ALKENES

CHEMICAL PROPERTIES OF ALKENES

1. The cloud of electrons which forms the bond in alkene lies above and below the plane of the molecule.
In this position, the electrons are susceptible to attack by electrophiles.
2. In an addition reaction of alkene, the bond of the carbon-carbon double bond breaks in order to release
electrons to form two new bonds with the reactant molecule and a saturated molecule is formed.
a)

Electrophilic addition
Hydrogenation, H2
1)
Halogenations, Cl2, Br2
2)
Hydrohalogenation, HCl, HBr
3)
Hydration, H2O
4)

b) oxidation
complete combustion
5)
present catalyst, Ag
6)
cold KMnO4, H+
7)
hot KMnO4, H+
8)
ozonolysis, O3
9)
c)

addition polymerization

ADDITION REACTIONS OF ALKENES (ELECTROPHILIC ADDITION)

(1) Addition Of Hydrogen (Hydrogenation)
carried out by passing hydrogen and the alkene, both in the gaseous state, over a metal catalyst(very
finely powdered nickel) at 150C and 5 atm pressure
(If platinum catalyst is used, the process takes place under normal laboratory conditions.)
An example of hydrogenation reaction of alkene is
the reaction of ethene with hydrogen to produce
ethane.

QUESTIONS
ANSWERS
(1) Write down the structure of the products, if any, of the following reactions
(a)

(ethene)
(b)

(c)

(2) Write down the structure of the products, if any, of the following reactions.
(a)
(b)

(3) 10.8 g of an alkene required 9.6 dm3 of hydrogen gas for complete hydrogenation at room conditions.
Write down the possible structural formula of the alkene. [Molar mass of the alkene = 54.0 g mol -1; 1 mol of gas
occupies 24.0 dm3 at room conditions]

(2) Addition Of Halogens (Chlorine Or Bromine) - Halogenation

1. Both chlorine, Cl2, and bromine, Br2,
add rapidly to the carbon-carbon double
bond at room temperature without the
need of any catalyst.
(a) Ethene reacts with chlorine gas at
room temperature to form1,2dichloroethane.
(b) Cyclohexene reacts rapidly with
bromine to form 1,2-dibromocyclohexane

(c)When an alkene is bubbled through a

solution of bromine in hexane or
tetrachloromethane (organic solvent), the
brown colour of bromine is rapidly
decolorised
(Decolorisation of bromine solution is a
useful test reaction to detect a double
bond)
THE MECHANISM OF ADDITION OF BROMINE TO ETHENE
(Electrophilic addition- the bromine molecule, Br2, acts as an electrophile because it is attracted to the electron-rich
carbon-carbon double bond.
(a) When a bromine molecule approaches an ethene
molecule, the pi electron cloud of ethene interacts with
the approaching bromine molecule, causing a
polarisation of the Br-Br bond.
The double bond of ethene induces a dipole on Br2.
(b) A loose association forms between the ethene and
bromine molecules. Electrons move from the double
bond towards the partially positively charged bromine
atom and at the same time electrons in the Br-Br bond
are repelled to the partially negatively charged bromine
atom .
This results in the formation of two ions, a carbocation
and a bromide ion, Br-.
(A carbocation is a species that contains a carbon atom
with only three bonds to it and bearing a positive
charge).
(c) The carbocation is very unstable and quickly
combines with the bromide ion, Br-, to form 1,2dibromoethane.
(Iodine does not add to the carbon-carbon double bond
and fluorine reacts explosively to give a mixture of
products)

QUESTION

ANSWER
3

(1) Give the equations, the conditions and the names of the products when
(a) propene reacts with bromine

(b) cydohexene reacts with bromine

(2)
Would you expect a species which attacks
alkenes to be an electrophile or a nudeophile?
Give a reason for your answer.

(3)Name and draw structural formulae for the products of the following halogenation

(a)

(b)

(4) How would you distinguish between

cyclohexene and cyclohexane using simple testtube reactiond?

(5) Briefly outline the mechanism for the

reaction between cyclohexene dan bromine in
hexane at room temperature.

REACTION WITH BROMINE WATER

1. An alkene reacts readily at room temperature with an aqueous solution of bromine (bromine water) to produce a
mixture of products, bromo alcohol and dibromoalkane.
2. The bromine water would be decolorised

1. Write a

Note: 2-B
unsymme

Water has lone pairs of electrons and can act as nucleophiles in competition with bromide ions, Br - .

2. Write a
(a) but-2-

(b) but-l-e

3. When ethene is bubbled into bromine water, the reddish-brown bromine water is rapidly decolorised
and a mixture of 2-bromoethanol and 1,2-dibromoethane is produced

4. If the bromine water is dilute, bromoalcohol would be the main product because there will be more
water molecules than bromide ions present.

(3) Reaction With Hydrogen Halides

1. Hydrogen halides readily add to the carboncarbon double bond in the cold to give haloalkanes.

2. Ethene produces chloroethane on bubbling

through concentrated hydrochloric acid at room
temperature.
(The rate of addition decreases in the order H-I > HBr > H-Cl because the bond energy of the hydrogen
halides increases from H-I to H-Cl. )
ADDITION OF HYDROGEN HALIDE TO UNSYMMETRICAL ALKENES

(a) When propene reacts with a hydrogen halide

such as hydrogen bromide, HBr, there are two
possible products.
1- Bromopropane (minor product).
2-Bromopropane(major product).

(b) The addition of hydrogen halide to a carbon-carbon double bond in an unsymmetrical alkene follows the
MARKOVNIKOFF'S RULE, that is, the hydrogen atom of the hydrogen halide adds to the carbon atom of
the double bond with the greatest number of hydrogen atoms.
(c)An unsymmetrical carbon-carbon double bond is
one whose two carbon atoms hold unequal number
of hydrogen atoms.

EXAMPLES :

The carbon-carbon double bond is a site that can accept a proton from an acid and forms carbocation

STABILITY OF CARBOCATION
(a) In the reaction between propene and hydrogen bromide, the initial attack is by the acid catalyst
(b) When the hydrogen ion, H+, attacks the double bond in propene, two different carbocatino
can be formed.

(c) In the primary carbocation there is only one alkyl

(ethyl) group pushing electrons onto the positively
charged carbon atom.

The secondary carbocation is more stable than the primary

carbocation. This is because in the secondary carbocation
there are two alkyl groups (methyl groups) pushing electrons
onto the positively charged carbon atom.
(d) As a result, the positive charge in the secondary carbocation is stabilised slightly more than that in the primary
carbocation. This is because the donated electrons tend to cancel out the charge.
(e) Secondary carbocation is therefore more stable of the two possible intermediate carbocations, making it more likely
to form and combine with Br- ion to form 2-bromopropane.

(f)
The order of stability of the carbocations is as follows:

The tertiary carbocation is the most stable because it has three electron-donating alkyl groups which tend to cancel out
the positive charge more than the secondary or primary carbocation.
QUESTIONS
(a) When but-1-ene, CH3 - CH2 - CH = CH2, reacts
with hydrogen bromide, what are the
structures of the two possible intermediate
carbocations formed?

ANSWERS

(b) Which one of those two ions is more stable?

(c) What will be the major product of the reaction

between but-I-ene and hydrogen bromide?
Arrange the following alkenes in order of increasing
reactivity on addition of hydrogen bromide.

QUESTIONS
ANSWERS
(1)Name and draw the structural formulae for the major products of these addition reactions of alkenes.
(a)

(b)

(c)

(2)
Suggest why when 2-methylpropene reacts with hydrogen iodide, the major product is 2 - iodo- 2 - methylpropane.

When 2-methylpropene reacts with hydrogen iodide, two different carbocations could be formed:

The tertiary carbocation is more stable than the primary carbocation.

The tertiary carbocation has three alkyl groups pushing electrons onto the positively charge carbon atom whereas
the primary carbocation has only one alkyl group. As a result, the positive charge in the tertiary carbocation is
stabilised slightly more because the donated electrons tend to cancel to charge.
Hence, the tertiary carbocation is more stable and more likely to form and react with iodide ions than the primary
carbocation. Thus, the major product is 2-iodo-2-methylpropane.
(3) Briefly outline the reaction mechanism for the reaction between ethene and hydrogen bromide at room
temperature
When ethene reacts with hydrogen bromide, a
carbocation forms together with a bromide ion.

In the second step, the bromide ion attacks the carbocation

(4) Name and draw structural formulae for the major products of these addition reactions of alkenes
(a)

(b)

(c)

REACTION WITH CONCENTRATED SULPHURIC (VI) ACID

1. An alkene undergoes addition

reaction with concentrated
sulphuric(VI) acid in the cold to give
alkyl hydrogensulphate

2.When added to water and warmed,

the alkyl hydrogensulphate is
converted to an alcohol. This is a
hydrolysis reaction, i.e. breaking up a
compound by reacting with water.
3. When ethene is bubbled into
concentrated sulphuric(VI) acid in the
cold, ethyl hydrogensulphate is
produced

4. The product, ethyl

hydrogensulphate, when added to
water and warmed, is hydrolysed to
ethanol.
(The addition of concentrated
sulphuric(VI) acid to unsymmetrical
alkenes follows Markovnikoff's
rule)

QUESTIONS

ANSWERS

1 (a) What is formed when propene

reacts with concentrated sulphuric(VI)
acid in the cold?

(b) What is the product of hydrolysis of

the compound formed in (a)?

2. Draw structural formulae for the major products of these acid-catalysed hydration reactions of alkenes.

(a)

(b)

(c)
(4)

Reaction With Steam (Hydration)

1. When steam and ethene are passed over a catalyst, ethanol is produced. A temperature of 330C and a pressure of
60 atm are used in the presence of phosphoric acid catalyst.

(a) The hydration of alkenes follows Markovnikoff's The hydration of propene:

Name and draw structural formulae for the major products of these addition reactions of alkenes
(a)

(b)

OXIDATION: REACTION WITH POTASSIUM MANGANATE (VII)

(1) Reaction With Cold Dilute Potassium Manganate(Vii) Acidified
With Dilute Sulphuric(Vi) Acid
1. An alkene will react with dilute potassium manganate(VII) in an acidic or alkaline solution to give a diol.
The reaction with manganate(VII) ion, Mn04-, involves both addition and oxidation.

2. When ethene is added to dilute potassium manganate(VII) acidified with dilute sulphuric(VI) acid at room

10

temperature, the purple colour of the potassium manganate(VII) is decolorised and ethene is oxidised to
ethane- I,2-diol.

3. If the reaction involves cold dilute potassium manganate(VII) in alkaline conditions, the purple colour of the
potassium manganate(VII) is decolorised, producing ethane-l,2-diol and a brown precipitate of manganese(IV) oxide.
(2) Reaction With Hot, Concentrated Potassium Manganate (Vii)
Acidified With Dilute Sulphuric(Vi) Acid
1. If an alkene is added to hot, concentrated potassium manganate(VII) acidified with dilute sulphuric(VI)
acid, the carbon-carbon double bond is oxidatively cleaved, i.e. the double bond breaks and produces
ketones, aldehydes, carboxylic acid (from further oxidation of aldehydes formed), carbon dioxide or
mixtures of these.

2. On addition of ethene to hot, concentrated acidified potassium manganate(VII), ethene is oxidatively

cleaved to give methanal (an aldehyde) which is further oxidised to methanoic acid (a carboxylic acid).
On further oxidation, methanoic acid will form carbon dioxide and water.

3. When 2-methylbut-2-ene is added to hot, concentrated acidified potassium manganate(VII), it is oxidised with the
breaking of the carbon-carbon double bond to give ethanal (an aldehyde) and propanone (a ketone). The ethanal is further
oxidised to ethanoic acid. The purple colour of the potassium manganate(VII) is decolorised.

1. An unknown alkene X with the formula CSH16 was found on oxidation with hot, acidified potassium manganate(VII) to

11

yield propanoic acid and pentanoic acid. Name the alkene X.

Realign the acids to give a better picture of the alkene:
Hence, the alkene is cis- or trans-oct - 3 -ene

2. Write structures for the product(s) that would form under the conditions shown:

(a)

(b)
(c)

(d)

(e)

QUESTIONS
ANSWERS
3.Write structures for the organic product(s) that would form under the conditions shown
(a)

(b)

(c)

12

(d)

4. Draw the structural formulae for the alkenes X and Y below.

(a)

(b)

(3) Reaction With Oxygen

Complete combustion
1. Alkenes burn in air with a sooty flame
.Since alkenes have a higher percentage of carbon than their corresponding alkanes, they burn with a more sooty flame
than alkanes. Hence alkenes are not used as fuels.
Present Catalyst, Ag
2. In the presence of finely divided silver
catalyst at about 180C, ethene reacts with
oxygen to produce epoxyethane.
Epoxyethane is an unstable compound
because of the ring strain.
(b) Epoxy thane reacts rapidly with water to
produce ethane-1,2-diol. This is an industrial
method to prepare ethane- l,2-diol which is
used to manufacture antifreeze and polyesters

POLYMERISATION
1. Alkenes containing carbon-carbon double
bonds can polymerise (addition
polymerization) joining together to form
long chain molecules. No atoms or
molecules are eliminated in this process.

2.Poly(ethene) is the most common

synthetic polymer whose monomer is
ethene.

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3. There are two types of poly(ethene), depending on the conditions used for preparation.
(a) (i) Low-density poly(ethene) is manufactured by
heating ethene at about 200C and a pressure of 1 200
atmosphere with traces of oxygen (initators).
(ii) Low-density poly(ethene) has chain branching
which makes it difficult to pack closely.
It has a low melting point, 105C, softens in boiling
water and deforms easily.
(iii) It is used for making plastic bags and wrappers.

(b) High-density poly(ethene) is manufactured by heating

ethene at a lower temperature (60C) and pressure with
the use of catalysts, a mixture a triethyl aluminium and
titanium(IV) chloride (Ziegler- Natta catalysts).
(ii) It has no chain branching and can be packed closely
together; hence, it is more rigid and has a higher melting
point, 135C.
(iii) High-density poly(ethene) is used in making bottle
crates and bottles.

IMPORTANCE OF ETHENE IN INDUSTRY

(a) Manufacture of a number of
plastics
Ethene is the raw material for the
manufacture of poly(ethenel),
poly( chloroethene) and polyester
fibres.

(b) Manufacture of ethane-I,2-diol

(c) Manufacture of ethanol

Ethane-1,2-diol is prepared by
reacting ethene with oxygen in the
presence of a heated silver catalyst,
followed by addition of water.

Ethanol is manufactured by
hydration of ethene using
phosphoric acid catalyst on silica al
300C and 60 atmospheres.

Ethane-l,2 -diol is used as antifreeze

in car radiators and for making
detergents.

Ethanol is used as a solvent for

varnishes, cosmetic and toilet
preparations and also in the
manufacture of ethanal.

IMPORTANCE OF ETHENE IN INDUSTRY

14

REACTIONS
1

TYPE OF
REACTION
Electrophilic
addition

Alkene alkane

Alkene dihaloalkane

Alkene haloalkane

4
5

Alkenedibromoalkane
+
bromoalcohol
Alkenealcohol

Alkenediol

Alkene ketones + aldehydes

Carboxylic
Alkene diol
(industrial method)

REAGENT(S)

CONDITION(S)

H2(g); Ni catalyst

150C; 5 atm

H2(g); Pt catalyst

Room temperature

Electrophilic
addition
Electrophilic
addition
Electrophilic
addition

Cl2 in CC14 or Br2 in CC14

Room temperature

Electrophilic
addition
Oxidation

Concentrated H2SO4 acid

followed by water
Dilute KMnO 4/H+
Dilute KMnO 4/OHConcentrated /KMnO 4/H+

Cold
Warm
Cold
Cold
Hot

Concentrated /KMnO 4/ OH-

Hot

O2(g); Ag catalyst
followed by water

180C
Room temperature

Oxidation and
cleavage

acid
Oxidation

15

Concentrated HCl or concentrated HBr

Room temperature
Bromine water