WORK DIVISION AND TIMELINE

Num
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Content
Table of content
Objectives
Division of work
Abstract
Introduction
Content (Body)
Conclusion
Islamization
Bibliography
Appendices

Activity

Person in Charge
Dini
All members
Athirah
Ainon
Dini
All members
Athirah
Fikriah
Fikriah
Ainon

Week Week
1
2

Week
3

Meeting 1 (13/1/16)
Decide topic
Consultation
Meeting 2 (29/1/16)
Division of work
Collecting information
Private study
Meeting 3 (6/3/16)
Discussion on
content
Editing
Consultation
Submission of project

Week
4

Week
5

Week
6

Week
7

Week
8

OBJECTIVES

To determine the factors that decide whether haloalkanes undergo

elimination reaction or nucleophilic substitution.

To find out whether the type of halides affect the mechanism of

reaction.
To study the products of elimination and substitution in haloalkanes.
2

To identify the differences between S1 and S2 mechanisms.

1.0 INTRODUCTION
Haloalkanes are also called halogenoalkanes or alkyl halides. All
halogenoalkanes contain a halogen atom - fluorine, chlorine, bromine or
iodine - attached to an alkyl group. There are three different types of
haloalkanes which are primary, secondary and tertiary haloalkanes. In a
primary (1) halogenoalkane, the carbon which carries the halogen atom is
only attached to one other alkyl group, while for secondary (2 ) haloalkane,
the carbon is connected directly to two alkyl groups. In a tertiary (3 )
haloalkane, the carbon with the halogen attached is joined directly to three
other alkyl groups, which may be the same or different.
Haloalkanes can also be classified into aliphatic haloalkanes and
aromatic haloalkanes. Aromatic haloalkanes are then divided into two types;
aryl halides and aromatic haloalkanes with the halogen atom in a side chain.
Haloalkanes can be prepared using several methods that are preparation
from alcohol by nucleophilic substitution, preparation from alkane by free
radical substitution, preparation from alkene by electrophilic substitution and
preparation from silver salts of acids. Generally, haloalkanes are denser than
alkane that they are derived from and insoluble in water but they are soluble
in organic solvents.
Organic compounds which contain halogen are relatively rare in
terrestrial plants and animals except for the thyroid hormones T 3 and T4 and
3

also fluoroacetate, the toxic agent in the South African shrub. However, the
halogen rich environment of the ocean has produced many interesting
natural products incorporating large amounts of halogen. The ocean is the
largest known source for atmospheric methyl bromide and methyl iodide.
Furthermore, the ocean is also estimated to supply 10-20% of atmospheric
methyl chloride, with other significant contributions coming from biomass
burning, salt marshes and wood-rotting fungi.
The functional group of alkyl halides is a carbon-halogen bond. With
the exception of iodine, these halogens have electronegativities significantly
greater than carbon. The electronegativity of the haloalkanes depends on the
halogen atom that they are linked to (electronegativity I < Br < Cl < F). This
functional group is polarized so that the carbon is electrophilic and the
halogen is nucleophilic. Different types of halogens linked give slightly
different physical properties to the haloalkanes. This is due to the factors of
electronegativity, bond length, bond strength, and molecular size.
It is useful to designate the halogen-bearing carbon as alpha and the
carbon atoms adjacent to it as beta to describe any reactions that involve
the haloalkanes. Replacement or substitution of the halogen on the -carbon
by a nucleophilic reagent is a commonly observed reaction. Elimination
reaction can also take place.
Elimination is the bond breaking process, while substitution is the
bond formation process. In elimination, the adjacent hydrogen and halogen
4

atoms are being removed as hydrogen halide via E 1 or E2 mechanism.

Meanwhile, in nucleophilic substitution, the halogen atom is substituted by a
nucleophile such as water (H2O), alcohol (ROH), ammonia (NH3) and cyanide
ion (CN-) and the halogen atom is displaced as halide ion. Nucleophilic
substitution is then divided into two types; S N1 and SN2. There are some
factors that affect the elimination and substitution reaction that is type of
haloalkanes, the solvent, the temperature, concentration of reagent and the
size of base or nucleophile.

2.0 CONTENT
2.1 FACTORS THAT DETERMINE EITHER SUBSTITUTION OR ELIMINATION
TAKES
PLACE
Nucleophilic

substitution

(SN2)

bimolecular with simultaneous bond-making

and

reaction
bond-breaking

is

steps

in

which a nucleophile displaces another nucleophile and takes its position.

Elimination (E2) reaction is a chemical reaction in which a small molecule is
removed from a larger molecule to produce a double bond or triple bond. For
comparison between S2 and E2 mechanisms, refer Figure 1 in appendices.
SN2 and E2 reactions are one step mechanisms and both favoured by a
high concentration of a strong nucleophile or base. When the nucleophile
(base) attacks hydrogen atom, elimination occurs. When the nucleophile
attacks the carbon atom bearing the leaving group, substitution results.

There are four factors that make a given haloalkane to favour

elimination rather than substitution, or vice versa. When the substrate is a
6

primary halide and the base is unhindered, like ethoxide ion, substitution is
highly favoured because the base can easily approach the carbon bearing
the leaving group.

With secondary halides, however, a strong base favours elimination

because steric hindrance in the substrate makes substitution more difficult.

With tertiary halides, steric hindrance in the substrate is severe and

an SN2 reaction cannot take place. Elimination is highly favoured, especially
when the reaction is carried out at higher temperatures.
The nature of the halogen substituent on the alkyl halide is usually not
very significant if it is Cl, Br or I. In cases where both S N2 and E2 reactions
compete, chlorides generally give more elimination than do iodides, since
the greater electronegativity of chlorine increases the acidity of betahydrogens. Even though alkyl fluorides are relatively unreactive, when
reactions with basic nucleophiles are forced, elimination occurs due to its
high electronegativity. In short, it can be said that similar reactions occur
when alkyl chlorides or iodides are used, but the speed of the reactions and
the exact distribution of products will change.
7

These are summarized in the table below.

Secondar
y
R2CH
Anionic
Rapid SN2 SN2
Nucleophi substituti substitutio
les
on.
n and / or
(Weak
E2

Bases:
I,
eliminatio

Br ,
SCN ,
n

N3 ,
(dependin

CH3CO2 ,
g on the

RS ,
basicity of

CN etc.)
the
nucleophil
e). Bases
weaker
than
acetate
give less
eliminatio
n.
Alkyl
Group

Primary
RCH2

Tertiary
R3C
E2
eliminatio
n
will
dominate
with most
nucleophi
les (even
if
they
are weak
bases).
No
SN2
substituti
on due to
steric
hindrance
.

Allyl
H2C=CHCH
2
Rapid
SN2
substitution
for 1 and
2-halides.
For
3halides
a
very
slow
SN2
substitution
or, if the
nucleophile
is
moderately
basic,
E2
elimination.

Benzyl
C6H5CH2
Rapid
SN2
substitution
for 1 and
2-halides.
For
3halides
a
very
slow
SN2
substitution
or, if the
nucleophile
is
moderately
basic,
E2
elimination.
.

By heating the solution it will definitely raise up the temperature.

Higher temperature is favourable by elimination reactions as it needs more
energy. According to the energy equation G = H-TS, for elimination with
increase in temperature, the term -TS will become more negative, and
hence G will become more negative. Thus, high temperatures favour
elimination.
Besides of that, strong sterically hindered base such as the tertbutoxide ion favors elimination over substitution. The bulky methyl groups of
of the tert-butoxide ion inhibit its reacting by substitution, allowing
elimination reactions to take precedence. For example, the relatively
unhindered methoxide ion reacts with octadecyl bromide primarily by
substitution, whereas the bulky tert-butoxide ion gives mainly elimination.

Another factor that affects the relative rates of S N2 and E2 reactions is

the relative basicity and polarizability of the base/nucleophile. Use a strong,
slightly polarizable base such as amide ion (NH 2-) or alkoxide ion especially a
hindered one tends to increase the likelihood of elimination E2. Use of a
weakly basic ion such as a chloride ion (Cl -) or a weakly basic and highly
polarizable one such as Br- or I- increases the likelihood of substitution (SN2).
9

Acetate ion, for example, reacts with isopropyl bromide almost exclusively by
the SN2 path:

2.2 PRODUCTS OF ELIMINATION AND SUBSTITUTION

Haloalkanes undergo elimination of hydrogen halide (HX) when boiled with alcoholic
solution of potassium hydroxide, resulting in the formation of alkenes and side products,
potassium halide and water.

When a haloalkane eliminates hydrogen halide in two different ways, then the major product of
alkene is the one in which carbon atoms joined by the double bond contains largest number of
alkyl groups. This follows 'Saytzeff's rule'.
For example,

10

The alkene with greater number of alkyl groups is

the

preferred

product

during

dehydrohalogenation of alkyl halide as it is formed faster than the other alkene.

Next, haloalkanes can undergo nucleophilic substitution when heated with aqueous
alkaline solution, ammonia in alcohol and alcoholic potassium cyanide. Reaction with aqueous
alkaline solution will produce alcohol

Reaction with ammonia (NH3) in alcohol will produce amines

Reaction with alcoholic potassium cyanide (KCN) will produce alkane nitriles as the major
product.

Alkyl nitriles can further be converted into acid amides, carboxylic acids and primary amines
under different conditions. Therefore, they are useful starting materials for these compounds.

11

2.3 DIFFERENCES BETWEEN S1 AND S2 REACTIONS

Differences
1) Mechanism
2) Rate Law
3) Barrier
4) Reactivity of alkyl
halide
5) Nucleophile
6) Solvent
7) Stereochemistry

S1 Reaction
Two steps
Unimolecular
Carbocation stability
3 > 2 > 1

S2 Reaction
One step
Bimolecular
Steric hindrance
1 > 2 > 3

Weak nucleophile
(neutral molecule)
Polar protic
(example: alcohol)
Mix of inversion and
retention

Strong nucleophile
(negative ions)
Polar aprotic
(example: acetone)
Inversion

12

1) Mechanism

In S1 mechanism, the reaction proceeds with two steps. The first step
of the reaction is the formation of carbocation which is a slow process.
Second step is the nucleophilic attack. The carbocation formed is very
reactive and it reacts rapidly with the nucleophile to form organic

product.
In S2 mechanism, the process of bond breaking and bond forming
occurs simultaneously. The nucleophile attacks the electron-deficient
carbon atom in alkyl halide at the same time as the halide leaves the

structure.
Refer Appendices (Figure 2).

2) Rate Law

In S1, the rate of reaction is dependent on the concentration of alkyl

halide only and therefore known as unimolecular. The slow process in
this reaction which is the formation of carbocation is the rate

determining step.
Rate = k[R-X]
In S2, the rate of reaction depends on both concentration of alkyl
halide and the nucleophile, therefore known as bimolecular. The
process of bond breaking and bond forming that occurs simultaneously
in this reaction are the rate determining step.
Rate = k[R-X] [nucleophile]

3) Barrier - refers to one factor that can prevent the reaction from
occurring.

13

In S1 reaction, the big barrier is carbocation stability. After the first

step in the process happens to form a carbocation, the rate of reaction
is now proportional to the stability of carbocation. Increasing the
number of substitutions at carbon atom makes carbocation becomes

even more stable.

Meanwhile in S2 reaction, the big barrier is steric hindrance or steric
effect. The reaction will only proceed if the empty orbital is accessible.
Bulky presences of alkyl group shield the carbon atom in the C-X bond
from attack by the incoming nucleophile. This hinders the approach of
the nucleophile to haloalkanes.

4) Reactivity of alkyl halide

For S1, the reactivity increase from primary to secondary to tertiary

alkyl halide as carbocation stability increase in that way as well.

3 > 2 > 1
For S2, steric hindrances become greater from primary to secondary
to tertiary alkyl halide. Thus, primary haloalkanes will reacts the
fastest, tertiary haloalkanes will reacts the slowest and secondarys
reactivity is moderate.
1 > 2 > 3

5) Nucleophile

In S1 reaction, nucleophilic attack occurs after rate determining step.

Hence, the strength of nucleophile has no effect on the rate of S1
14

reaction. Example of weak nucleophile or neutral molecule that can be

used in this mechanism is water, and alcohol.

In S2 reaction, the attack of nucleophile is involved in the rate
determining step. Thus, the stronger the nucleophile, the faster the
reaction.

6) Solvent

Polar protic solvents such as water, alcohol and carboxylic acid favor
S1 mechanism. A polar protic solvent contains proton that is attached
to an electronegative atom such as oxygen, make it easier to donate
the proton in solution. As the atoms become polarized, the partially
negative ion in the solvent is attracted to partially positive carbon. This
attraction between the opposite charges helps to stabilize the

carbocation even more.

Acetone, DMSO (dimethyl sulfoxide) and DMF (dimethyl formamide) are
polar aprotic solvents that favor S2 mechanism. Proton in these
solvents is attached to carbon, a less electronegative atom thus the
proton is quite hard to be donated. Polar aprotic solvents help to
increase the nucleophilic strength by bonding to the cation of the
reactant.

7) Stereochemistry

S1 reaction allows the nucleophile to attack from either faces of the

carbocation, producing a mixture of retention (nucleophile attack at

15

the same place of leaving group) or inversion (nucleophile attack at the

opposite side of leaving group) stereochemistry.

Nucleophile can only attack from the backside or opposite side of the
leaving

group

in

S2

reaction,

thus

giving

only

inversion

of

stereochemistry.
3.0 CONCLUSION
In conclusion, there are several factors that determine whether a halogenoalkanes undergo
either substitution or elimination. It includes types of halogenoalkanes, temperature, the strength
of

steric

hindrance,

and

basicity and

polarizability of

base/nucleophile.

Primary

halogenoalkanes favours substitution over elimination, secondary halogenoalkanes can undergo

both substitution and elimination, while tertiary halogenoalkanes prefer mainly elimination
rather than substitution. This reaction will then produce different types of products.
Furthermore, reaction in higher temperature favours elimination more than substitution because
elimination requires more energy. Besides, strong sterically hindered base such as
the tert-butoxide ion favors elimination over substitution. Next, use a strong
and slightly polarizable base tends to increase the likelihood of elimination
E2 while weak base and highly polarizable one increases the likelihood of
substitution (SN2). The product of substitution reaction will produce ethanol, amines and
alkane nitriles depending on the reactant used while elimination will produce double bond.

16

4.0 ISLAMISATION
In Surah Fatir; 35:28,

And among people and moving creatures and grazing livestock are various
colours similarly. Only those fear Allah, from among His servants, who have
knowledge. Indeed, Allah is Exalted in Might and Forgiving.
-Translation Sahih InternationalAccording to Ibn Kathir in his commentary, he states that those who
have knowledge truly fear Allah as He should be feared, because the more
they know about the Almighty, All Powerful, All Knowing Who, has the most
perfect attributes and is described with the most beautiful Names, the more
they will fear Him. In this project, we search and revise on chemical
processes involving ions, atoms and other tiny particles that cannot be seen
by naked eyes. The information that we gain reflects on the perfect
attributes of Allah, proving that He takes care of every creation, even the
smallest molecule that exist. We discover a lot about His Greatness and
these inspire us to have a greater faith in Him.
17

Whoever loves that he would be granted more sustenance and that his life
span would be prolonged, then he should unite his ties of kinship.
-Al Bukhari 5986 and Muslim 2557Ones man who seeks for knowledge should not forget his manners,
including the manners with friends or the person he is learning or working
with. Based on the hadith above, uniting the ties of kinship does not literally
prolong lifespan or increase the amount of provision, but it does enhance the
blessings of them both. Muslims are all related, thus we need to take care of
each other as much as we care for ourselves. For instance, we treat our
family and friends with justice, forgiving their mistakes and wrongdoings.
Throughout the project, we learn on how to tolerate with each members of
the group. Despite of many societies activities that some of us are involved
with, we try to have a meeting session and any discussions that is doable for
all members. The commitments that were given to the group are a big help
to finish this project.
Last but not least, Islamic scholars have stressed on the importance of
time management. Time is considered as one of the greatest and most
valuable blessings given by Allah to human being. According to Dr. Khaled Al-

18

Jeraisy (2010), Time management embodies the optimal utilization of time

as well as other available resources in the way that leads to the achievement
of objectives. In a students life, time management is very crucial in order to
get our works done. Therefore, we draw an outline at the beginning of the
assignment to alert us with the important dates for drafts and project
submission, and also to complete our own tasks within the allocated time.

5.0 BIBLIOGRAPHY

Comparing the SN1 and SN2 Reactions. (n.d.). Retrieved March 03, 2016, from
http://www.masterorganicchemistry.com/2012/08/08/comparing-the-sn1-and-sn2-

reactions/
Competition between Substitution and Elimination. (2014). Retrieved February 29,
2016,from
http://chemwiki.ucdavis.edu/Textbook_Maps/Organic_Chemistry_Textbook_Maps/Map:
_Organic_Chemistry_(Bruice)/09:_Elimination_Reactions_of_Alkyl_Halides_(Competiti
on_between_Substitution_and_Elimination)/9.08:_Competition_between_Substitution_a

nd_Elimination
Dr. Khaled Ibn Abdul Rahman Al-Jeraisy, (2010). Time Management from Islamic and
Administrative Perspective. Lebanon: University of Imam Al Awzay

19

Elimination vs nucleophilic substitution in halogenoalkanes. (n.d.). Retrieved March 02,

2016, from http://www.chemguide.co.uk/mechanisms/elim/elimvsubst.html

No person severs ties of kinship would enter Paradise. (n.d.). Retrieved February 27,
2016, from http://en.islamway.net/article/11913/no-person-severs-ties-of-kinship-would-

enter-paradise
Quran Tafsir

http://www.qtafsir.com/index.php?option=com_content
Sn2 mechanism and stereochemistry. (n.d.). Retrieved March 03, 2016, from

Ibn

Kathir.

(n.d.).

Retrieved

February

26,

2016,

from

https://www.khanacademy.org/science/organic-chemistry/substitution-eliminationreactions/sn1-sn2-tutorial/v/sn2-mechanism-and-stereochemistry

Substitution

or

Elimination?

(n.d.).

http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch08/ch8-9.html
Tan, Y.T. (2015). Chemistry for Matriculation Semester 2 Fourth Edition Updated (pp.
195-198). Selangor: Oxford Fajar.

20

Retrieved

February

20,

2016,

from

6.0 APPENDICES

Figure 1: Comparison

between
mechanisms of S2 and E2

21

Figure 2: Mechanisms for S1 and S2 reactions.

22