STUDY PACK : 5

ORGANIC CHEMISTRY

ALKENES
First Edition Jan 2006
Second Edition Jun 2009
Third Edition Jun 2011
Fourth Edition Jun 2021 (Revised New Syllabus)

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Unauthorized duplication contravenes applicable laws.

No part of this publication may be reproduced or utilized in any form or by electronic,

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& recording, without the prior permission in writing from the copyright owner.

Published by:

Copyright owner:

Imran Razeek I.Chem.C (P1), M.Ed, Ph.D (Reading)

Lecturer in Chemistry cum Chairman

Chembase - School of Chemistry,

34, 1/2, Galle Road, Dehiwela, Sri Lanka.

(+94) 776 534 233 / (+94) 776 136 047

www.chembase.lk I www.ChembaseAcademy.com
info@chembase.lk
1. Write down the general formula of Alkenes & cyclo alkenes.

2. Explain the bonding in alkenes using ethene as an example, hence comment on

the shape of the molecule
C2H4 contains 2 pairs of electrons shared between 2’C’ atoms resulting a C=C
double bond, one being a strongly held sigma bond and the other is a weakly
held pi (π) bond. The π bond is a result of lateral overlapping of p-orbitals.
The 4 hydrogen’s is covalently bonded to carbon and they are directed to
the corners of an equilateral triangle.

3. Explain why Alkenes undergo addition reactions?

The pi (π) bond has a high electron density and which is weaker than the
sigma bond. Therefore, positively charged ions attract the π bond hence
undergo addition reaction.

4. State why alkenes are more reactive than alkanes?

Alkenes contain a loosely held π electron cloud whereas alkanes contain only
C-C single sigma bonds, which are relatively unreactive.

5. State the physical properties of alkenes

They are similar to alkanes as the number of electrons increases down the
homologous series, their boiling and melting points will increase.

6. Comment why boiling & melting points of alkenes are lower to the alkanes
bearing the same number of carbon atoms
Alkanes possess extra number of hydrogen atoms than the corresponding
alkenes with the same no. of ‘C’ atoms. This results in stronger
intermolecular force in alkanes than the corresponding alkene.

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7. What are the chemical properties of alkenes?
Due to the high electron density of the π electron cloud, it attracts
positively charged species, hence alkenes show addition reactions.

Electrophilic Addition Reactions

1. Explain why alkenes undergo electrophilic addition reactions?

The double bond between the 2 ‘C’ atoms consist of a sigma bond and a
loosely held pi bond formed by lateral overlapping of p-orbitals on the 2 ‘C’
atoms. The pi bond is much weaker than the sigma bond resulting a high
electron density which attracts positively charged entities, which are
referred to as electrophiles.

2. Write notes on below addition reactions

a) Electrophilic Addition Reactions of hydrogen to alkenes (Hydrogenation)

H2 gas and alkene does not react under normal conditions. When alkene is
mixed with H2 & passed over Ni’ catalyst at a temperature of 3000C, the
electrophile hydrogen attacks the C=C to form an alkane. This is important in
industry in the manufacture of margarine from vegetable oil.

b) Electrophilic Addition Reactions of halogens to Alkenes (Halogenation)

Alkenes react with halogens in absence of light at room temperature. The

halogen should be mixed in an inert solvent such as tetrachloro methane
(CCl4) to get a pure product.

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If bromine water is added [Br(aq)] OH- from water will also be added instead
of Br- across the C=C double bond.

The brown colour of bromine will turn colourless as the reaction proceeds.
Therefore, the reaction with Br2 (aq) is a qualitative test for unsaturation.

c) Electrophilic Addition Reactions of Pottasium manganate (VII) with Alkenes

KMnO4 is a very powerful oxidizing agent. An alkene treated with cold,

dilute, acidified KMnO4 will be oxidized to the di-ol.

d) Preparation of alcohols by the catalytic addition of steam to alkenes

A mixture of steam and alkene is passed over a H3PO4 catalyst at a

temperature of 3000C and a pressure of 60atm to produce the
corresponding alcohol.

3. Describe in detail the experimental procedure for the preparation of

cyclohexene from cyclohexanol

Cyclohexene can be made by the dehydration of cyclohexanol in the

presence of phosphoric acid catalyst by heating and distilling of the product.

OH
H3PO4
+ H2O
HEAT

cyclohexanol cyclohexene

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SAFETY:

Cyclohexanol and cyclohexene are flammable. The substances should be kept

away from naked flames.

Cyclohexanol is also harmful if inhaled or spilt on skin.

Concentrated phosphoric acid is very corrosive. Wear gloves when using it.

The fumes from this experiment are unpleasant. Carryout the reaction in a fume
cupboard.

PROCEDURE:

Dehydration of cyclohexanol:

1) Place 10cm3 of cyclohexanol into a pear shaped flask.

2) In a fume cupboard, holding the flask with a clamp and pointing the flask towards the
back of the fume cupboard, carefully add 4cm 3 of phosphoric acid dropwise with
swirling.
3) Set up the apparatus for distillation.

4) Heat the flask very slowly and gently, collecting the liquid that distils between 70-
90°C. Do not let the flask boil dry.

Purification of cyclohexene

5) The distillate will be a mixture of mainly cyclohexene and water, together with
other impurities such as unreacted cyclohexanol. Pour this mixture into a separating
funnel.
6) Add an equal volume of sodium chloride solution to help separate the organic and
aqueous layers. Stopper the funnel and shake before allowing the layers to settle.

7) Run off the aqueous lower layer into a beaker, and then collect the organic layer in a
small conical flask.
8) Add two or three small pieces of anhydrous calcium chloride, a drying agent, and
stopper the flask. Shake for a few minutes until the liquid is clear.

9) Decant the alkene into a clean flask and redistil it, collecting the liquid distilling
between 81-85°C.

10) Find the mass of your product.

Testing the cyclohexene

11) Use some bromine water to check that the product is unsaturated.
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 4.
a) Explain what are symmetrical & unsymmetrical (asymmetrical) alkenes?

When same types of atoms are bonded to both ‘C’ atoms across the C=C
double bond, they are symmetrical and possess a center of symmetry.

When different types of atoms are bonded to the C across the C=C, they
are asymmetrical and possess no center of symmetry.

b) Describe the Electrophilic Addition of Hydrogen halides to symmetrical alkenes

Symmetrical alkenes react with hydrogen halides when alkene gas is passed
through conc. HBr acid. This produces a haloalkane. If the alkene is a liquid,
then an organic solvent such as CCl4 should be mixed. If not, OH- from water
will be added instead of Br- . The H+ ion acts as an electrophile attacking the
C=C bond forming intermediate carbo cation.

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c) Describe the Electrophilic Addition of Hydrogen halides to unsymmetrical alkenes

When hydrogen halide reacts with asymmetrical alkenes, two possible

products are formed.

The major product is 2-bromopropane. The reason for this can be explained
by the mechanism, which depends on the stability of the carbocation.

d) The major product of asymmetrical addition reaction can be predicted by a useful

general rule, known as “markovnikoff’s rule”. What does it state?

When a molecule of hydrogen halide reacts with an asymmetrical alkene, the

major product is the one in which the ‘H’ atom attaches itself to the carbon
atom already carrying the higher no. of ‘H’ atoms.

(N:B: The stability of the carbocation is what is expected as an explanation

to the major product at the exam and not Markovnikoff’s law)

e) Predict the major products of the below reactions.

CH3CH2CH=CH2 + HCl

(CH3)2C = CH + HBr
CH3

CH3CH=C(C2H5)CH3 + HCl

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 Mechanisms of Alkenes

Heterolytic electrophilic Addition Reactions

▪ Mechanism for the reaction of halogens with alkenes:

The halogens Br2 & Cl2 undergo heterolytic electrophilic addition reaction
with alkene. When the halogen is added it will polarize as X+δ & X-δ, when
come closer to the π electron cloud, as the bond is relatively weak.
Therefore, the bond will be easily broken as the π electron of Alkene
approach a molecule of halogen. The X+δ halogen accept the electron and
release the shared electron to the other halogen atom. Therefore, the
electrophile X- adds to the alkene followed by X- which attacks the
carbocation.

▪ Mechanism for the reaction of hydrogen halides with symmetrical alkenes

Alkenes undergo heterolytic electrophilic addition reaction with hydrogen

halide. The electrophile H-Br is a polar molecule and is polarized as H+δ-Br-δ.
The 1st step is the slow addition of electrophile H+δ to the nucleophile alkene
to form a carbocation intermediate. The positively charged intermediate
reacts rapidly with the negative Br- in the 2nd step of the reaction

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 ▪ Describe the relative stabilities of carbocations

Carbocations are classified according to the number of alkyl substituents

that are bonded to the positive carbon. A primary carbocation has one
substituent, a secondary has two and a tertiary has three.

The alkyl groups are electron releasing (because ‘C’ is more electronegative
than ‘H’). Therefore, alkyl groups decrease the concentration of positive
charge on the ‘C’. Decreasing the positive charge increases the stability of
the carbocations. Therefore, the greater the number of alkyl groups at the
positive carbon, the greater the stability. So tertiary carbocations are more
stable than secondary, and secondary carbocations are more stable than
primary.

▪ Mechanism for the reaction of hydrogen halides with asymmetrical alkenes

Addition of a HX to an asymmetrical alkene is according to the

Markownikov’s rule. The ‘H’ atom will be attached to the ‘C’ that already
carries a higher number of the ‘H’ atom to produce the major product.

The formation of the major product can be explained according to the

stability of the carbocation formed during the reaction. Unlike in
symmetrical alkenes, asymmetrical alkenes produce two different
carbocations.

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Secondary carbocation will give rise to the major product 2-chloro propane,
whereas primary carbocation will result in the minor product 1-chloro
propane.

The major product depends on the stability of the carbocation. Secondary

carbocation is more stable than the primary carbocation. Therefore, the
lower energy of secondary carbocation means, its formation will require less
activation energy. Thus, the formation of secondary carbocation will be much
faster and easier.

Synthetic Polymers
1.
i. What are Polymers?

Polymer is an organic macromolecule formed by many small molecules joining

together.

ii. What are monomers?

The small molecules referred above are called monomers.

iii. What is Polymerization?

The process of joining monomers to form polymers.

2. Polymers are made by two different processes. Name them & describe each in
detail giving examples.

I. Addition Polymer (homo polymer):

▪ Addition reaction takes place across a C=C bond.

▪ No bi-product formed during polymerization.
▪ Mostly same kind of monomers joins together to form the polymer.

II. Condensation Polymer (co-polymer):

▪ Elimination reaction takes place between two monomers.

▪ Simple molecules such as H2O, HCl is given off as bi product.
▪ Mostly different kinds of monomers join together to form the
polymer.

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3. Describe the formation of poly(ethene) [polythene] & draw the structure of the
monomer unit & the polymer stating all the conditions

Monomer ethene is used in the manufacture of the addition polymer

polyethene. polythene/polythene is produced as a white waxy solid when
ethene monomer is heated to high temperature and pressure. Ethene
monomers join together across the C=C by addition reaction.

4. Draw the structures of the below monomers, which are derivations of ethene
monomer

Styrene Vinyl Chloride (Chloroethene)

Propene Tetrafluroethene

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5. Apply the principles of addition polymerization to describe the formation of
Polystyrene (Phenylethene) from styrene

The reaction is exactly same as for ethene. The extra group C6H5 repeats
throughout the polymer structure.

6. Similarly apply the principles of addition polymerization to the below monomers

& draw the structures of their respective polymers & name them.

i. Propene

ii. Vinyl Chloride (chloroethene)

iii. Tetrafluoroethene.

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7. Preparation of poly(methyl 2-methylpropenoate) known commercially as Perspex.

The monomer is the methyl ester of 2-methylpropenoic acid, methyl 2-

methylpropenoate

Addition Polymerization of methyl 2-methylpropenoate (Perspex) is shown

below:

Perspex is a transparent thermoplastic often used in sheet form as a

lightweight or shatter-resistant alternative to glass.

8. Explain how the use of renewable resource, recycling & energy recovery can
contribute to the more sustainable use of polymers

Monomers if manufactured by cracking of petroleum products, it will be

be non-renewable and a finite resource.
E.g.: ethene can be manufactured by cracking of long chain alkanes to
produce short chain alkene molecules such as ethene.

If ethene can be manufactured by dehydration of ethanol, it will be

renewable and infinite resource, which will result in more sustainable use
of polymers.
Recycling of plastics will reduce the demand on raw materials (monomers).
This also will be a solution for many environmental problems, which are
caused by the disposal of non-biodegradable polymers.

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9. Discuss how reducing waste preventing pollution of the environment contributes
to greener environment.

Plastic waste is a major environmental problem using less packaging,

recycling & the use of biodegradable materials are the ways to reduce
waste.
Plastic such as PVC are non-biodegradable. Therefore, take up a lot of space
in landfill sites. When incinerated (burnt) produces harmful gases such as
HCl. The best solution for non- biodegradable plastic is to recycle them.
However, this is expensive as the plastics have to be sorted first.

Another way is to manufacture plastic that are easily broken down by the
environment, either by the action of light or by organism. Starch granules
can be added to plastic before it is made into the object. The microorganism
breakdown the starch that turns the plastic in to a fine powder. Such
plastics are called biodispersible as organism causes the plastic to become
dispersed in the environment. Therefore, it is not appropriate to call them
as biodegradable plastics.

To reduce the emissions of from incineration, the flue gases of incinerators

are treated in various ways. Electrostatic precipitators are devices that
confer an electrical charge onto the particulates, and then collect them at a
charged electrode. A baghouse is a physical filter, which collects
particulates as flue gases are forced through a fine fabric. Some flue gas
chimneys contain chemicals which reacts / absorbs toxic gases. i.e Ca(OH) 2
absorbing SO2.

Steam Distillation

Steam distillation is a special type of distillation (a separation process) for temperature

sensitive materials like natural aromatic compounds. Steam distillation is useful to
extract volatile liquids which would decompose at its boiling point, which is immiscible
with water, from a complex mixture. It is used to extract perfumes from fruits & flowers.

Many organic compounds tend to decompose at high sustained temperatures.

Separation by normal distillation would then not be an option, so water or steam is
introduced into the distillation apparatus. By adding water or steam, the boiling points
of the compounds are depressed, allowing them to evaporate at lower temperatures,
preferably below the temperatures at which the deterioration of the material becomes
appreciable. After distillation the vapors are condensed as usual, usually yielding a two-
phase system of water and the organic compounds, allowing for simple separation.

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Applications

Steam distillation is employed in the manufacture of essential oils, for instance,

perfumes. In this method, steam is passed through the plant material containing the
desired oils. Eucalyptus oil and orange oil are obtained by this method on the industrial
scale.

Extracting limonene from oranges by steam distillation

The peel of oranges is boiled in water and the oil produced (limonene) distilled in steam
at a temperature just below 100 °C, well below its normal boiling point. The immiscible
oil can then be separated. Direct extraction by heating would result in decomposition
whereas steam distillation does not destroy the chemicals involved.

Limonene is an unsaturated hydrocarbon which can be tested for using bromine water
or potassium manganate (VII).

Structure & Properties of limonene:

Chemical formula C10H16

Molar mass 136.24 g·mol−1
Appearance colorless to pale-yellow liquid
Odor Orange smell
Density 0.8411 g/cm3
Boiling point 176 °C (349 °F; 449 K)
Solubility in water insoluble
Solubility Miscible in ether, ethanol.

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Procedure:

a. Grate the outer orange coloured rind of two oranges and add to 100 cm 3 of distilled
water in the 250cm3 round bottomed flask. Add anti-bumping granules to the round
bottomed flask. (anti-bumping granules ensure smooth boiling)

b. Set up the Steam distillation apparatus as shown in the apparatus section.

c. Heat the flask so that distillation proceeds at a steady rate, approximately one drop
per second of distillate.

d. Collect approximately 50 cm3 of distillate in the measuring cylinder. The oil layer will
be on the surface.

e. Transfer the distillate to a separating funnel. You cannot simply remove water as
water molecules cling strongly to limonene molecules, if try to evaporate the water it
will also carry limonene with it. Inorder to separate limonene from water the limonene
is extracted into an organic solvent ether.

Add the solvent ether, mix it well and let it stand for some time to allow the layers to
separate well. Limonene will get extracted in to the ether solvent and leave off water.
This gives a very high yield of limonene at the end.

f. Drain the lower aqueous layer off, leaving the upper limonene layer in the separating
funnel.

g. If the limonene is cloudy it still contains water, use a small amount of magnesium
sulfate (drying agent) to dry it, and then remove the limonene from the solid drying
agent by decanting it (if the solid dry agent has formed a clump) or filtering through a
small plug of cotton.

h. To finalize the extraction, the ether layer (b.pt. 37oC) has to be evaporated on a water
bath to leave the limonene (b.pt. 176oC).

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