathered in table form in pages 3 to 4 for information on the
reactions on how much time will they react. This is experiment is quite simple but it requires
proper handling of chemicals since the chemicals used are toxic. Also, this experiment requires
proper observation. The group had hard time in observing some of reactions since some reactions
are fast. At the end, the students managed to answer all the questions needed and proved the
theory behind.
Keywords: Nucleophile, Substrates, Polarity, Bimolecular, Unimolecular
INTRODUCTION If the substituents in the substrate are small
atoms, there would be less steric hindrance. As
Nucleophilic substitution is a reaction wherein a result, the ease of nucleophilic substitution is
a nucleophile attacks a partially positive high. And if the substituents of the substrate
charge or an atom called the electrophile. After are bulky, there would be a great amount of
attacking the substrate, atoms called the repulsion which diminishes the rate of reaction.
leaving group departs bringing with it an This is because the bulky groups hider the
electron pair. There are two types of backside attack of the nucleophile to the
nucleophilic substitution. They are the electrophile. However, in unimolecular
unimolecular and bimolecular. Unimolecular substitution, it is the other way around. Next,
substitution reaction is also called as SN1. In the nucleophiles strength affects the rate of
this type of reaction, there are two steps, the reaction. The stronger the nucleophile, the
formation of a carbocation or slow step and the faster the reaction can be. However, in
nucleophilic attack or the fast step. This unimolecular substitution, the nucleophile has
reaction is found to be first order with respect no effect since it is not included in the rate law.
to the substrate. This means that all other The effect of solvent on the two types of
factors do not have any effect and only the reaction also varies. Polar aprotic solvents are
concentration of the substrate affects the rate used in bimolecular substitution and protic
of the reaction. Also, the slow step determines solvents are used in unimolecular substitution.
the rate of the reaction. Regarding bimolecular Lastly, the effect of the leaving group on both
substitution, two molecules which are the reactions is the same. The weaker the leaving
nucleophile and the substrate are involved in group is as a conjugate base and thus the
the rate determining step. Thus, its rate is stronger its corresponding acid, the better the
second order overall. This type of reaction is leaving group. Examples of good leaving
also called as SN2. The rates of these two groups are therefore the halides. The purposes
types of reaction are affected by many factors. of this experiment are to identify the factors
These factors are the substrate, nucleophile, affecting the rates of unimolecular and
leaving group and solvent. In bimolecular bimolecular substitution and to differentiate
substitution, the nucleophile must be able to SN1 from SN2 reactions.
attack he electrophilic center substrate,
resulting to the expulsion of the leaving group.

Experiment 06 Group No. 4 Date 12/12/14 1 of 5

 CHM142L Organic Chemistry 1 Laboratory
2nd Quarter SY 2014-2015
The objectives of the experiment are: (1) to
identify the factors affecting the relative rates
of Sn2 reaction (2) to identify the factors
affecting the relative rates of Sn1 reactions
and also (3) to differentiate Sn1 and Sn2
reactions.
MATERIALS AND METHODS
The part one of the experiment entitled
Factors Affecting the Rate of Nucleophilic
Bimolecular Substitution Reaction, there are
four parts, first is the Structure of the Substrate
Halide Effect and Steric Effect, Leaving Group
Effect, and concentration of Nucleophilic
Effect . In part A of the experiment, the group
followed the following procedures with the use
of 1-Bromobutane, 2-Bromobutane, 2-bromo-2-
methylpropane, and benzyl bromide reagents.
First is in the micro test tubes, 0.50 mL of 15%
NaI in acetone was placed then test
compounds were dropped to each micro test
tubes and covered them with corks and were
shaken. The group then recorded the time
when formation clouds or precipitation begin in
each micro test tubes containing different test
compounds. In part B of the experiment, the
group first get two micro test tubes filled with
0.50 mL of 15% NaI in acetone then placed a
drop of 1-bromobutane to one test tube and 1-
bromo-2,2-dimethylpropane to the other and
covered them then shaken. The group recorded
the time when formation of clouds or
precipitation begins in each micro test tubes
and observations. In part C of the experiment,
the group first get two micro test tubes filled
with 0.50 mL of 15% NaI in acetone then
placed a drop of 1-bromobutane to one test
tube and 1-chlorobutane to the other and
covered them then shaken. The group recorded
the time when formation of clouds or
precipitation begins in each micro test tubes
and observations. In part D of the experiment,
the group first get two micro test tubes filled
with 0.50 mL of 15% NaI in acetone then
placed a drop of 1.0M 1-bromobutane to one
test tube and 2.0M 1-bromobutane to the other
and covered them then shaken. The group
recorded the time when formation of clouds or
precipitation begins in each micro test tubes
and observations. After the reaction is visible
after 5-10 minutes, 0.50 mL of 1.0 M 1-
bromobutane solution was transferred into two
micro test tubes then a drop of 7.5% NaI was
placed on one micro test tube and 15% NaI
Experiment 06 Group No. 4 Date 12/12/14
was placed pn the other. Observations was
recorded after 5-10 minutes.
In part two of the experiment entitled Factors
Affectin the Rate of Nucleophilic Unimolecular
Substitution Reaction, there are four parts
entitled Structure of Substrate Effect, Leaving
Group Effect, Solvent Polarity Effect, and
Effects of Concentrations of the Nucleophile
and the Alkyl Halide. In part A of the
experiment, the group followed the following
procedures with the use of 1-Bromobutane, 2-
Bromobutane, 2-bromo-2-methylpropane, and
benzyl bromide reagents. First is in four micro
test tubes, 0.50 mL of 0.1 M Silver Nitrate in
absolute ethanol solution was placed in four
micro test tubes then test compounds were
dropped to each micro test tubes and covered
them with corks and were shaken. The group
then recorded the time when formation clouds
or precipitation begin in each micro test tubes
containing different test compounds. In part B
of the experiment, the group first get two
micro test tubes filled with 0.50 mL of 0.1 M
Silver Nitrate in absolute ethanol then placed a
drop of tert-butyl bromide to one test tube and
tert-butyl chloride to the other and covered
them then shaken. The group recorded the
time when formation of clouds or precipitation
begins in each micro test tubes and
observations. In part C of the experiment, 0.5
mL of 0.1 M Silver Nitrate in absolute ethanol
was transferred in a micro test tube then
added one drop of tert-butyl bromide then
solution was covered and shaken. Then after
recording the observations, 0.50 mL of 0.1 M
Silver Nitrate in 5% ethanol/95% acetone
solution was transferred in a micro test tube,
and added a drop of tert-butyl bromide then
covered and shaken the mixture and observed
its reaction and time of reaction to begin. In
part D of the experiment, the group first get
two micro test tubes filled with 0.50 mL of 0.1
M Silver Nitrate in absolute ethanol then placed
a drop of 1.0M tert-butyl bromide to one test
tube and 2.0 M tert-butyl bromide to the other
and covered them then shaken. The group
recorded the time when formation of clouds or
precipitation begins in each micro test tubes
and observations. After the reaction is visible
after 5-10 minutes, 0.50 mL of 0.1 M Silver
Nitrate in ethanol and 0.5 mL 0.1 M tert-butyl
bromide in ethanol was transferred. Time of
2 of 5
 CHM142L Organic Chemistry 1 Laboratory
2nd Quarter SY 2014-2015

formation of clouds or precipitation was noted. precipitate

Then transfer 0.25 mL 0.1 M silver nitrate and
0.25 mL of absolute enthanol and added 0.50
mL 0.1 M tert-butyl bromide in ethanol.
Observations and time of reactions was noted.

B. Steric Effect (Table 2)

The apparatuses used in the experiment are
Compound Time of Observations
the following: micro test tubes, 5.0 mL pipette
Reaction,
for getting the reagents, and small corks.
s
The reagents used for the experiment are the
following: 1-Bromobutane, 2-Bromobutane, 1-bromobutane 3.5 Colorless to
light yellow
Benzyl Bromide, 1-Chlorobutane, Absolute
ethanol, 1.0M 1-Bromobutane, 2.0M 1- solution
Bromobutane, 2-bromo-2-methylpropane, 7.5%
NaI in acetone, 15% NaI in acetone, 1-Bromo- 1-bromo-2,2- 106 Forms
2,2-dimethylpropane, 0.1M Silver Nitrate in dimethylpropane precipitate
absolute ethanol, 0.1M Silver Nitrate in 5%
ethanol/95% acetone, 1.0M tert-butyl bromide C. Leaving Group Effect (Table 3)
in ethanol, 0.2M tert-butyl bromide in ethanol,
2-Chloro-2-methylpropane. Compound Time of Observations
Reaction, s

1- 15.23 Colorless to light

RESULTS and DISCUSSIONS bromobutan yellow solution
e
The tables below show the data gathered in
the first part of the experiment, factors 1- None Remains
affecting the rate of nucleophilic bimolecular chlorobutan
substitution reaction and rate law expressions e
for others.
D. Concentration of Nucleophilic Effect
A. Structure of a Substrate Effect(Table 1) (Table 4)

Compound Time for Observations Compound Time of Observations

Reaction, Reaction, s
s
15% NaI in 6.67 Colorless to
1-bromobutane 84 Cloudy with acetone + 1 M light yellow
powder-like bromobutane solution
precipitate
15% NaI in 4.97 Colorless to
2-bromobutane 425 Forms acetone + 1 M light yellow
precipitate bromobutane solution

2-bromo-2- 58 Forms 7.5% NaI in 6 Colorless to

methylpropane precipitate acetone + 1 M light yellow
bromobutane solution
Benzyl bromide 1.5 Forms
15% NaI in None Remains

Experiment 06 Group No. 4 Date 12/12/14 3 of 5

 CHM142L Organic Chemistry 1 Laboratory
2nd Quarter SY 2014-2015

acetone + 1 M bromobutan yellow solution

bromobutane e

Rate Law Expression = k[I-][bromobutane] 1- 1.82 White precipitate

chlorobutan
e

D. Concentration of Nucleophilic Effect

The tables below show the data gathered in Compound Time of Observations
the second part of the experiment, factors Reaction, s
affecting the rate of nucleophilic unimolecular
substitution reaction and rate law equation for 0.1 M 2-Bromo- 4.2 Cloudy/
others. 2- Colloidal
methylpropane Precipitate
A. Structures of Substrate Effects (Table 5) in ethanol +
0.1 M silver
Compound Time for Observations nitrate solution
Reaction, in ethanol
s
0.2 M 2-Bromo- 10.6 Cloudy/
1-bromobutane 1 Forms black 2- Colloidal
precipitate methylpropane Precipitate
+ 0.1 M silver
nitrate solution
2-bromobutane 29 Forms gray
in ethanol
precipitate
0.1 M silver 4.31 Cloudy/
2-bromo-2- 5.80 Forms yellow
nitrate in Colloidal
methylpropane precipitate
ethanol + 0.1 Precipitate
M 2-Bromo-2-
Benzyl bromide 6.74 Forms gray methylpropane
precipitate in ethanol

B. Leaving Group Effect (Table 6) 0.1 M silver 3.69 Cloudy/

nitrate solution Colloidal
Compound Time of Observations in absolute
Reaction, ethanol and 1
s mL absolute
ethanol + 0.1M
2-bromo-2- 1.78 Forms 2-Bromo-2-
methylpropane precipitate methylpropane
in ethanol
2-chloro-2- 2.98 Forms gray
methyl propane precipitate Rate Law Expression=k[2-Bromo-2-
methylpropane]
C. Solvent Polarity Effect (Table 7)

Compound Time of Observations

Reaction, s Nucleophilic unimolecular substitution
reaction:
1- 1.35 Colorless to light

Experiment 06 Group No. 4 Date 12/12/14 4 of 5

 CHM142L Organic Chemistry 1 Laboratory
2nd Quarter SY 2014-2015
R----X R+ + X- (Slow step rate
determining step)
R++ + Nu- R ---- Nu (Fast step)
Rate = k[R----X]
Nucleophilic bimolecular substitution
reaction:
R----X + Nu- R----Nu + X-
Rate = k[X-][R----X]
In this experiment, nucleophilic substitutions
and factors affecting their rates were
observed. The factors that affect the rate of
the reactions are substrate, concentration of
the nuchleophile, leaving group and the
solvent. In the first part of the experiment, the
effect of the structure of the substrate was
shown. The benzyl bromide is the fastest to
react while 2-bromo-2-methylpropane is the
slowest. It shows that primary reacts faster
because there is a less amount of hindrance
and so the nuchleophile can attack easily.
Considering the two alkyl halides, 1-
bromobutane and benzyl bromide, the benzyl
bromide has faster rate. The explanation
behind the reaction is that since carbons are
electron donating, they hinder the attack
which hinders the SN2 reaction. Since 1-
bromobutane has one electron donating
group, this group slows down the attack. In
the leaving group effect experiment, 1-
bromobutane has faster rate than 1-
chlorobutane therefore bromide ion is the
better leaving group. Bromide ion is better
because it is a weaker base than chloride ion.
It is classified as weak base because its
conjugate acid is strong. In part D of the first
part of the experiment, it is clear seen that
higher concentration yields faster reaction.
In part two, letter A of the experiment, the
explanation is just the opposite of part one,
Experiment 06 Group No. 4 Date 12/12/14
letter A. In part B, the table shows that the
reaction conducts faster. In part C, the
solution with the absolute ethanol reacted
faster because of the pure protic solvent
involved in the reaction. Lastly, the
concentration of the nucleophile in part D has
no effect to rate and doubling it also has no
effect because it is not included in the rate
law. Only the concentration of the substrate
has an effect to the rate of the reaction.
CONCLUSIONS AND RECOMMENDATIONS
In the information given by the reactions of
bimolecular and uni-molecular nucleophilic
reactions, it is concluded that the two reactions
are different. It is different in terms of how they
happen and what factors affect their rates. To
the next students who will perform this
experiment, It is recommended that they must
observe properly because there are fast
reactions. And also, safety precautions must be
done before conducting the experiment like the
absence of any flames and goggles must be
worn at all times to avoid eye irritation caused
by vapors released by the toxic compounds.
REFERENCES
1. Nucleophilic Substitution. Retrieved from
http://en.wikipedia.org/wiki/Nucleophilic_substit
ution
2. Hornback, J.M. 1998. Organic
Chemistry.Brooks/ Cole Publishing Company,
Pacificgrove. p.p 816-817
3. L. Gattermann, Die Praxis des organischen
Chemikers, 40th ed., de Gruyter & Co., Berlin,
1961, pp 260-261.
4. Unimolecular Substitution. Retrieved from
http://www.cartage.org.lb/en/themes/Sciences/
Chemistry/Organicchemistry/CommonReaction/
Unimolecular/Unimolecular.htm
5 of 5