Alkenes

General
Akenes and cycloalkenes are aliphatic unsaturated hydrocarbons.
e.g. hex-1-ene ,
cyclohexene

The alkenes form a homologous series with general formula CnH2n. Each member of the
series differs by a -CH2- unit.
Benzene (C6H6) is an aromatic arene (rather than the alkene "cyclohexatriene" that you
might expect), since the double bonds and single bonds are not alternating around the ring
as the displayed formula would suggest, but all equivalent, with the double bond
delocalised all around the ring.
That's why we use the symbol:

rather than:

Bonding
In addition to the single covalent sigma- bonds which hold the carbon atoms to the
hydrogen atoms, in an alkene there is double bond >C=C< between two of the carbon
atoms.

A double bond consists of:

a bonding pair of electrons in a sigma bond between the two carbon atoms, formed
by the end-on overlap of two orbitals
a bonding pair of electrons in a pi bond formed by sideways overlap of adjacent porbitals to form a second bond between the two carbon atoms. The electrons in the
pi bond are localised held in place between the two carbon atoms, so this region
has high electron density.
The pi-bond is formed parallel to the sigma bond, and it is this bond that restricts rotation of
a C=C bond, since the pi bond has to be broken before rotation can take place.

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Note also the spatial arrangement at each carbon atom: The three bonds from each carbon
are trigonal planar with approx 120 bond angle because the bonding pairs repel each
other as far as possible. The pi-bond is above and below the plane of the three sigma
bonds.
e.g. in propene we have CH3CH=CH2, so we have one carbon with 109 bond angles and
four sigma bonds, and two carbons with 120 bond angles and 3 sigma bonds plus a pi
bond between them:

Physical properties
Because of the double bond having different bond angles (120) to the rest of the chain
(109.5), alkenes can't pack as closely as the corresponding alkanes and therefore have
correspondingly lower melting and boiling points.
e.g.

boiling points in Kelvin:

ethene
169K
propene
226K

ethane
propane

185K
231K

Reactions of Alkenes
Most alkene reactions involve breaking the pi-bond, which has a lower bond enthalpy and
is therefore weaker than the sigma- bond. This leaves the sigma bond intact allowing the
attacking species to be attached to the chain to form a saturated molecule. These are
addition reactions.
With lots of negative charge in the area of high electron density between the two C=C
carbons, species wanting to accept an electron pair (often positively charged species, but
not always) are attracted here where they can attack the double bond.
We call species which are electron pair acceptors electrophiles (electron loving). Thus
these reactions are termed electrophilic addition reactions.
i) reaction with hydrogen, H2
H

e.g.

C C
H

+ H2

H H
H C C H
H H

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Reagents: Hydrogen
Conditions: Nickel catalyst, 150C
ii) reaction with halogens, Cl2, Br2, I2
H

e.g.

C C

H H

+ Br2

H C C H
Br Br

ethene

1,2-dibromoethane

Reagents: Bromine
Conditions: mix at room temp
Use:
test for the presence of a C=C bromine loses its orange colour and is
decolourised.
Note:
F2 is too powerful an oxidising agent and tends to ignite the hydrocarbon !
Chlorine and iodine produce similar addition products.
iii) reaction with hydrogen halides, HF, HCl, HBr, HI
H

e.g.

C C

+ HCl

H H

H C C H
Cl H

ethene

chloroethane

Reagent:
hydrogen chloride
Conditions: mix gases at room temperature
Note that reactivity increases from HF to HI. HF will react with an alkene only under
pressure.
Note also that addition of a hydrogen halide to an unsymmetrical alkene can result in two
possible isomeric products:
CH3CH=CH2 + HBr
H
H

CH3CHBrCH3

or

CH3CH2CH2Br

H H

H H H

H H H

C C C H

H C C C H

H C C C H

propene

H Br H

2-bromopropane

Br H H

1-bromopropane

iv) reaction with water (steam)

Where water is added to a molecule, as here, we call this a hydration reaction. This is not
to be confused with a hydrolysis, which is breaking a molecule up due to a reaction with
water forming two products.

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With an unsymmetrical alkene two isomeric products are possible.

e.g.

CH3CH=CH2 + H2O(g)
H

CH3CH2CH2OH

or CH3CH(OH)CH3

H H

H H H

H H H

C C C H

H C C C H

H C C C H

O H H

H O H

propene

propan-1-ol

propan-2-ol

Reagent:
water (steam)
Conditions: an acid catalyst such as H3PO4 at 300C and 6MPa pressure
Use:
this is the industrial route to alcohols not for drinking methylated spirits,
industrial alcohol etc.
Check your understanding:
Write equations (displayed or skeletal formulae) and show all the possible products
produced when:
i)
chlorine reacts with pent-2-ene
ii)
limonene (right) reacts with bromine water
iii)
hydrogen chloride reacts with 1,2-dimethylcyclohex-2-ene
iv)
hydrogen iodide reacts with buta-1,3-diene
v)
steam reacts with methylpropene
vi)
pent-1-ene is burnt in excess oxygen
Mechanism of electrophilic addition
The reaction begins with the approach of a molecule with a dipole
- either permanent, e.g. with HCl
- or induced by the presence of the double bond e.g. with Br2. The area of high
electron density in the C=C repels the electrons in Br-Br, pushing them towards the end of
the molecule furthest away from the C=C which therefore becomes - while the end of the
molecule nearest the C=C becomes +, and is therefore attracted towards the negative
charge of the C=C.
There are two steps.
This example shows the reaction of bromine with ethane, but these can be replaced by any
other halogen or alkene in this mechanism.
Step 1: Approach of electrophile and movement of an electron pair from
the pi-system to form a bond to the + end, followed by heterolytic
fission of the bond in the electrophile.
A curly arrow show where the electron pair comes from and
where they go. They always come FROM a bond or a lone pair
on an atom, and go TO an atom where the new bond is being
formed.

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Step 2: The intermediate carbocation (ion containing a carbon atom with a + charge) is
very reactive and immediately reacts with the negative ion from step 1, forming a covalent
bond

Note: when drawing mechanisms, there are marks for

- relevant dipoles
- lone pairs
- curly arrows (showing the movement of a PAIR of electrons)
Check your understanding:
vii)
Draw the mechanism for the electrophilic addition of HCl to propene to form
2-chloropropane.
viii)

Draw the mechanism for the addition of H2O(g) to cyclohexa-1,3-diene to form

cyclohexane-1,4-diol

Markownikoffs Rule
Reactions of hydrogen halides with unsymmetrical alkenes produce two different possible
products, but these are not equally likely to be formed. One will be the major product, and
one the minor product. Markownikoffs rule states that: the hydrogen atom of the H-X is
added to the carbon of the C=C which has the greatest number of hydrogen atoms/least
number of carbon atoms bonded to it.
To understand why this happens, we need to look again at the mechanism in particular
the intermediate carbocation that is formed when the H atom from the H-X has been added
in the first step. The most stable carbocation will be most likely to be formed.
Stability of carbocations increases with the number of alkyl groups bonded to the carbon
with the positive charge:
>

>

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Application
If we add HCl to propene, CH3CH=CH2, then we can see that the carbon in the middle of
the propene has one H and one C attached, while the one on the end has two H bonded to
it. Markownikoffs rule says the H of the HCl will be added here so the major product will be
2-chloropropane and the minor product 1-chloropropane.
To explain this, in step 1 we could form a primary carbocation, CH3CH2CH2+, by adding the
hydrogen to the middle carbon, or we could form a secondary carbocation CH 3CH+CH3 by
adding the hydrogen to the end carbon. The secondary carbocation is more stable, so this
is formed preferentially so that in the second step the chloride ion is added to the middle
carbon to form 2-chloropropane as the major product.
Check your Understanding:
ix)
Draw the structure of the major product formed when HBr reacts in an electrophilic
addition with 1-methylcyclohex-1-ene.
More about stereoisomerism in alkenes
It is easy to determine with is the cis- and which is the trans- isomer, because this definition
is based on there being two identical groups on either carbon of the C=C which are either
on the same side (cis-) or opposite sides (trans-).
Of more general use is the notation of E- and Z- isomers because it can be applied to any
alkene having different groups on each carbon of the C=C. The rules for determining which
isomer is E- and which is Z- are known as the CIP rules (Cahn-Ingold-Prelog).
The essence of the rules is that an E- isomer has the highest priority groups on either side,
and a Z- isomer has the highest priority groups on the same (zame?) side. The priority of
of the groups increases with the atomic number of the bonded atoms, stepping outwards
from the carbon atoms of the C=C to the first point of difference.
Application
e.g. isomers of 1-chloropropene:
The right C=C carbon is bonded to a C
atom (of the -CH3) and an H atom. This
is the first point of difference, where the
higher atomic number of the C makes the -CH3 the priority group.
The left C=C carbon is bonded to a Cl atom and an H atom. The higher atomic number of
the Cl atom makes the Cl the priority group. The E- isomer therefore has the CH3 and -Cl
on either side of the C=C, and the Z- isomer has them on the same side.
e.g. isomers of 1-chloro-2-methylbut-2-ene:
The right C of the C=C has a C (of the CH3) and an H atom
bonded to it, so the highest priority group is the CH3.
The left C of the C=C has two carbon atoms bonded to it,

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so this is not a point of difference, ands we have to step outwards, to where there is a
difference one carbon has an H and one has a Cl bonded to it, so the one with the Cl
becomes the priority group. The illustrated stereoisomer has the priority groups on either
side, so is the E- isomer.
Check your Understanding:
x)
Draw and label the E- and Z- isomers of 2-bromo-1-chloropropene
xi)

Draw and label the E- and Z- isomers of 3-methylpent-2-ene

xii)

A molecule has structural formula CH3CH=C(CH2CH2Cl)CH2CH2OH. Draw the

skeletal formula of the Z-isomer.

Addition Polymers
Alkenes can undergo addition reactions in which alkene molecules join to each other to
form long chains often tens of thousands of carbon atoms long.
The individual alkene molecules are referred to as monomers, and the resulting chain as a
polymer. Note that (ignoring the ends of the chain) the empirical formula of the monomer
and of the polymer are the same. We ignore the ends of the chain because they are
insignificant compared with the length of the polymer chain.
Examples:
But-1-ene and but-2-ene both react to form polymers. We may be required to draw the
monomers, sections of the polymers, the repeat units, or write a balanced equation for the
reactions:

but-1-ene

but-2-ene

It may be helpful to re-draw the monomer molecules starting with the C=C and adding to
each carbon the atoms/groups which are connected to it above and below:

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We then draw adjacent monomers, replacing the C=C with C-C and using these
dangling bonds to join the C=C carbons into a section of the polymer chain.

Drawing a repeat unit:

A repeat unit can be found by taking any two linked carbons in the polymer chain and
drawing a ring around them and their attached side groups.

If starting with the monomer, simply draw the monomer then turn the double bond into a
single bond and add connecting bonds to the two carbons which were originally doublebonded.
Drawing the monomer from repeat unit or a section of chain:
Take two adjacent carbons in the chain, plus their attached side groups. Remove the
connecting bonds and replace them with the double bond. For example, here's a repeat
unit of poly(pent-2-ene), from which we can construct the monomer:

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Writing a balanced equation:

We don't know how many monomers form the chain, so we use 'n' to be the number of
monomers. This will produce a chain 'n' repeat units long. Note the connecting bonds
sticking through the brackets, and don't forget the 'n' after the brackets to show the number
of times the repeat unit repeats.

Disposal of Waste Polymers

While addition polymers from crude-oil derived raw materials tend to be cheap, they are
also non-biodegradable (not broken down by micro-organisms). Having strong covalent
bonds which are mostly non-polar makes them resistant to chemical attack too. This makes
polymer waste hard to dispose of because it endures in the environment without
decomposing. It is unsuitable for disposal in landfill sites (although that is where much
polymer waste currently turns up) because more and more land has to be found.
More sustainable use of polymer waste can be achieved by:
combustion for energy generation, although it is necessary to remove toxic waste
products such as HCl formed during the combustion of halogenated plastics such as
PVC (polychloroethene). This reduces our dependence on finite fossil fuel
resources.
use as an organic feedstock for the production of plastics and other organic
chemicals (e.g. polymer waste can be cracked to produce shorter chain alkanes plus
alkenes)
reuse and repurposing of polymer waste materials
Research chemists can reduce environmental damage and improve sustainability in our
use of polymers by the development of photodegradable polymers or biodegradable
polymers, making use of sustainable sources of raw materials such as plant starches. This
reduces our dependence on finite crude-oil resources.
Check your understanding:
xiii) Write a balanced equation for the addition polymerisation used to form polyethenol
xiv) Draw a section of the polymer formed by addition polymerisation of methypropene
xv) Draw the monomer from which this
polymer is made:

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Answers to Check your Understanding questions:

Write equations (displayed or skeletal formulae) and show the product(s) produced when:
i)
chlorine reacts with pent-2-ene
Cl

Cl2 +

Cl

Br

ii)

Br

2 Br2 +

Br
Br

iii)

Cl

HCl +

or
Cl
I

iv)

2 HI

I
or

or

v)

H2O(g) +

HO

or
OH

vi)

vii)

+ 7 O2

H H
C C C H

H +
|
Cl -

5 CO2

H H H

H H H

H C C C H
H

5 H2O

H C C C H
H Cl H

:Cl-

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viii)

N.B. mechanism could be drawn

with both H2O attacking
simultaneously rather than
sequentially

Br

ix)
HBr

Br

Br

x)
Cl

Cl
E- isomer

Z- isomer

xi)

Z- isomer

E- isomer

OH

xii)

The first point of difference on the right C of the

C=C is at the Cl and O atoms. The Cl has the higher
atomic number, so is on the same side as the higher
priority CH3 group on the other carbon in the Z-isomer.

Cl

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xiii)
H H

H H

C C

H OH
xiv)

xv)

methypropene can be drawn as

C C
H OH

n
so the section of the polymer is

H CH3

H CH3 H CH3 H CH3

C C

C C

H CH3

H CH3 H CH3 H CH3

C C

C C

the monomer is phenylethene:

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