3.

4 Alkenes
Alkenes contain a carbon-
Alkenes are unsaturated hydrocarbons General formula is CnH2n carbon double bond
somewhere in their structure.
H H H H

C C C H The arrangement of bonds around the

C C Ethene Propene
H H H
>C=C< is planar and has the bond angle 120o
H H
H H H H
Numbers need to be H
added to the name when H C C C C H But-2-ene
C C C C H But-1-ene
positional isomers can
occur. H H H H H H H H

π bonds are exposed and have high

C=C double covalent bond electron density.
consists of one sigma (σ)
bond and one pi (π) bond. They are therefore vulnerable to attack
by species which ‘like’ electrons: these
species are called electrophiles.

Stereoisomerism

Stereoisomers have the same structural formulae Alkenes can exhibit a type of isomerism
but have a different spatial arrangement of atoms. called E-Z stereoisomerism

E-Z isomers exist due to restricted E-Z stereoisomers arise when:

rotation about the C=C bond (a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of
Single carbon-carbon covalent the double bond.
bonds can easily rotate

H H

H H
two different groups H C C H But-1-ene
H C C H attached either end of
C C
the restricted double H H
C C H
bond- leads to EZ H two identical groups attached to
H H H H isomers one end of the restricted double
Z- but-2-ene bond – no E-Z isomers

But-1-ene is a structural isomer of But-2-

H
H These are two ene but does not show E-Z isomerism.
C H isomers as the lack
H of rotation around Naming E-Z stereoisomers
C C the double bonds
H
means one cannot First determine the priority groups on both sides of
H C
be switched to the the double bond
H
H other.
Priority Group: The atom with the bigger
E -but-2-ene Atomic number is classed as the priority atom

Priority Priority Cl H
group Cl Cl group
side 1 side 2 C C
C C
Z-1,2-dichloroethene
H H H Cl E-1,2-dichloroethene
If the priority atom is on the same side of the If the priority atom is on the opposite side of
double bond it is labelled Z from the german the double bond it is labelled E from the
zusammen (The Zame Zide!) german entgegen (The Epposite side!)

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Electrophilic Addition Reactions of Alkenes
Definition Electrophile: an electron pair acceptor
The double bonds in alkenes are areas with high
electron density. This attracts electrophiles and the
Addition reaction: a reaction where two
alkenes undergo addition reactions.
molecules react together to produce one
1. Reaction of Bromine with Alkenes
H H
Change in functional group: alkene  dihalogenoalkane
H H
Reagent: Bromine
Conditions: Room temperature (not in UV light) C C + Br2  H C C H

Mechanism: Electrophilic Addition

H H Br Br
Type of reagent: Electrophile, Br+
1,2-dibromoethane

As the Br2 molecule H H

H H H H
approaches the alkene,
the pi bond electrons + The INTERMEDIATE
C C H C C H H C C H formed, which has a
repel the electron pair in
the Br-Br bond. This positive charge on a
H Brδ+ H Br carbon atom is called a
INDUCES a DIPOLE. Br2 Br Br
becomes polar and :Br - CARBOCATION
ELECTROPHILIC (Brδ+). Brδ-
2. Reaction of Hydrogen Bromide with Alkenes
Change in functional group: alkenehalogenoalkane H H H H H H
Reagent: HCl or HBr
H C C C C H + HBr  H C C C C H
Conditions: Room temperature
Mechanism: Electrophilic Addition H H H H H H Br H
Type of reagent: Electrophile, H+ But-2-ene 2-bromobutane

HBr is a polar
H H
H H H This reaction can
molecule because H
Br is more lead to two
H3C C C CH3 +
electronegative H3C C C CH3 H3C C C CH3 products when the
than H. The H δ + is δ+ alkene is
attracted to the H H Br H unsymmetrical
-
electron-rich pi Br δ :Br -
bond.

‘Markownikoff’s Rule’
H :Br -
In most cases, bromine will be added to the + H H H H
carbon with the fewest hydrogens attached to it C CH2
Major
H C C C C H
If the alkene is H3C CH3 product
unsymmetrical, δ+ δ- :Br - 90%
addition of hydrogen H Br H H Br H
bromide can lead to H H
two isomeric
H2C CH CH2 CH3 C
+
C CH2 CH3 CH2 CH2 CH2 CH3 Minor
products. product
H Br 10%
H
WHY? In electrophilic addition to alkenes, the major product is
This carbocation intermediate H H H formed via the more stable carbocation intermediate.
is more stable because the
methyl groups on either side H C C C H In exam answers
of the positive carbon are +
•Draw out both carbocations and identify as primary, secondary
electron releasing and reduce and tertiary
H H
the charge on the ion which •State which is the more stable carbocation e.g. secondary more
stabilises it. stable than primary
•State that the more stable carbocation is stabilised because the
The order of stability for carbocations is methyl groups on either (or one) side of the positive carbon are
tertiary > secondary >primary electron releasing and reduce the charge on the ion.
•(If both carbocations are secondary then both will be equally 2
stable and a 50/50 split will be achieved)
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3. Reaction of Sulphuric acid with Alkenes
Stage 1
Stage 2
Change in functional group
Change in functional group
alkene  alkyl hydrogensulphate alkyl hydrogensulphate  alcohol
Reagents: concentrated H2SO4 Reagents: water
Conditions: room temperature Conditions: warm mixture
Mechanism: Electrophilic Addition Type of reaction: hydrolysis
Type of reagent: Electrophile, H2SO4
CH3CH2OSO2OH + H2O  CH3CH2OH + H2SO4
CH2=CH2 + H2SO4  CH3CH2OSO2OH

Stage 1: electrophilic addition

H2SO4 is best
H H H H H drawn as
H

H3C C C H
+
H3C C C H
H-OSO2OH
H3C C C H
in exams. Its real
δ+ H H
H OSO 2OH structure is
-:OSO
2OH H O O
OSO 2OH
δ-
S
Stage 2: hydrolysis
H O O
H H H

H3C C C H + H2O H3C C CH3 + H2SO4 Overall role of

sulphuric acid is that
H OH of a catalyst (as it is
OSO 2OH regenerated)

With unsymmetrical alkenes a minor and major product can also be formed similar to the
addition of HBr. The same explanation applies.

Definition: Hydrolysis – a reaction where the molecule is split by the addition of water

Direct Industrial hydration of alkenes to form alcohols This reaction can be called
Industrially alkenes are converted to alcohols in one step rather than the hydration: a reaction where
two in the above sulphuric acid reaction. They are reacted with water in water is added to a molecule
the presence of an acid catalyst.
Essential Conditions

CH2=CH2 (g) + H2O (g)  CH3CH2OH High temperature 300 to 600°C

(l)
High pressure 70 atm
Catalyst of concentrated H3PO4

The high pressures needed mean this cannot be done in the laboratory. It is preferred industrially, however,
as there are no waste products and so has a high atom economy. It would also mean separation of products
is easier (and cheaper) to carry out. See equilibrium chapter for more on the industrial conditions for this
reaction.
Testing for Alkenes with Bromine water
Bromine water decolourises in the presence of a double bond. This can be used as a
test for the presence of an double bond in a molecule. It can be used quantitatively to
show the presence of multiple double bonds in compounds like polyunsaturated oils.

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Addition Polymers
Addition polymers are formed from alkenes Poly(alkenes) like alkanes are unreactive due to
the strong C-C and C-H bonds
This is called addition polymerisation

be able to recognise the repeating unit in a poly(alkene)

n

Monomer H H H H H H
Polymer
Ethene polyethene C C C C C C
H H H H
CH3 H CH3 H CH3 H
n C C C C

H CH3
H CH3 n
propene
poly(propene)
Add the n’s if writing an equation showing the
Poly(propene) is recycled
reaction where ‘n’ monomers become ‘n’ repeating
units

H H
If asked to draw one
repeating unit, don’t add
the n on to your diagram, C C
because n represents a
large number H CH3

It is best to first draw out H CH3

You should be able e.g. For but-2-ene the monomer with groups H CH3
to draw the polymer of atoms arranged around
C C C C
repeating unit for any H3C CH CH CH3 the double bond
alkene H3C H
CH3 H

Poly(chloroethene) is a polymer that is water proof, an electrical

insulator and doesn’t react with acids.
H H In its pure form it is a rigid plastic due to the strong intermolecular
bonding between polymer chains prevents them moving over each
C C other. In this un-plasticised form it is used make uPVC window frame
coverings and guttering.
If a plasticiser is added the intermolecular forces are weakened which
H Cl allows the chains to move more easily resulting in more flexibility in the
polymer. In this form PVC is used to make insulation on electrical wires,
and waterproof clothing

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