ALKANES

LEARNING OBJECTIVES
❑Know the general formula for alkanes.

❑Explain why alkanes are classified as saturated hydrocarbons.

❑Understand how to draw the structural and displayed formulae for alkanes with
up to five carbon atoms in the molecule and to name the unbranched-chain
isomers.

❑Describe the reactions of alkanes with halogens in the presence of ultraviolet

radiation, limited to mono-substitution.
Alkanes
• The alkanes are the simplest family of organic compounds.
• The majority of compounds found in the mixture of hydrocarbons we call crude oil are alkanes.
• Note that all the carbon–carbon bonds are single covalent bonds (bonding in alkanes is single
covalent).
• They form a homologous series, with the general formula CnH2n+2.
• Because alkanes possess only carbon–carbon single covalent bonds, they are said to be saturated
hydrocarbons, as no further atoms can be added. This means that alkanes have the maximum number
of hydrogen atoms in their molecules.

A displayed formula shows how the

various atoms are bonded and shows all
the bonds in the molecule as individual
lines.

The fully displayed formulae of some alkane molecules

 ALKANE STRUCTURES

H H H H H H
H–C–H H–C–C–H H–C–C–C–H
H H H H H H

METHANE ETHANE PROPANE

CH4 C2H6 C3H8

THESE ARE DISPLAYED STRUCTURES

THEY SHOW ALL THE
COVALENT BONDS IN THE MOLECULE

Each covalent bond is represented by a line

Sources of the alkanes
• They are found in petroleum and natural gas.
Petroleum contains alkanes with up to 70 carbon
atoms. Natural gas is mainly methane, with small
amounts of ethane, propane, butane, and other
compounds.

The first four alkanes are gases at room temperature. The next twelve
are liquids. The rest are solids. Boiling points increase with chain
length because attraction between the molecules increases – so it takes
more energy to separate them. Solids start to appear at about C18H38.
The molecules of the members of a homologous series increase in size in a regular way
and you can see that the boiling points also increase in a regular way.

As the molecules become bigger, the strength of the intermolecular forces of attraction
between them increases. This means that more energy has to be put in to break the
attractions between one molecule and its neighbours. One effect of this is that the
boiling points increase in a regular way.
 Naming the alkanes
All the alkanes have names ending in -ane. The rest of the name tells you the number of carbon
atoms present in the molecule. For example, the compound whose name begins with:
➢ meth- has one carbon atom
➢ eth- has two carbon atoms
➢ prop- has three carbon atoms
➢ but- has four carbon atoms
And so on…..

In the next slide, we will look at the system (or rules) for
naming the organic compounds (e.g. alkanes)
Naming the alkanes: The “principles” of naming
Chemists have a system of naming organic compounds that can be applied consistently. The class of hydrocarbons
called alkanes provide the basis of the naming system.
• First, identify the longest continuous carbon chain (also called the parent chain) within the molecular structure.

• The position of side-chains (substituents) or functional groups is indicated by numbering the carbon atoms in the
longest chain. The numbering starts at the end that produces the lowest possible numbers in the name.
➢ Note that the hydrocarbon side-chain is named by adding –yl to the normal alkane stem. This means, methane now becomes methyl,
ethane becomes ethyl and so on. This type of group is called an alkyl group.

• If there is more than one of the same alkyl side-chain or functional group we indicate how many by inserting di
(for two), tri (for three) or tetra (for four) in front of its name.

• If there is more than one type of alkyl side-chain, they are listed in the name in alphabetical order.

• Note that adjacent numbers in a name have a comma between them, whereas numbers and words are separated
by hyphens.
Naming the alkanes: The “principles” of naming
Hydrocarbon chains can have side branches on them.
Naming the alkanes: The “principles” of naming
Name the compounds (remember to apply the principles of naming)

2,4,6-trimethyloctane 3-ethyl-3-methylheptane

butane
2-methylpropane
Naming the alkanes
STRUCTURAL ISOMERISM
• A compound’s molecular formula tells us the number and type of each atom in one molecule of the
compound.
• However, for a given molecular formula there may be different ways of arranging these atoms.
• This means different molecules can be formed, with different structures, resulting in different
compounds. Such compounds with the same molecular formula but different structural formulae are called
structural isomers.
Structural isomers: Are compounds with the same molecular formula, but different structural formulae.

Structural formulae: The structural formula of an organic compound is an unambiguous description of

the way the atoms are arranged, including the functional group.

Types of structural isomerism

• position isomerism
• functional group isomerism
• chain isomerism.
STRUCTURAL ISOMERISM
• The more carbon atoms in a compound,
the more isomers it has. There are 75
isomers with the formula C10H22.

• Since isomers have different structures,

they also have slightly different
properties.

Compare these alkane molecules.

Both have the same formula, C4H10.
The first has a straight or unbranched chain. In the second, the chain is branched.
The two compounds are isomers. They have the same formular, but different structures.
STRUCTURAL ISOMERISM
The alkane C5H12 have the following isomers:

Pentane
2-methylbutane

2,2-dimethylpropane
STRUCTURAL ISOMERISM
The alkane C5H12 have the following isomers:
PHYSICAL PROPERTIES OF ALKANES
Boiling point
➢ Boiling point increase along the alkane homologous series.
✓ Boiling point increases with increasing intermolecular forces. The intermolecular forces increase with increasing
size (molecular weight). The sizes of the alkanes increase along the homologous series.
CH4 < CH3CH3 < CH3CH2CH3 e.t.c
Increasing boiling point

➢ For isomeric alkanes, boiling point decreases with increasing branching.

✓ With increasing branching, the surface area of the molecule decreases and intermolecular forces of attraction
decreases and so the boiling point decreases.

> >

Decreasing boiling point

PHYSICAL PROPERTIES OF ALKANES
Boiling point
PHYSICAL PROPERTIES OF ALKANES
Solubility
➢ Alkanes are not soluble in water (a polar substance), but soluble in non-polar organic solvents (such as benzene
and ether). The two substances do not meet the usual criterion of solubility: “Like dissolves like”. Water
molecules are too strongly attracted to each other (by hydrogen bonds) to allow non-polar alkanes to slip in
between them and dissolve.

➢ Note however that, the solubility of the alkanes (in non-polar solvents) decreases along the homologous
series due to increasing intermolecular forces of the alkanes along the series.
The Chemical Behaviour of Alkanes
• Chemical properties are dependent on the functional groups and bonding
within the molecules.

• Because alkanes only contain carbon–carbon single bonds and carbon–

hydrogen bonds, they are all going to behave in the same way.

• These are strong bonds, therefore alkanes are fairly unreactive organic
compounds
The Chemical Behaviour of Alkanes
Alkanes are rather unreactive compounds. For example, they are generally not affected by alkalis, acids or many
other substances. However, they can take part in substitution reactions, particularly with chlorine (Chlorine is
quite a reactive non-metal and will react with, for example methane in the presence of sunlight or ultraviolet
light).
Combustion of Alkanes
Alkanes are often used as fuels. We burn them for many reasons:
• to generate electricity in power stations
• to heat our homes and cook our food
• to provide energy needed in industrial processes
• to provide power for ships, aeroplanes, trains, lorries, buses, cars and motorbikes.

If an alkane is burnt in plenty of oxygen, it will undergo complete combustion, forming carbon dioxide and water as well
as plenty of heat energy.
The Chemical Behaviour of Alkanes
Combustion of Alkanes

methane + oxygen → carbon dioxide + water CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

ethane + oxygen → carbon dioxide + water 2C2H6(g)+ 7O2(g) → 4CO2(g) + 6H2O(g)
butane + oxygen → carbon dioxide + water 2C4H10(g)+ 13O2(g) → 8CO2(g) + 10H2O(g)
octane + oxygen → carbon dioxide + water 2C8H18(g)+ 25O2(g) → 16CO2(g) + 18H2O(g)
OR
𝟏
C8H18+ 12 O2(g) → 8CO2(g) + 9H2O(g)
𝟐

The same products are obtained whichever alkane is burnt, so long as there is a sufficient oxygen supply.
The Chemical Behaviour of Alkanes
Combustion of Alkanes
If there isn’t enough oxygen, there is incomplete combustion of the
hydrocarbon, and you obtain carbon monoxide or carbon (soot) instead of
carbon dioxide, for example:
The Chemical Behaviour of Alkanes
Pollution from burning hydrocarbon fuels
When the petrol or diesel is mixed with air inside a car engine, there is a limited supply of oxygen.
Under these conditions, not all the carbon in the hydrocarbon fuel is fully oxidised to carbon
dioxide. Some of the carbon is only partially oxidised to form carbon monoxide gas. This is called
incomplete combustion. For example:
methane + oxygen → carbon monoxide + water

2CH4(g) + 3O2(g) → 2CO(g) + 4H2O(g)

Carbon monoxide is a toxic gas that bonds with the haemoglobin in your blood. The haemoglobin molecules
can then no longer bond to oxygen and so cannot transport oxygen around your body.

The incomplete combustion of fossil fuels is a major cause of air pollution.

The Chemical Behaviour of Alkanes
Substitution reactions
A substitution reaction is a reaction in which an atom (or atoms) of a molecule is (are) replaced by different
atom(s), without changing the molecule’s general structure.
Alkanes undergo substitution reactions with halogens such as chlorine. In these reactions a hydrogen atom of
the alkane is replaced by a chlorine (or halogen) atom.

The substitution reaction of an alkane with chlorine

Sunlight

This is known as a photochemical reaction, with the UV

light (sunlight) providing the activation energy (Ea) for the
reaction.
The Chemical Behaviour of Alkanes
Substitution reactions A mixture of methane and
methane with bromine gas bromine gas is orange because of
the presence of the bromine. If it
is exposed to sunlight, it loses its
colour, and a mixture of
bromomethane and hydrogen
bromide gases is formed.

An exactly similar reaction happens between

ethane and chlorine exposed to UV light. In this
case, you get a mixture of chloroethane and
hydrogen chloride gases:
The Chemical Behaviour of Alkanes
Mono-substitution occurs when only one hydrogen atom in the alkanes is
replaced by a halogen atom.

When propane reacts with bromine, it is possible to form two organic products
even when only mono-substitution occurs. The two products are structural
isomers of each other, they have the same molecular formula but different
structural formulae.
The products formed from substitution reactions
of alkanes with halogens are called
halogenoalkanes. They are named according to the
format x-haloalkane, where x indicates the
position of the halogen atom in the longest carbon
chain. So, when bromine reacts with propane we
get 1-bromopropane and 2-bromopropane.
The Chemical Behaviour of Alkanes
Substitution reactions
Complete the reaction equation
• CH4 + Cl2
• CH3CH3 + Cl2
• C6H6 + Br2
QUESTIONS
1. Name the alkane that has the formula C7H16.
2. Draw the displayed formulae for the isomers of C5H12.
3. Write a balanced chemical equation to represent the combustion of propane.
4. In what mole proportions should chlorine and methane be mixed to produce
chloromethane?
5. Draw the covalent bonding diagram for chloromethane, CH3Cl.