CHM142L Organic Chemistry 1 Laboratory

Vol.1, Issue 6, Submitted: November 2015, Accepted: November 27, 2015

Factors Affecting the Relative Rates of Nucleophilic Substitution

Ralph Carlo T. Evidente1, Melina Michelle D. Virata2, and Dr. Kathlia A. De Castro-Cruz3, School of Chemical Engineering and Chemistry,
Mapua Institute of Technology
1

Ralph Carlo T. Evidente, CHM 142L/B21; Email: rctevidente@mymail.mapua.edu.ph 3 Dr. Kathlia A. De Castro-Cruz; Email:kadecastro@mapua.edu.ph

ABSTRACT
Substitution reactions occur when a substrate is treated with nucleophile. For the reaction to take place, it must
contain at least good leaving group, which has its ability to part with the substrate. If the rate depends on the
substrate and the nucleophile, it is said to be bimolecular substitution reaction. On the other hand, if it depends
only for the substrate, it is said to be unimolecular. For both these reaction, the structure of substrate has
something to do with the stability of the reaction. In bimolecular, the nucleophile will back-side attack
simultaneously as the leaving group leaves. To achieve this, the nucleophile will attack with stability if the substrate
has less steric hindrance. On the other hand, Sn1 reaction rate depend solely on the substrate, on how excellent
the leaving group leaves, and on how it will generate a more stable carbocation for the nucleophile to attack. It is a
stepwise mechanism, in which the concentration of the nucleophile is negligible. These factors will be examined
throughout this experiment. The choice of solvent is also crucial, since polar aprotic solvents favor Sn2, while
protic solvents favor Sn1.
Keywords: substitution, substrate, leaving group, nucleophile, relative rate, stability

INTRODUCTION
In nucleophilic substitution reactions, a nucleophile, a
functional group that is attracted to positive charge (nucleus
lover), replaces a functional group called a leaving group
(LG). The two types are: unimolecular and bimolecular.
In the SN2 reaction, the addition of the nucleophile and the
loss of a leaving group occur in a concerted (simultaneous)
manner, hence the name SN2: substitution, nucleophilic,
bimolecular. In the SN2 reaction, the nucleophile
approaches the carbon atom to which the leaving group is
attached. As the nucleophile forms a bond with this carbon
atom, the bond between the carbon atom and the leaving
group breaks. The bond making and bond breaking actions
occur simultaneously. Eventually, the nucleophile has
formed a complete bond to the carbon atom and the bond
between the carbon atom and the leaving group is
completely broken.
According to Klein (2015), reaction mechanism has
something to do with arrow pushing. Electrons compose the
bonds in molecules. In arrow pushing, the movement of
electrons is indicated by arrows. Arrows may show
electrons forming or breaking bonds or traveling as lone
pairs or negative charges on atoms. A complete schematic
showing all steps in a reaction, including arrow pushing to
indicate the movement of electrons, constitutes a reaction
mechanism.

Using the principle above, one may generate a major and

minor product. To be able to come up with this, the
nucleophile must attack from the side of the molecule
opposite to the leaving group. This geometry of reaction is
called back side attack (Badahdah, 2012). In a back side
attack, as the nucleophile approaches the molecule from
the side opposite to the leaving group, the other three
bonds move away from the nucleophile and its attacking
electrons.
Eventually, these three bonds are all in the same plane as
the carbon atom. As the bond to the leaving group breaks,
these bonds retreat farther away from the nucleophile and
its newly formed bond to carbon atom. As a result of these
geometric changes, the stereochemical configuration of the
molecule is inverted during an SN2 reaction to the opposite
enantiomer. This stereochemical change is called inversion
of configuration (Klein, 2015).
The concerted mechanism and nature of the nucleophilic
attack in an SN2 reaction give rise to several important
results:
1. The rate of the reaction depends on the
concentration of both the nucleophile and the
molecule undergoing attack. The reaction requires
a collision between the nucleophile and the

molecule, so increasing the concentration of either

will increase the rate of the reaction.
2. Since the unique geometry of back side attack is
required, the most important factor in determining
whether an SN2 reaction will occur is steric effects.
Steric effects refer to the unfavorable interaction
created when atoms are brought too close
together.
In effect, if the nucleophile or the molecule undergoing
attack have too many substituents or substituents which are
too bulky, the reaction cannot occur since the nucleophile
will be unable to get close enough to the molecule to do a
backside attack.
The most important factor in deciding whether an SN2
reaction occurs is steric effects. When we describe the
nature of the molecule being attacked, called the substrate,
we can look at how many alkyl substituents are present on
the molecule. Given that such a molecule has almost no
steric hindrance (substituents blocking access to the carbon
atom), an SN2 reaction will be highly favored in a molecule
with a methyl carbon.
A major factor affecting the SN2 reaction is strength of the
nucleophile. Several general trends (Wiberg, 1960)
determine the strength of a nucleophile:
1. A molecule which has lost a proton and is
negatively charged (base) is stronger than the
neutral, protonated version of the same molecule

2. Nucleophilicity of the attcking atom decreases

from left to right in the periodic table because
atoms because atoms are more electronegative
(hold electrons more closely) going from left to
right.

3. Nucleophilicity of the attacking atom increases

down the periodic table as electronegativity
decreases and polarizibity increases. Polarizibility
refers to the ability of larger atoms lower in the
periodic table to share electrons more easily
because their electrons are more loosely held.
In addition to the strength of the nucleophile, the structure
of the nucleophile also influences the capacity of an S N2

Experiment 04 Group No. 1 Date Nov. 27, 2015

reaction to proceed. Steric effects are the most important

factor in determining whether an SN2 reaction can proceed.
A small, unbranched nucleophile will be more effective in an
SN2 reaction than a large, branched nucleophile
(Badahdah, 2012).
In contrast to an SN1 reaction, in which the bond-making
addition of the nucleophile and the bond-breaking departure
of the leaving group occur in a single step, the S N1 reaction
involves two separate steps: first the departure of the
leaving group and then the addition of the nucleophile.
In the SN1 reaction, the bond between the substrate and the
leaving group is broken when the leaving group departs
with the pair of electrons that formerly composed the bond.
As a result, the carbon atom to which the bond was
formerly made is left with a carbocation.
Only after the leaving group has departed and a
carbocation has formed, a nucleophile forms a bond to the
carbocation, completing the substitution. This step is more
energetically favorable and proceeds more quickly.
There are several important consequences to the
unimolecular nature of the rate-determining step in the the
SN1 reaction. First, since the rate is controlled by the loss of
the leaving group and does not involve any participation of
the nucleophile, the rate of the reaction is dependent only
on the concentration of the substrate, not on the
concentration of the nucleophile. Second, since the
nucleophile attacks the carbocation only after the leaving
group has departed, there is no need for back-side attack.
The carbocation and its substituents are all in the same
plane, meaning that the nucleophile can attack from either
side.
As a result, both enantiomers are formed in an the SN1
reaction, leading to a racemic mixture of both enantiomers.
Finally, since the nucleophile does not participate in the
rate-determining step, the strength of the nucleophile does
not affect the rate of the SN1 reaction.
EXPERIMENTAL SECTION
The experiment consists of two parts: One is for
Bimolecular, and the second is for Unimolecular Reactions.
Since both qualitative and quantitative methods will be
used, one needs to prepare lots of micro test tubes, pipette,

2 of 11

tape for labelling the test tube, cork (so that the gas formed
will not be inhaled).

good LG, and not the excellent one as the latter favors
more the Sn1 reaction.

Before starting the experiment, one should already have

done doing a chemical review. Since most of the chemicals
that will be used are highly toxic, a high precaution with
careful observation is needed. Hence, one must prepare
goggles and mask. While pipetting, one should wear
gloves. It is noted that it is not anymore a general chemistry
laboratory, but an advanced chemistry. Thus, one should be
more professional both mentally and physically. Meanwhile,
the rate of reaction is to be measured; therefore, one
should need a timer in measuring the time.

Most importantly, in 1D, one should be able to determine

the relationship of rate and the concentration of nucleophile
and the concentration of the substrate. After determining its
relationship, one should proceed to the experiment, as you
test 1.0 M butyl bromide and 2.0 M butyl bromide, both of
which are substrate. It will all be tested to 15 % NaI in
acetone.

For the 1A, the test compounds are: butyl bromide, secbutyl bromide, tert-butyl bromide, and benzyl bromide. The
solvent to be used is assumed to be a mixture of solvent
and/or nucleophile. The latter will be 15% NaI in acetone.
Since Iodide ion is a strong nucleophile, it is understood
that it will favour Sn2 substitution reaction. For accuracy,
predict first which of the following will be the fastest and the
slowest. Knowledge on this will give you an idea about the
rate of reaction. Since in the lecture, one already knows the
trend, that is, the methyl/primary alkyl halide will be the
fastest, and the tertiary alkyl halide will be the slowest. The
reason behind this will be discussed in the results and
discussion.
For the 1B, the test compounds will be butyl bromide and
neopentyl bromide. The solvent is the same from previous
one. However, one should take note the difference between
the test compounds before proceeding to the experiment.
Both of the test compounds are primary alkyl halide.
However, you are testing the steric effect. Given the
structures of the two, one can predict which of the two test
compounds is highly sterically hindered or exhibit steric
hindrance. After several predictions, you may proceed to
the experiment by careful observation. Another thing to take
note is that one should really need a lot of patience. In the
experiment, we are asked to wait until 10 minutes if there
are no yet signs of reaction, such as miscibility, cloudiness
or precipitation. One should take note all the reaction
kinetics, even though it will take long, since this is the
overall goal of the experiment.
For 1C, the test compounds will be butyl bromide and butyl
chloride. The solvent is just the same from previous one.
One might predict the halides, such as bromide ion and
chloride ion, are the best possible options to be a good
leaving group. Since it is an Sn2 reaction, we just need a

Experiment 04 Group No. 1 Date Nov. 27, 2015

Next is, one should prepare 7.5 % solution of NaI in

acetone and 15 % NaI in acetone. One should take note
that in this part, there are differences in the concentration of
the nucleophile. They will all be tested to 1.0 M butyl
bromide. From this, one can be able to verify if the rate is
consistent on the relationship between the rate and the
concentration of the substrate and the nucleophile that you
have predicted.
For the second part of the experiment, one will be able to
determine to factors affecting the nucleophilic unimolecular
substitution reaction. In 1A, one will be able to examine how
different the trend will be in the effect of the structure of the
substrate compared to its effect if the reaction undergoes
bimolecular or Sn2. Since it is already discussed in the
lecture, one should be able to determine the trend based on
the principle that as the LG leaves, the intermediate that will
be formed, since it is a two-step mechanism, will be stable
carbocation. The test compounds will be butyl bromide,
sec-butyl bromide, tert-butyl bromide, and benzyl bromide.
The solvent, however, is expected to be different. We all
know that polar protic solvents favour Sn1; the H atom is
bonded with an electronegative. The solvent used will be
0.1 M AgNO3 in absolute ethanol. There is a dilemma in this
part, since we do not know which of the following will be the
nucleophile or a solvent, unless the nucleophile itself
functions as the solvent, which is called solvolysis.
For 2C, one will compare, given that the test compound is
tert-butyl bromide, if treated with different solvents. One is
0.1 M AgNO3 in absolute ethanol and the other is 5%
ethanol/95% acetone solution. One should be able to
predict that the acetone is a polar aprotic, while ethanol is a
polar protic solvent.
RESULTS AND DISCUSSION
Substitution reactions are class of reactions, in which one
group is exchanged for another. For the both Sn1 and Sn2

3 of 11

reactions, the electrophile is treated with a nucleophile. In

the former, it serves as the substrate, the electrophile in the
substitution reaction. To be able to function as a substrate
in the substitution reaction, it should have a good leaving
group, which has the ability to separate from the parent
substrate.
In the term SN2, the S stands for substitution, the N stands
for nucleophilic, and the number two stands for bimolecular,
meaning there are two molecules involved in the rate
determining step. The rate of bimolecular nucleophilic
substitution reactions depends on the concentration of both
the substrate and the nucleophile. The mechanism is
concerted, since the reaction mechanism only requires
one step. In its transition state, the nucleophile is in the
process of forming a bond with the substrate, and the
leaving group is in the process of breaking its bond with
the substrate.
The rate of a reaction is commonly influenced to a
significant degree by structure of the substrate. In SN2
reactions, the reaction rate depends considerably on the
reaction center's degree of substitution. In addition, the
reaction rate may be controlled by the substituent's
ability to delocalize electrical charge. The substrate plays
the most important part in determining the rate of the
reaction. This is because the nucleophile attacks from
the back of the substrate, thus breaking the carbonleaving group bond and forming the carbon-nucleophile
bond. Therefore, to maximise the rate of the SN2

Figure 1. The Reactions Involved in both Substrate and

Steric effect
In Figure 1, it should be noted that these reactions occur in
a concerted process. Although in the actual lecture, one
Compound

Time of
Reaction

Butyl bromide
(1-bromobutane)

2 seconds

Sec-butyl
bromide
(2-bromobutane)

18 seconds

Tert-butyl bromide
(2-bromo-2methylpropane)

No reaction

Benzyl bromide

1 second

Butyl bromide
(1-bromobutane)

2 seconds

Structure

should include the transition state, so that one may know

that at this point, there is a simultaneous bond forming with
the nucleophile and bond breaking with the LG. The
nucleophile here is the Iodide ion, because it is electron
rich.
reaction, the back of the substrate must be as unhindered
as possible.

Experiment 04 Group No. 1 Date Nov. 27, 2015

4 of 11

Table 1. The Structure of the Substrate and the

corresponding time of reaction with Sodium Iodide as the
Nucleophile

Neopentyl
Bromide
(1-bromo-2,2dimethylpropane)

8 minutes

The Table 1 just implies that primary alkyl halides (butyl

bromide) has the fastest rate of reaction, followed by the
secondary alkyl halides(sec-butyl bromide) which reacts
slowly, and the last on the list will the tertiary alkyl
halides(tert-butyl bromide) which are basically unreactive
towards SN2 reaction. The experimental data is consistent
with the theory in which the nucleophile is expected to
encounter steric hindrance as it approaches the substrate.
Hence, in SN2, the most favored reaction will be the
reaction in which the substrate is primary alkyl halide,
because in the latter, there is less steric hindrance.
However, in the experiment, the top 2 on the list will be the
benzyl bromide. As a 1O 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. Also, benzyl bromide reacts faster than the secbutyl bromide because its transition state is more stable
than the transition state of 2-bromobutane in terms of
electronics. The benzyl CH2 is more electrophilic than the
CH2 attached to an alkyl chain.

Figure 2. The Comparison between the most table Primary

alkyl halide and the least stable Tertiary alkyl halide
Although 2o alkyl halide is not included in Figure 2, since it
favors both Sn1 and Sn2 reaction, we can see that the
Carbon in tertiary alkyl halide is very crowded. It will lead to
a 5-coordinate Sn2 transition state. Hence, the reaction is
less likely to happen, because it is crowded around that
tertiary Carbon. The transition state will be too high energy
to form easily. Meanwhile, there is more room around the
primary carbon. Hence, the transition state is lower in
energy and therefore will be more stable and easier to form.
Going back to Table 1, one can see that there is a faster
rate of reaction if the substrate is butyl bromide rather than
the neopentyl bromide. The latter consumes a lot of time, 8
minutes to form a reaction between the Sodium Iodide as
the nucleophile. As you see the structure of neopentyl
bromide, steric hindrance at the beta position (the next
Carbon after the alpha position where the Bromine atom is
attached) decreases the rate of reaction. If one may notice,
both the butyl bromide and neopentyl bromide are a primary
alkyl halide, considering the alpha position. However, the
latter has three methyl groups attached to the beta position.
These methyl groups provide steric hindrance which results
in high energy of its transition state. Therefore, it is harder
for the nucleophile to attack from back side at C of C-Br
bond.
To summarize, in SN2 reactions, the nucleophile attacks at
the same time as the leaving group leaves: a bond is being
formed as a bond is being broken. Because of crowding,
SN2 reactions work best on the least substituted alkyl
halides: 1 is better than 2 which is better than 3. The
effects of crowding are also called steric effects.
Table 2. The rate of reaction of butyl bromide and butyl
chloride with NaI as the nucleophile
Compound
Butyl bromide
Butyl chloride

Experiment 04 Group No. 1 Date Nov. 27, 2015

Time of Reaction
2s
21 s

5 of 11

For this part, one may see the difference in the rate of
reaction of these substrates. The reason behind this is that
butyl bromide has a good leaving group, while butyl chloride
has a poor leaving group.
Both of them are primary
Compound
alkyl halide. To account
these differences, one
should take note that good
leaving groups are weak
1.0 M
bases. It is so far the most
bromobutane
15 % NaI
simplifying
factor
to
in Aceconsider when it comes to
tone +
good leaving group.

Reaction

Observation

6s

After several time,

the solution turned
orange and
precipitated at 1.53
minutes with small
bubbles at the
bottom

Just like what discussed in

2.0 M
The solution turned
2s
the Organic Chemistry
bromobutane
light yellow
Lecture, if the pKa table is
given, one may use it to
7.5 % NaI in
The solution turned
determine if the leaving
18 s
Acetone
light yellow
group is a weak base.
1.0 M
However, in the pKa table,
bromobuColor changes
sometimes, the identity of
tane +
15 % NaI in
2
s
were
observed in
acids is only given. Hence,
Acetone
the
mixture
one should know its
corresponding conjugate
Rate Law
base. The conjugate base
Rate = k [I-] [bromobutane]
Expression
is the part left over when it
loses hydronium ion. The
stronger the acid, the weaker its conjugate base, the better
the leaving group is.

Figure 3. The Conjugate Bases

In the experiment, one should take note the differences
between the bromide and chloride ion. As you see in the
Figure 3, Bromide ion is weaker base than the Chloride ion,
because HBr is stronger acid than the HCl. However, the
easiest way is to remember the ARION. The larger the
atom, the stronger the acid is. Here, iodide is the largest
atom among the halogens, and therefore a conjugate base
of the strongest acid which is the HI.
Since Bromide ion is weaker base, then it is a better leaving
group than the chloride ion. Although not included in the
experiment, the most commonly used leaving groups are
halides and sulfonate ions. The leaving group affects the
rate of reaction because the more stable it is, the more
likely that it will take the two electrons of its carbon-leaving
group bond with it when the nucleophile attacks the carbon.

Experiment 04 Group No. 1 Date Nov. 27, 2015

6 of 11

Table 3. The Effect of the Concentration of the Substrate

and the Nucleophile on the Rate of Reaction
Secbutyl

10 s

Light green
precipitate/
Solution is not
cloudy

1s

Finer green
precipitate formed

bromide

Since the rate law of reaction for SN 2 reactions follows

Reaction rate = k [substrate] [nucleophile], increasing the
concentration of any would result to an increased reaction
rate as both starting products participate in the ratedetermining step. The reaction rate depends directly on the
suitable reactant's number of collisions. Therefore, doubling Tertthe concentration of one starting product also doubles the butyl
reaction rate. Even though no precipitation was observedbromide
on the reaction of 7.5% NaI in Acetone and 15% NaI in
Acetone with 1.0 M bromobutane, the changing of color
(reaction) is much faster when 15% NaI is combined with
1.0 M bromobutane.

The second part of the experiment follows S N1 mechanism,Benzyl

Large yellow
3s
which is considered as stepwise mechanism in which thebromide
precipitate formed
leaving group should first leave before the nucleophile
attacks. As the LG leaves, it will generate a carbocation
intermediate. Hence, the energy diagram will have two
peaks. The first peak is expected to be taller than the
Since the rate depends on the nature of the substrate, we
second, since the transition state for the first step is higher
have to determine how its structure affects the rate of
in energy than the transition state in the second one.
reaction. In Table 4, one may notice that tert-butyl bromide
Hence, the first step is the rate-determining step, from
reacts fastest among them, while butyl bromide is quite
which the rate is solely dependent on the concentration of
unreactive. Since the rate-determining step shows that
the substrate. As the name implies, it is indeed the
there is no involvement of nucleophile, it has something to
unimolecular substitution reaction because only the
do when the LG leaves the substrate and generate an
substrate participates in the rate-determining step.
intermediate carbocation. The main factor in this
experiment is how fast the LG leaves and how stable the
carbocation will be.
Table 4. The Effect of the Structure of the Substrate to the
rate of reaction
Compound

Time of
Reaction

Butyl

No
reaction

bromide

Structure

Observation

Light green
precipitate/
Cloudy solution

Experiment 04 Group No. 1 Date Nov. 27, 2015

7 of 11

Figure 4. The difference between the most stable tertiary

alkyl halide and the least stable primary alkyl halide
The Figure 4 already answers the question. Tert-butyl
bromide is the fastest among them because it will generate
a stable tertiary carbocation. Since carbocations are
stabilized by neighboring alkyl groups, the most stable one
will be tertiary, followed be secondary, and so on. The butyl
bromide has no reaction because it will generate an
unstable primary carbocation. In fact, generating a tertiary
carbocation lowers the activation energy, making the
substrate reactive in fastest rate.

residue
The above table is consistent on the theory that bromide is
much weaker base than the chloride ion; therefore, it is
good leaving group, and there is a faster rate at which the
bromide ion leaves from the substrate than the chloride.
This will affect the reaction rate, since it is solely dependent
on the substrate.
Table 6. Summary of the Reactions for 2A and 2B

Another thing to notice is that benzyl bromide undergoes

both Sn2 and Sn1 reactions readily, as the latter is top 2 on
the list of the fastest reaction rate. Same principle
mentioned, it ionizes readily because the carbocation
formed (benzyl cation) is highly stabilized by resonance.
An SN1 reaction speeds up with a good leaving group. This
is because the leaving group is involved in the ratedetermining step. A good leaving group wants to leave so it
breaks the Carbon-LG bond faster. Once the bond breaks,
the carbocation is formed and the faster the carbocation is
formed, the faster the nucleophile can come in and the
faster the reaction will be completed.
A good leaving group is a weak base, because weak bases
can hold the charge. They are happy to leave with both
electrons, and in order for the leaving group to leave, it
needs to be able to accept electrons. Strong bases, on the
other hand, donate electrons. It is most likely the reason
why they cannot be good leaving groups. As you go from
left to right on the periodic table, electron donating ability
decreases and thus ability to be a good leaving group
increases. Halides are an example of a good leaving group
whose leaving-group ability increases as you go down the
column. Other examples of good leaving groups, in addition
to the previously mentioned, are sulfur derivatives such as
methyl sulfate ion and other sulfonate ions, such as methyl
sulfate ion, mesylate ion, triflate and tosylate ion.
Table 5. The Effect of Leaving Group on the Rate of
Unimolecular Substitution Reaction
Compounds

Reaction Time

Tert-butyl bromide

3s

Tert-butyl chloride

21s

Experiment 04 Group No. 1 Date Nov. 27, 2015

Observations
Purple
residue
Yellow to gray
to purple

Meanwhile, protic solvents contain at least one hydrogen

atom connected directly to an electronegative atom (N, O,
F). Since the hydrogen atom in a polar protic solvent is
highly positively charged, it can interact with the anionic
nucleophile which would negatively affect an Sn2, but it
does not affect an Sn1 reaction because the nucleophile is
not a part of the rate-determining step. Polar protic solvents
actually speed up the rate of the unimolecular substitution
reaction because the large dipole moment of the solvent

8 of 11

helps to stabilize the transition state. The highly positive

ethanol
layer
and highly negative parts interact with the substrate to Rate Law
Rate = k [2-bromo-2-methylpropane]
lower the energy of the transition state. Since the Expression
carbocation is unstable, anything that can stabilize this
even a little will speed up the reaction.
In Table 8, we can easily see the differences. In the first
part, given the constant concentration of nucleophile, there
Table 7. Effect of Solvent Polarity
are different concentrations of the tert-butyl bromide. There
is a faster rate of reaction in 0.2 M rather than 0.1 M. It is
Compound
Reaction Time
Observation
based on the definition of the rate law expression, that rate
tert- butyl
directly proportional to the concentration of the substrate.
bromide + silver
Green to gray
17 s
nitrate in absolute
precipitate
The rate law for the SN1 reaction is rate = k [substrate].
ethanol
Referring to Table 8, it was observed that the doubling of
tert- butyl
the concentration of tert-butyl bromide resulted into a
bromide + silver
decrease of reaction time by almost half, therefore having a
Bigger yellow
nitrate in 5 %
2s
more rapid reaction. Ethanol is a polar protic solvent, and a
green precipitate
ethanol/ 95 %
poor nucleophile which decreases the rate of reaction as
acetone
observed in Table 8. The silver ion coordinates with the
halide ion in the alkyl halide and enhances carbocation
Since this is a unimolecular substitution reaction, the
formation.
concentration of ethanol is negligible on the rate of reaction.
However, the difference between them is that in the first
CONCLUSION
trial, we used absolute ethanol, and in the second trial, we
used a 5:95 ratio of ethanol and acetone. The acetone, as
Overall, we examine the differences between the SN2 and
we know, is a polar aprotic solvent. These solvents all have
SN1 reactions, and the factors affecting them. The study of
large dielectric constants (>20) and large dipole moments,
this is initiated in the lecture by exposing us in the reaction
but they do not participate in hydrogen bonding (no O-H or
mechanisms. Although in the discussion part, I intent not to
N-H bonds). Their high polarity allows them to dissolve
put all the reaction mechanisms, because I believe, the
charged species such as various anions used as
latter is just the supporting evidence how the product is
nucleophiles (e.g. CN(-), HO(-), etc.). The lack of hydrogen
formed. However, after this experiment, we more appreciate
bonding in the solvent means that these nucleophiles are
all the mechanisms, as we learn not just the latter, but the
relatively free in solution, making the latter more reactive.
factors affecting the rate of nucleophilic substitution
Because they have large dipole moments, the second one
reactions.
is faster than the former.
Table 8. Effect of Concentrations of the Nucleophile and the
Alkyl Halide
Reaction
Compound
Observation
Time
White
0.1 M tert0.1 M silver
3.9 s
precipitate
butyl bromide
nitrate
layer
solution in
White
absolute
0.2 M tert2.8 s
precipitate
ethanol +
butyl bromide
layer
0.1 M tertYellowish
0.1 M AgNO3
butyl
3s
precipitate
in ethanol
bromide +
layer
0.1 M AgNO3
10 s
Yellowish
in absolute
precipitate

Experiment 04 Group No. 1 Date Nov. 27, 2015

One factor is the structure of the substrate. To summarize

this part, in SN2 reactions, the nucleophile attacks at the
same time as the leaving group leaves: a bond is being
formed as a bond is being broken. Because of crowding,
SN2 reactions work best on the least substituted alkyl
halides: 1 is better than 2 which is better than 3. The
effects of crowding are also called steric effects.
Not only is this, in the experiment, there a higher rank on
the list of the fastest rate of both Sn2 and Sn1 reactions if
the substrate will be benzyl bromide. As a 1 O 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.
The Carbon in tertiary alkyl halide is very crowded. It will
lead to a 5-coordinate Sn2 transition state. Hence, the

9 of 11

reaction is less likely to happen, because it is crowded

around that tertiary Carbon. The transition state will be too
high energy to form easily. Meanwhile, there is more room
around the primary carbon. Hence, the transition state is
lower in energy and therefore will be more stable and easier
to form. Also, steric hindrance at the beta position
decreases the rate of reaction, just like the neopentyl
bromide. The latter has three methyl groups attached to the
beta position. These methyl groups provide steric hindrance
which results in high energy of its transition state.
Therefore, it is harder for the nucleophile to attack from
back side at C of C-Br bond.
Also, for both the SN2 and SN1 reactions, the good leaving
group depends on its basicity. The stronger the acid is, the
weaker the conjugate base, the better the leaving group will
be.
Since the rate law of reaction for SN 2 reactions follows
Reaction rate = k [substrate] [nucleophile], increasing the
concentration of any would result to an increased reaction
rate as both starting products participate in the ratedetermining step. The reaction rate depends directly on the
suitable reactant's number of collisions. Therefore,
increasing the concentration of one starting product or both
also increases the reaction rate.
The rate of reaction for Sn1 will depend solely on the
substrate. Considering its structure, the fastest will be the
one with a tertiary intermediate carbocation, immediately
after the LG leaves the substrate. Since carbocations are
stabilized by neighboring alkyl groups, the most stable one
will be tertiary, followed be secondary, and so on. The butyl
bromide has no reaction because it will generate an
unstable primary carbocation. In fact, generating a tertiary
carbocation lowers the activation energy, making the
substrate reactive in fastest rate.
A good leaving group is a weak base, because weak bases
can hold the charge. They are happy to leave with both
electrons, and in order for the leaving group to leave, it
needs to be able to accept electrons. Strong bases, on the
other hand, donate electrons. It is most likely the reason
why they cannot be good leaving groups. As you go from
left to right on the periodic table, electron donating ability
decreases and thus ability to be a good leaving group
increases. Halides are an example of a good leaving group
whose leaving-group ability increases as you go down the
column.

Experiment 04 Group No. 1 Date Nov. 27, 2015

On the other hand, protic solvents contain at least one

hydrogen atom connected directly to an electronegative
atom (N, O, F). Since the hydrogen atom in a polar protic
solvent is highly positively charged, it can interact with the
anionic nucleophile which would negatively affect an Sn2,
but it does not affect an Sn1 reaction because the
nucleophile is not a part of the rate-determining step.
Polar protic solvents actually speed up the rate of the
unimolecular substitution reaction because the large
dipole moment of the solvent helps to stabilize the transition
state. The highly positive and highly negative parts interact
with the substrate to lower the energy of the transition state.
Since the carbocation is unstable, anything that can
stabilize this even a little will speed up the reaction.
Polar aprotic solvent all have large dielectric constants
(>20) and large dipole moments, but they do not participate
in hydrogen bonding (no O-H or N-H bonds). Their high
polarity allows them to dissolve charged species such as
various anions used as nucleophiles (e.g. CN(-), HO(-),
etc.). The lack of hydrogen bonding in the solvent means
that these nucleophiles are relatively free in solution,
making the latter more reactive. Because they have large
dipole moments, the second one is faster than the former.
To summarize everything, these types of nucleophilic
substitution reactions are basically derived from the
molecularity of the rate-determining step of each type of
reaction. Sn1 has rate-determining steps that involve only
the substrate of the reaction. If other factors are held
constant, the rate of an Sn1 reaction will depend only on
the concentration of the substrate and not on the
concentration of the nucleophile, although poor nucleophile
favors Sn1 reactions. For bimolecular nucleophilic
substitution, the rate-determining step involves both the
nucleophile and the substrate.
REFERENCES
1. Badahdah, M.S. (2012). Nucleophilic Substitution.
New Delhi: K. International Pvt. Ltd. pp. 200-203

2. Cruz, K. D., and Baluyot, J. Y. G. Organic

Chemistry for Chemical Engineering Students.
School of Chemical Engineering, Chemistry and
Biotechnology, Mapua Institute of Technology.

10 of 11

3. Durst, H. (1980). Experimental Organic Chemistry.

New York: McGraw-Hill, Inc. pp. 106-109

4. Klein, D. (2015). Organic Chemistry. 2nd edition.

John Wiley and Sons, Inc. pp.288-326

5. Wiberg, K.B. (1960). Laboratory Technique in

Organic Chemistry. New York: McGraw-Hill Higher
Education.p.102
SUPPORTING INFORMATION

Experiment 04 Group No. 1 Date Nov. 27, 2015

11 of 11