Experiment #3: Competition Studies of Substitution and

Elimination Reactions
Name:
Jordan Wilson-Morrison 6767554
Lab Partner:
Chloe Stewart 7745210
Demonstrator:
Samuel Oteng-Pabi
Date:
October 5, 2015
Laboratory of Organic Chemistry II
CHM2123
Section A1
Department of Chemistry
University of Ottawa
Introduction:
In the majority of chemical reactions, it is rare for the product to consist of just one compound.
Of these multiple products, the one to which the reaction is most favourable is known as the
major product, and will form in greater amounts. To decide the outcome of the major product,
the type of reaction - elimination or substitution - that the reagents undergo will be paramount.
This experiment explores S 2 reactions, which are one of the two types of substitution reactions,
as well as the E2 reaction, which conforms to one of the two types of elimination reactions.
Under very similar conditions, these two types of reactions produce different products; this
causes constant competition between the reactions. Subsequently, the other types of reactions are
the elimination E1 reactions, as well as the S 1 substitution reaction, however, their competing
reactions were not studied throughout this experiment. Schematics of both the E2 and S 2
reactions are shown below, respectively:
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Schematic 1: E2 Reaction

Schematic 2: S 2 Reaction
N

As previously discussed, there are similar conditions between the E2 and S 2 reactions
that cause competing reactions between them. The first similar condition includes the fact that
most nucleophiles may act as the base, providing both the E2 and S 2 mechanisms a chance to
proceed with the formation of their respective major products. However, the experimenter's
choice of nucleophile or base can assist with a solution to the issue of competing reactions
between the two types. If one introduces a compound that is a strong base but a weaker
nucleophile, an elimination reaction would be more favourable over that of a substitution. In
contrast, the S 2 pathway demands use of a strong nucleophile, not one of a weaker nature. Thus,
E2 reactions can only proceed with a strong base rather than a weaker one, making this situation
more favourable towards an E2 mechanism, and vice versa.
N

Furthermore, the structure of the molecules that are undergoing the reaction is another
condition that determines the pathway the reaction will take. An S 2 reaction is most favoured
when the -carbon is in the primary position, or will form a primary carbocation. It is also
moderately favoured with a secondary-carbon. However, due to steric hindrance, the E2
mechanism will be more favourable for the reactants. Subsequently, if the -carbon is branched or substituted - then the E2 mechanism an increasingly favourable pathway for the secondary carbon. Furthermore, if the -carbon is of a tertiary nature, then the S 2 reaction will not be
favoured whatsoever, providing certainty that the reaction will adhere to an E2 mechanism. In
retrospect, S 2 pathways are not favoured when there is increased branching and steric
hindrance.
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During this experiment, the competing reactions between the E2 and S 2 reaction
pathways will be observed with 1-bromobutane and 2-bromobutane. Under conditions which will
favour the elimination reaction, the two products that are to be expected include 1-butene and 2butene for each respective reaction. Furthermore, by measuring the amount of gas obtained by
the eudiometer during the reaction progress with 1-bromobutane at reflux, 1-bromobutane at
50, and 2-bromobutane at reflux, the ratio of products for S 2:E2 will be determined. This all
occurs while reacting with basic KOH.
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Additionally, specific calculations must be performed in order to resolve each ratio. This
includes the pressure and moles of each product. Making use of the following formula, one can
deduce the pressure of the gas:
P =P -P
gas

atm

water

- P*

Where P is the pressure of the gas that is collected in the eudiometer tube, P is the
atmospheric pressure, P is the vapour pressure of the water at a definitive temperature, and P*
is the pressure that is exerted by the height of the water column situated above the water level in
the beaker. To expand, one may resort to the Ideal Gas Law formula, PV=nRT, to conclude the
moles of the gas formed within the eudiometer tube. Factors such as temperature, pressure, and
volume are recorded experimental values. The following equation is conducive to the calculation
of the moles of solid KBr that is produced:
gas

atm

water

n =n +n
KBr

gas

butanol

=n +n
E2

SN2

Proceeding forward, the ratio of the E2:S 2 products can be consolidated using the integrated
information.
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Table of Reagents:
Table 1: Table of reagents use for the competition studies of S 2 and E2 reactions.
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Compound

Molar Mass
(g/mol)

Quantity
(g or mL)

Density
(g/mL)

Number of Moles
(mol)

KOH (for 2bromobutane)

56.1056

8.04 g

2.12

0.1433

95% EtOH

46.0684

45 mL

0.789

0.7707

2-bromobutane

137.028

0.70 mL

1.25

6.386x10

1-bromobutane

137.018

1.5 mL
(x2)

1.25

1.368x10 (x2)

KOH (for 1bromobutane)

56.1056

8.02 g

2.12

0.1429

Refluxed KBr

119.002

0.41 g

2.75

3.445x10

-3

-2

-3

Experimental Procedure:
Refer to the experimental procedure for Experiment #3 of the Laboratory of Organic
Chemistry II Laboratory Manual posted on Blackboard Learn, pages 4-6.
Modifications: The water bath was heated to 57 rather than 50.
Observations:
Table 2: Table of experimental observations and key steps.
Organic Substance
1-bromobutane
(Observations cited
from Sarah Zhang
7618401)

Key Step/Observation

The Tygon tube was attached only 30 seconds before adding

bromobutane to prevent EtOH vapours from condensing onto
the tube.
~0.01 mL of bubbles escaped into the eudiometer when the
Tygon tube was inverted.
Solution turned a yellow colour as reflux progressed.

1-bromobutane in a
57 water bath
(Observations cited
from Sarah Zhang
7618401)
2-bromobutane

The salt was white and powdery.

The KOH was not fully dissolved before the reaction had
begun.
Some KOH reacted with the air before being added to the flask.
The salt was white and powdery.

Step 1: The initial KOH solid was oily, white, and oval-shaped.
Step 3: The solution turned clear and colourless once the 95% ethanol
was added to the KOH crystals.
Step 10: Large gas bubbles formed rapidly within the eudiometer tube
initially, and as equilibrium was reached, the gas bubbles became
smaller and more infrequent. Two eudiometer tubes were required for
the gas in order for the reaction to reach equilibrium.
Step 11: The solution turned a pale yellow, cloudy and opaque colour
once the 2-bromobutane was added.
Step 14: Bubbles began to form rapidly, requiring two eudiometer
tubes to capture the full volume of the gas bubbles, until the the gas
reached the water level of the 1L beaker.
Step 18: As the solution cooled, a white and powdery precipitate
formed on the bottom of the round-bottom flask. The liquid solution
surrounding it was clear and colourless.
Step 19: The KBr crystals retrieved were a dry white powder.

Results:
Table 3: Results of the competition studies of S 2 and E2 reactions with 1-bromobutane at
reflux, 1-bromobutane at 57, and 2-bromobutane at reflux. Results from
1-bromobutane at reflux and 1-bromobutane at 50 have been cited from Sarah Zhang,
student number 7618401.
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Reaction
Conditions

Pressure
of Gas
(atm)

Volume
of Gas
(mL)

Moles of
Butene
(mol)

Mass
of
KBr
(g)

Moles of
KBr (mol)

Moles of
Butanol
(mol)

Conversion
(%)

Selectivity
(%)

S 2:E2
Value
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1bromobutane
at reflux

0.968

1bromobutane
at 57

0.945

2bromobutane
at reflux

0.982

9.397x10

23.6

0.35

2.941x10

2.001x10

21.5

31.95

2.129

15.97

8.00

11.49

53.9

83.5

0.198

1.749x10

0.45

0.26

2.185x10

2.01x10

-3

0.002876

71.2

0.41

3.445x10

0.000569

Sample Calculations
*all calculations pertain to the reaction of 1-bromobutane at reflux*
P :
P* = (500 mmH2O - 109 mmH2O - 250 mmH2O) 13.6 mmH20= 10.368 mmHg
gas

P = P - P - P* = 767.313 mmHg - 21.0 mmHg - 10.368 mmHg

= 735.945 mmHg x 0.00131578947 atm1 mmHg
= 0.968
gas

atm

water

the pressure of the gas was 0.968 atm.

Moles of Butene:
n = PVRT, where R = 0.0821 L atm/(mol K), P is in atm, V is converted to L:
n = (0.968 atm)(0.0236 L)(0.0821)(296.1K)= 9.397x10 mol butene
-4

the moles of butene are equivalent to 9.397x10 mol, or 9.397 mmol.

-4

Moles of Butanol:
n =n +n
n = n - n = 2.941x10 mol KBr - 9.397x10 mol butene = 2.001x10 mol butanol
KBr

butanol

gas

butanol

KBr

gas

-3

-4

-3

the moles of butanol are calculated to be 2.001x10 mol, or 2.001 mmol.

-3

Conversion:
C H Br + KOH C H O + KBr
4

(l)

(s)

10

(g)

(s)

Limiting Reagent:
1 mol C4H9Br0.01368 mol = 1 mol KOHx x = 0.01368 mol KOH needed
1 mol C4H9Brx = 1 mol KOH0.1429 x = 0.1429 mol 1-bromobutane needed; it is limiting
because we

do not have 0.1429 mol of 1-bromobutane for a complete

reaction.
Conversion = n + ndn limiting reagentx 100 = n butene + n butanoln 1-bromobutanex 100 =
2.941x10-3 mol 0.01368 molx100
= 21.5%
c

Selectivity:
Selectivity = ncnc + ndx 100 = n butenen butene + n butanolx100 = 9.397x10-4 mol2.941x10-3
molx100
= 31.95%
S 2:E2 Ratio:
nSN2nE2 = n butanoln gas = 2.001x10-3 mol butanol9.397x10-4 mol butene= 2.129
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Discussion:
The objective of this experiment was to determine the ratio of the competing reaction products
resulting from the S 2 and E2 reactions involving 1-bromobutane at reflux, 1-bromobutane at
57, and 2-bromobutane at reflux. For each experiment, approximately 8g of solid KOH was
used and placed in a 100 mL flask, mixed with 95% ethanol. The solution began to reflux as it
was heated and stirred, subsequently forming bubbles within the eudiometer tube until the
solution had reached equilibrium. The purpose of refluxing during the experiment is to allow the
solution to reach a gentle boil, which permits the vapour to circulate up the condenser and cool,
forcing it into a descent down the reflux condenser. Thus, if a molecule or compound has a lower
boiling point than the others within the mixture, that particular compound will circulate up the
condenser and travel through the Tygon tube and into the eudiometer tube, creating a pressure
that forces the water inside of it downward, allowing for a measurement of the gas volume. Once
the reagent - being either 1-bromobutane or 2-bromobutane - was added, the reaction begins and
the product with the lowest boiling point travels up and into the eudiometer tube. In each
corresponding experiment, the gaseous product was butene. Due to the presence of double bonds
within its alkene structure, butene has a lower boiling point, which allows it to react faster than
the other products consisting of butanol and KBr because of the highly electronegative halogen
group (Br) in the KBr product, and the alcoholic functional group in butanol (OH). The higher
electronegativity of those molecules make it more difficult for those atoms to interact and move
due to strong bonds caused by high electronegativity.
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Also, suction filtration was performed for each experiment to isolate the KBr precipitate
from the liquid butanol. From here, the mass of the KBr product was measured. This allowed the
conversion - or the ratio of all products produced to the total that could have been produced - to
be determined. For the trial of 1-bromobutane at reflux, the conversion was 21.5%. For 1bromobutane at 57 and 2-bromobutane, the conversion values were 15.97% and 53.9%,
respectively. Furthermore, the selectivity - or the ratio of the desired product among all products
- was also calculated. For 1-bromobutane at reflux, 1-bromobutane at 57, and 2-bromobutane
at reflux, the respective selectivity values were 31.95%, 8.00%, and 83.5% respectively. With 1bromobutane and 2-bromobutane at reflux, errors in the trial that may have caused these lower
values could be that the solution did not reach proper reflux conditions. Furthermore, some of the

butene vapours could have escaped from the tubes during the reaction. Also, the fact that the
water bath was not exactly 50 may have caused the reaction to not proceed optimally. Also, of
all three experiments, the experiment with 2-bromobutane at reflux has the highest conversion
value, as well as the highest selectivity. Of all three reactions, this reaction produced as close to
the maximum amount of products as possible, and also produced the most desired product
among the ones produced.
Finally, the last goal of this experiment was to determine the S 2:E2 ratios. The reaction
of 1-bromobutane at reflux yielded a ratio of 2.129; the reaction of 1-bromobutane at 57
yielded a ratio of 11.49, and 2-bromobutane at reflux gave a ratio of 0.198. Of all three reactions,
the 1-bromobutane at 57 yielded the highest ratio of S 2 products, and thus was most selective
towards the S 2 product over the E2. This is an error however, because heat promotes
elimination reactions, even though this R-X group is primary. KOH is a strong base, thus this
rule should apply to this reaction. Errors that may have caused this include rounding errors in
calculation, as well as possible escaping of gas product, which would lower the amount of moles
of gas, altering the ratio. The reaction of 1-bromobutane also yielded more S 2 product than E2,
as is expected of a primary R-X group. Also, the reaction of 2-bromobutane at reflux 0.198,
which indicates that the elimination product was favoured. This is also expected, as the product
of a secondary R-X group will promote the substitution.
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Conclusion:
The overall objective of all three experiments, respectively, was to determine the ratio of
products - S 2:E2 - as well as the conversion and selectivity of each reaction. The reaction of 1bromobutane at reflux yielded a conversion of 21.5%, a selectivity of 31.95%, and an S 2:E2
ratio of 2.129, thus favouring a substitution reaction. Next, the reaction of 1-bromobutane at
57 gave a conversion value of 15.97%, a selectivity value of 8.00%, and an S 2:E2 ratio of
11.49, also favouring the substitution reaction. Finally, the reaction of 2-bromobutane at reflux
gave a conversion of 53.9%, a selectivity of 83.5%, and an S 2:E2 ratio of 0.198, promoting the
elimination product.
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Questions:
1. a) An experimental method that can ensure the production of 1-butene from the reaction
of 2-bromobutane in its entirety would include the introduction of a strong, bulky base;
thus, KOC(CH ) would one qualified base. To justify this, a strong and bulky base would
avoid the deprotonation of the most substituted region in 2-bromobutane due to steric
hindrance. Thus, use of a strong, bulky base would favour the deprotonation of the least
substituted hydrogen, yielding a final product of 1-butene.
3 3

b) One experimental method that ensures the entire production of 2-butene from the
reaction of 2-bromobutane is the use of a strong - yet small - base. A base such as
NaOCH would satisfy these parameters. Since the base is small and strong, steric
hindrance will not be a factor in determining the method of attack; thus, deprotonation of
the hydrogen located in the most substituted region would be more favourable. This
yields a final alkene product of 2-butene.
3

2.

V
=?
1-bromobutane + KOH butene
T = 298.15 K
n
= (1.5 mL)(1.25 g1 mL)(1 mol137.018 g)
P = 101.325 kPa
= 0.01368 mol
1-bromobutane butene
n
= n = 0.01368 mol
V
= 0.0015 L
V = nRTP = 0.335 mL
max butane

1-bromobutane

1-bromobutane

1-bromobutane

butene

max

the maximum volume at standard temperature and pressure is 0.335 mL, or 335 L.

3.

4.

a) Elimination, as the haloalkane is tertiary.

b) Substitution, as the haloalkane is primary.
c) Substitution, as the R-X group is a methyl.
d) Elimination, as the R-X group is secondary.

The first experimental modification one can make to facilitate the production of 1-pentene over
1-pentanol would be to use a weaker nucleophile but a stronger base than that of NaOH. If the
base has a pKa value greater than 10, then the reaction will favour an elimination reaction over
the substitution pathway; thus, forming 1-pentene will be favoured over 1-pentanol. The second
modification you could make would be to heat 1-bromopentane, since E2 reactions are more
commonly favoured when for a primary -carbon when heat is added to the reacti
H