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CHM145L Organic Chemistry 1 Laboratory

2nd Quarter SY 2014-2015

Factors Affecting Relative Rates of Nucleophilic 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
Alkyl halides are defined as halogenated organic compounds that are commonly used as electrophiles in substitution
reactions. This functional group is a carbon-halogen bond, whereas, the halogens are commonly identified as fluorine,
chlorine, bromine and iodine. Most of these halogens, excluding iodine, have greater electronegativities than that of carbon.
Therefore, we can say that polarization for this functional group is necessary, in order for the carbon to be electrophilic and the
halogen to be nucleopilic. This experiment has two major parts, one for the S N2 mechanism or the bimolecular substitution
reaction and the other is for SN1 or the molecular substitution reaction. In this experiment different alkyl halides are observed,
its structure, substituent and concentrations as well to determine its rate. The purpose of the experiment is to distinguish the
mechanisms of SN1 and SN2 and its factors that affects the relative rates between the said reactions.
Keywords: : nucleophile, SN1, SN2, alkyl halide

INTRODUCTION

Alkyl halides are defined as halogenated organic


compounds that are commonly used as electrophiles
in substitution reactions. This functional group is a
carbon-halogen bond, whereas, the halogens are
commonly identified as fluorine, chlorine, bromine and
iodine. Most of these halogens, excluding iodine, have
greater electronegativities than that of carbon.
Therefore, we can say that polarization for this
functional group is necessary, in order for the carbon
to be electrophilic and the halogen to be nucleopilic.
Upon polarization, there are two characteristics that
make up the alkyl halides. One is the covalent
strength, a feature with the highest in line carbonfluorine bond, while the other is the relative stability of
the corresponding halide anions. The said stability
may be estimated from the relative acidities of the H-X
acids, wherein, we can assume that the strongest acid
releases the most stable conjugate base or the halide
ions. An electron rich species that reacts with an
electron deficient species is called a nucleophile. Its
function is to attack and replace the leaving group of a
certain organic compound. This process can happen
simultaneously, in a concerted process , or in a stepwise manner as well, wherein, the carbocation formed
by the leaving group, is attacked by the nucleophile.

Experiment 08 Group No. 03 11 18 14

Specifically, the mechanism of a step-wise manner is


unimolecular, that includes the observation of a firstorder rate equation,
R = k [substrate]
which is referred as SN1. Moreover, this substitution
reaction produces a racemic mixture as a product, for
the reason that this mechanism proceeds via
carbocation inetmediate, whereas, the nucleophile
attacks equally from either side of the plane. On the
other hand, the mechanism of a concerted process is
bimolecular, and follows a second-order rate equation,
R = k [substrate] [ nucleophile]
which is referred as S N2. In contrast with the
mechanism of SN1, the product produced by S N2,
consists of an inversion of configuration, for the reason
that its mechanism, begins when an electron pair of
the nucleophile attacks the back lobe of the leaving
group. In theory, there are four factors that affect the
relative rates of the said reactions, specifically, the
substrate, nucleophile, leaving group and solvent used
in the reaction. Moreover, the structure of the

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CHM145L Organic Chemistry 1 Laboratory


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substrates plays a major role in the mechanism of S N1


and SN2. In the case of the mechanism of S N1, a
tertiary carbocation is favored due to the fact that this
particular mechanism, considers the stability in the
formation of carbocation rather than the steric
hindrance for the reason that the rate determining step
of this reaction does not involve the nucleophilic
attack. However, in the mechanism of S N2, the
nucleophiles attack is hindered due to steric
hindrance, wherein, a large number of groups are
bonded to the same carbon that bears the leaving
group. Thus, the larger and bulkier the group, the
greater the steric hindrance this will cause the reaction
to slow down, which will then favor a methyl or primary
carbocation. Knowing this, we could say that the rate
equation for an SN2 mechanism is dependent to both
substrate and nucleophile. The stronger the
nucleophile, SN2 is more favored, on the other hand, if
the nucleophile is weak the S N1 will be favored. In
addition, the mechanism of SN1 is more sensitive in
terms of dealing with the leaving group, considering
the fact that the rate determining step favors the
formation of the carbocation. A choice of solvent
would likely have an effect on the rates of S N1 and SN2
reactions. For instance, a polar protic solvent favors a
SN1 reaction. This particular solvent contains hydrogen
that are bonded directly to the most electronegative
atom, in addition this solvent stabilizes the polar
intermediate and transition states of a particular
organic compound. Alternatively, the polar aprotic
solvent favors a SN2 reaction by raising the energy of
the nucleophile, which results a smaller activation
energy. The purpose of the experiment is to distinguish
the mechanisms of SN1 and SN2 and its factors that
affects the relative rates between the said reactions.
MATERIALS AND METHODS

The experiment was divided into two parts; both of


these parts had the same procedures. In the first part,
a 0.5 milliliter of 15% or 7.5% sodium iodide in acetone
was placed in different micro test tubes that contained
different compounds, such compounds were the butyl
bromide, sec-butyl bromide, tert-butyl bromide, benzyl
bromide, neopentyl bromide and butyl chloride each of

Experiment 08 Group No. 03 11 18 14

the said compounds, particularly, its reaction with the


addition of 0.5 milliliter 15% sodium iodide in acetone,
was observed for 5-10 minutes. In the second part of
the experiment, the same process was done, only this
time, a 0.5 milliliter of 0.1 M sodium iodide in absolute
ethanol was added in different micro test tubes that
contained the following compounds; the butyl bromide,
sec-butyl bromide, tert butyl bromide, benzyl
bromide , and tert butyl chloride, again, in this part, the
same process was applied as for the first part.
RESULTS
I.

Factors Affecting the Rate of Nucleophilic


Bimolecular Substitution Reaction

Compound
1-bromobutane

Time for
reaction
19.5 sec.

2-bromobutane

28 sec.

2-bromobutane2-methylpropane
benzyl bromide

58 sec.
4.5 sec.

Table 1.1 SN2 effect by the substrates structure


Compound
1-bromobutane

Time for
reaction
3 sec.

1-bromo-2,218 sec.
dimethylpropane
Table 1.2 SN2 effect by steric effect
Compound
1-bromobutane

Time for
reaction
10 sec.

1-chlorobutane

16 sec.

Table 1.3 SN2 effect by leaving group


Compound

Time for reaction

15% NaI in acetone + 1 M


bromobutane
15% NaI in acetone + 2 M
bromobutane
7.5% NaI in acetone + 1 M
bromobutane

3 sec.
2.09 sec.
6 sec.

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CHM145L Organic Chemistry 1 Laboratory


2nd Quarter SY 2014-2015

15% NaI in acetone + 1 M


bromobutane
Rate Law Expression

4 sec.

R = k [ bromobutane ]
[ NaI]
Table 1.4 SN2 effect by concentration of nucleophile.
II.

Factors Affecting the Rate of Nucleophilic


Unimolecular Substitution Reaction

Compound
1-bromobutane

Time for
reaction
82 sec.

2-bromobutane

24 sec.

2-bromobutane2-methylpropane
benzyl bromide

4.5 sec.
11 sec.

Table 2.1 SN1 effect by the substrates structure


Compound

3 sec.

2 sec.
4 sec.

R = k [ CH3C(CH3)2BR ]

Table 2.4 SN1 effect by concentration of nucleophile.


DISCUSSION

Time for
reaction
2 sec.

Alkyl halides are considered as halogen-carbon bonds.


In this bond, the electronegative halogen acts as the
nucleophile while the carbon acts as the electrophile
when a certain bond undergoes a substitution reaction,
this then makes the bond polarized. It is said that there
are two kinds of nucleophilic substitution reaction,
specifically, the bimolecular, which is commonly known
as SN2, and unimolecular or the SN1.

2-Bromo-2methylpropane
2-Chloro-23 sec.
methylpropane
Table 2.2 SN1 effect by leaving group

Compound

methylpropane in ethanol +
0.1 M silver nitrate sol. in
ethanol
0.2 M 2-Bromo-2methylpropane in ethanol +
0.1 M silver nitrate sol. in
ethanol
0.1 M silver nitrate in ethanol
+ 0.1 M 2-Bromo-2methylpropane in ethanol
0.1 M silver nitrate in
absolute ethanol and 1 mL
absolute ethanol + 0.1 M 2Bromo-2-methylpropane in
ethanol
Rate Law Expression

Time for
reaction
1.35 sec.

For the first part of the experiment, as observed in


table 1.1, it is apparent that benzyl bromide had the
fastest reaction among the other alkyl halides such as
the 1-bromobutane, 2-bromobutane, and 2-bromo-2methylpropane. This result satisfies the fact that the
structure affects the relative rate of an S N2
mechanism.

2-Bromo-2methylpropane +
silver nitrate in
absolute ethanol
2-Chloro-21.82 sec.
methylpropane +
silver nitrate
solution in 5%
ethanol/95%
acetone
Table 2.3 SN1 effect by solvents priority

Fig. 1 Resonance Stabilized Carbocation


Compound

Time for reaction

0.1 M 2-Bromo-2-

4.2 sec.

Experiment 08 Group No. 03 11 18 14

As stated earlier, the benzyl bromide had the fastest


reaction among the alkyl halides, even though, this
compound contained the same leaving group as the
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others, for instance the 1-bromobutane, the loss of the


leaving group of a benzyl bromide generated a

Between the 1-bromobutane and 1-bromo-2,2dimethylpropane, 1-bromobutane is not sterically


hindered contains a primary carbocation. While the
sterric effect in 1-bromo-2,2-dimethylpropane causes
the energy of the transition state to be very high.(Fig 2)

is a crucial step in a certain reaction. This increases


the lifetime of carbocations in a certain solution to
which is equivalent in increasing the concentration of
carbocations in the solution, thus, we can say that the
rate-limiting step of an SN1 reaction is the formation of
carbocations. In the case of a SN2 mechanism, it was
stated that the stability of a good leaving group are
mostly observed on the conjugate bases of strong
acids, this is also true for the S N1 reaction, but , one
must first consider that a compound with a tertiary
carbocation or more stable compounds will be more
favored and will have a faster reaction.

Fig. 2 Structure of 1-bromo-2,2-dimethylpropane

As observed from the gathered result (Table 2.2)


judging its reaction time we can say that the 2-Bromo2-methylpropane is more stable compared to 2-Chloro2-methylpropane and that it contains a tertiary
carbocation.

resonance stabilized carbocation (Fig. 1), unlike for the


1-bromobutane.

Based on the gathered data on table 1.3, we could say


that a bromide ion is a better leaving group compared
to chlorine. Hence, the bromide ion is larger in nature
compared to chlorine, then this means that bromine is
more stabilized than that of chlorine. In determining
the stability of a good leaving group, usually the
conjugate bases of strong acids are observed. It is
said that the rate of a SN2 mechanism is dependent to
both concentrations of the nucleophile and its
substrate.

For table 2.3, the metal halide reactants are


deactivated in protic solvents such as water and
alcohol, rendering these reactants is relatively useless
for inducing SN1 reactions. However, there is a related
halophilic reactant that accomplishes this, particularly
the silver nitrate, and it is said that in aqueous or
alcoholic solution, it promotes ionization of the alkyl
halide and the formation of S N1 products.Thus, having
an absolute solution promotes more ionization of the
alkyl halide and makes the rate faster as seen in table
2.3.

As seen on table 1.4, the addition of 15% sodium


iodide in acetone to 2 M bromobutane produced the
fastest reaction among the others, basing on the
gathered data, we can say that, the stronger the
nucleophile, and the more concentrated the substrate
the faster the reaction, wherein, the reaction will then
favor a SN2 mechanism.

In table 2.4, the gathered result simply shows the


different concentration of the reagents. As the
concentration of the substrate change, the faster the
reaction, however in the addition of nucleophile, as
observed, nothing changed for the reason that the rate
of SN1 mechanism is dependent only to the substrate.

In the case of the mechanism of SN1, it was discovered


that benzyl bromide has a fast rate(table 2.1) which
correspond to table 1.1, wherein, the more substituted
the intermediate the carboacation will be, the more
substituted carbocations tend to be more stable. It is
said that, stabilizing the intermediate carbocation for
long enough that it may react with other nucleophiles,

Experiment 08 Group No. 03 11 18 14

REFERENCES :

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CHM145L Organic Chemistry 1 Laboratory


2nd Quarter SY 2014-2015

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 08 Group No. 03 11 18 14

Thomson

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