AN INTRODUCTION TO

THE CHEMISTRY
OF ALKANES

KNOCKHARDY PUBLISHING
 KNOCKHARDY PUBLISHING

THE CHEMISTRY OF ALKANES

INTRODUCTION
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THE CHEMISTRY OF ALKANES

CONTENTS
• Structure of alkanes
• Physical properties of alkanes
• Chemical properties of alkanes
• Breaking covalent bonds
• Chlorination via free radical substitution
• Cracking
• Revision check list
THE CHEMISTRY OF ALKANES

Before you start it would be helpful to…

• Recall the definition of a covalent bond

• Be able to balance simple equations
• Be able to write out structures for hydrocarbons
 ALKANES

General members of a homologous series

general formula is CnH2n+2 - for non-cyclic alkanes
saturated hydrocarbons - all carbon-carbon bonding is single
bonds are spaced tetrahedrally about carbon atoms.

Isomerism the first example of structural isomerism occurs with C4H10

BUTANE 2-METHYLPROPANE

Structural isomers have the SAME MOLECULAR FORMULA BUT

DIFFERENT STRUCTURAL FORMULA

They possess different physical properties such as boiling point,

melting point and density
 HYBRIDISATION OF ORBITALS

2p
The electronic configuration of a 2
carbon atom is 1s22s22p2 2s

1 1s
 HYBRIDISATION OF ORBITALS

2p
The electronic configuration of a 2
carbon atom is 1s22s22p2 2s

1 1s

If you provide a bit of energy you 2p

2
can promote (lift) one of the s 2s
electrons into a p orbital. The
configuration is now 1s22s12p3
1 1s

The process is favourable because the of arrangement of

electrons; four unpaired and with less repulsion is more
stable
 HYBRIDISATION OF ORBITALS IN ALKANES

The four orbitals (an s and three p’s) combine or HYBRIDISE to give four
new orbitals. All four orbitals are equivalent.

Because one s and three p orbitals are used, it is called sp3 hybridisation

2s22p2 2s12p3 4 x sp3

 THE STRUCTURE OF ALKANES

In ALKANES, the four sp3

orbitals of carbon repel each
other into a TETRAHEDRAL
arrangement with bond angles
of 109.5º.

Each sp3 orbital in

109.5º
carbon overlaps with
the 1s orbital of a
hydrogen atom to form
a C-H bond.
 PHYSICAL PROPERTIES OF ALKANES

Boiling point increases as they get more carbon atoms in their formula
more atoms = greater intermolecular Van der Waals’ forces
greater intermolecular force = more energy to separate the molecules
greater energy required = higher boiling point

CH4 (-161°C) C2H6 (-88°C) C3H8 (-42°C) C4H10 (-0.5°C)

difference gets less - mass increases by a smaller percentage

 PHYSICAL PROPERTIES OF ALKANES

Boiling point increases as they get more carbon atoms in their formula
more atoms = greater intermolecular Van der Waals’ forces
greater intermolecular force = more energy to separate the molecules
greater energy required = higher boiling point

CH4 (-161°C) C2H6 (-88°C) C3H8 (-42°C) C4H10 (-0.5°C)

difference gets less - mass increases by a smaller percentage

Straight chains molecules have greater interaction than branched

STRUCTURAL ISOMERS OF C5H12

HIGHEST BOILING POINT LOWEST BOILING POINT

“The greater the branching, the lower the boiling point”

 PHYSICAL PROPERTIES OF ALKANES

Melting point general increase with molecular mass

the trend is not as regular as that for boiling point.

Solubilityalkanes are non-polar so are immiscible with water

they are soluble in most organic solvents.
 CHEMICAL PROPERTIES OF ALKANES

Introduction - fairly unreactive; (old family name, paraffin, meant little reactivity)
- have relatively strong, almost NON-POLAR, SINGLE covalent bonds
- they have no real sites that will encourage substances to attack them

Combustion - make useful fuels - especially the lower members of the series
- react with oxygen in an exothermic reaction

complete CH4(g) + 2O2(g) ——> CO2(g) + 2H2O(l)

combustion

incomplete CH4(g) + 1½O2(g) ——> CO(g) + 2H2O(l)

combustion

the greater the number of carbon atoms, the more energy produced
BUT the greater the amount of oxygen needed for complete combustion.

Handy tip When balancing equations involving complete combustion, remember...

every carbon in the original hydrocarbon gives one carbon dioxide and
every two hydrogen atoms gives a water molecule.

Put the numbers into the equation, count up the O’s and H’s on the RHS
of the equation then balance the oxygen molecules on the LHS.
 POLLUTION
Processes involving combustion give rise to a variety of pollutants...

power stations SO2 emissions produce acid rain

internal combustion engines CO, NOx and unburnt hydrocarbons

Removal
SO2 react effluent gases with a suitable compound (e.g. CaO)
CO and NOx pass exhaust gases through a catalytic converter

Catalytic converters
In the catalytic converter ... CO is converted to CO2
NOx are converted to N2
Unburnt hydrocarbons are converted to CO2 and H2O

e.g. 2NO + 2CO ———> N2 + 2CO2

• catalysts are made of finely divided rare metals Rh, Pd, Pt

• leaded petrol must not pass through the catalyst as the lead
deposits on the catalyst’s surface and “poisons” it, thus blocking
sites for reactions to take place.
 BREAKING COVALENT BONDS

There are 3 ways to split the shared electron pair in an unsymmetrical covalent bond.

UNEQUAL SPLITTING
produces IONS
known as HETEROLYSIS or
HETEROLYTIC FISSION

EQUAL SPLITTING
produces RADICALS
known as HOMOLYSIS or
HOMOLYTIC FISSION

• If several bonds are present the weakest bond is usually broken first
• Energy to break bonds can come from a variety of energy sources - heat / light
• In the reaction between methane and chlorine either can be used, however...
• In the laboratory a source of UV light (or sunlight) is favoured.
 FREE RADICALS

TYPICAL PROPERTIES

• reactive species (atoms or groups) which possess an unpaired electron

• their reactivity is due to them wanting to pair up the single electron

 FREE RADICALS

TYPICAL PROPERTIES

• reactive species (atoms or groups) which possess an unpaired electron

• their reactivity is due to them wanting to pair up the single electron

• formed by homolytic fission (homolysis) of covalent bonds

• formed during the reaction between chlorine and methane

• formed during thermal cracking

• involved in the reactions taking place in the ozone layer

 CHLORINATION OF METHANE

Reagents chlorine and methane

Conditions UV light or sunlight - heat is an alternative energy source

Equation(s) CH4(g) + Cl2(g) ——> HCl(g) + CH3Cl(g) chloromethane

CH3Cl(g) + Cl2(g) ——> HCl(g) + CH2Cl2(l) dichloromethane
CH2Cl2(l) + Cl2(g) ——> HCl(g) + CHCl3(l) trichloromethane
CHCl3(l) + Cl2(g) ——> HCl(g) + CCl4(l) tetrachloromethane

Mixtures free radicals are very reactive - they are trying to pair their electron
with sufficient chlorine, every hydrogen will eventually be replaced.
 CHLORINATION OF METHANE

Reagents chlorine and methane

Conditions UV light or sunlight - heat is an alternative energy source

Equation(s) CH4(g) + Cl2(g) ——> HCl(g) + CH3Cl(g) chloromethane

CH3Cl(g) + Cl2(g) ——> HCl(g) + CH2Cl2(l) dichloromethane
CH2Cl2(l) + Cl2(g) ——> HCl(g) + CHCl3(l) trichloromethane
CHCl3(l) + Cl2(g) ——> HCl(g) + CCl4(l) tetrachloromethane

Mixtures free radicals are very reactive - they are trying to pair their electron
with sufficient chlorine, every hydrogen will eventually be replaced.

Mechanism Mechanisms portray what chemists think is going on in the reaction,

whereas an equation tells you the ratio of products and reactants.

Chlorination of methane proceeds via FREE RADICAL SUBSTITUTION

because the methane is attacked by free radicals resulting in
hydrogen atoms being substituted by chlorine atoms.

The process is a chain reaction.

In the propagation step, one radical is produced for each one used
 CHLORINATION OF METHANE

Initiation Cl2 ——> 2Cl• RADICALS CREATED

The single dots represent UNPAIRED ELECTRONS

During initiation, the WEAKEST BOND IS BROKEN as it requires less energy.

There are three possible bonds in a mixture of alkanes and chlorine.

412 348 242

Average bond enthalpy kJ mol-1

The Cl-Cl bond is broken in preference to the others as it is the weakest and
requires requires less energy to separate the atoms.
 CHLORINATION OF METHANE

Propagation Cl• + CH4 ——> CH3• + HCl RADICALS USED and

Cl2 + CH3• ——> CH3Cl + Cl• then RE-GENERATED

Free radicals are very reactive because they want to pair up their single electron.
They do this by abstracting a hydrogen atom from methane; a methyl radical is formed
The methyl radical is also very reactive and attacks a chlorine molecule
A chlorine radical is produced and the whole process can start over again
 CHLORINATION OF METHANE

Termination Cl• + Cl• ——> Cl2 RADICALS REMOVED

Cl• + CH3• ——> CH3Cl
CH3• + CH3• ——> C2H6

Removing the
reactive free
radicals brings an
end to the reaction.

This is not very

likely at the start of
the reaction
because of their low
concentration.
 CHLORINATION OF METHANE

OVERVIEW

Initiation Cl2 ——> 2Cl• radicals created

Propagation Cl• + CH4 ——> CH3• + HCl radicals used and

Cl2 + CH3• ——> CH3Cl + Cl• then re-generated

Termination Cl• + Cl• ——> Cl2 radicals removed

Cl• + CH3• ——> CH3Cl
CH3• + CH3• ——> C2H6

Summary
Due to lack of reactivity, alkanes need a very reactive species to persuade them to react
Free radicals need to be formed by homolytic fission of covalent bonds
This is done by shining UV light on the mixture (heat could be used)
Chlorine radicals are produced because the Cl-Cl bond is the weakest
You only need one chlorine radical to start things off
With excess chlorine you get further substitution and a mixture of chlorinated products
 CHLORINATION OF METHANE

RADICALS
Initiation
PRODUCED

Propagation
RADICALS USED
AND REGENERATED

Termination

RADICALS
REMOVED
 CHLORINATION OF METHANE

Further
propagation If excess chlorine is present, further substitution takes place
The equations show the propagation steps for the formation of...

dichloromethane Cl• + CH3Cl ——> CH2Cl• + HCl

Cl2 + CH2Cl• ——> CH2Cl2 + Cl•

trichloromethane Cl• + CH2Cl2 ——> CHCl2• + HCl

Cl2 + CHCl2• ——> CHCl3 + Cl•

tetrachloromethane Cl• + CHCl3 ——> CCl3• + HCl

Cl2 + CCl3• ——> CCl4 + Cl•

Mixtures Because of the many possible reactions there will be a mixture of products.
Individual haloalkanes can be separated by fractional distillation.
 CRACKING
Involves the breaking of C-C bonds in alkanes
Converts heavy fractions into higher value products

THERMAL proceeds via a free radical mechanism

CATALYTIC proceeds via a carbocation (carbonium ion) mechanism

THERMAL

HIGH PRESSURE ... 7000 kPa

HIGH TEMPERATURE ... 400°C to 900°C
FREE RADICAL MECHANISM
HOMOLYTIC FISSION
PRODUCES MOSTLY ALKENES ... e.g. ETHENE for making polymers and ethanol
PRODUCES HYDROGEN ... used in the Haber Process and in margarine manufacture

Bonds can be broken anywhere in the molecule by C-C bond fission or C-H bond fission
 CRACKING
Involves the breaking of C-C bonds in alkanes
Converts heavy fractions into higher value products

THERMAL proceeds via a free radical mechanism

CATALYTIC proceeds via a carbocation (carbonium ion) mechanism

CATALYTIC

SLIGHT PRESSURE
HIGH TEMPERATURE ... 450°C
ZEOLITE CATALYST
CARBOCATION (IONIC) MECHANISM
HETEROLYTIC FISSION
PRODUCES BRANCHED AND CYCLIC ALKANES, AROMATIC HYDROCARBONS
USED FOR MOTOR FUELS

ZEOLITES are crystalline aluminosilicates; clay like substances

 REVISION CHECK
What should you be able to do?

Recall and explain the physical properties of alkanes

Recall the use of alkanes as fuels
Recall and explain the different ways to break a covalent bond
Write balanced equations representing combustion and chlorination
Understand the conditions and mechanism of free radical substitution
Recall the conditions and products from thermal and catalytic cracking

CAN YOU DO ALL OF THESE? YES NO

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WELL DONE!
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AN INTRODUCTION TO

THE CHEMISTRY
OF ALKANES
TH E
EN D

© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING

 PETROCHEMICALS
In the past, most important organic chemicals were derived from coal.
Nowadays, natural gas and crude petroleum provide an alternative source.

the composition of crude petroleum varies according to its source

it is a dark coloured, viscous liquid
consists mostly of alkanes with up to 40 carbon atoms, plus water, sulphur and sand
can be split up into fractions by fractional distillation
distillation separates the compounds according to their boiling point
at each level a mixture of compounds in a similar boiling range is taken off
rough fractions can then be distilled further to obtain narrower boiling ranges
some fractions are more important - usually the lower boiling point ones
high boiling fractions may be broken down into useful lower boiling ones - CRACKING

CONTENTS
PETROCHEMICALS
Boiling C’s per Name of Use(s)
range / °C molecule fraction

< 25 1-4 LPG (Liquefied Calor Gas

Petroleum Gas) Camping Gas

40-100 4 - 12 GASOLINE Petrol

100-150 7 - 14 NAPHTHA Petrochemicals

150-200 11 - 15 KEROSINE Aviation Fuel

220-350 15 - 19 GAS OIL Central Heating Fuel

> 350 20 - 30 LUBRICATING OIL Lubrication Oil

> 400 30 - 40 FUEL OIL Power Station Fuel

Ship Fuel
> 400 40 - 50 WAX, GREASE Candles
Grease for bearings

> 400 > 50 BITUMEN Road surfaces

Roofing

CONTENTS