Alkanes

Alkanes are aliphatic saturated hydrocarbons (no C=C double bonds, C and H atoms only). They are
identified by having a ane name ending.
The alkanes have similar chemistry to one another because they are a homologous series: a series of
organic compounds having the same functional groups, each successive member differing by CH2Their general formula is CnH2n+2 where n is the number of carbon atoms in the alkane.
We need to recognise the first 10 alkanes by name and formula, and be able to recognise chains
attached as branches to an organic molecule as being alkyl groups.
Alkane
methane
pentane

e.g.

Molecular formula
CH4
C5H12

Alkyl group
methylpentyl-

Structural formula
CH3CH3(CH2)4-

The cycloalkanes are alicyclic saturated hydrocarbons, having two less H atoms, and a ring rather than a
chain structure. e.g. cyclohexane C6H12
compared to
hexane C6H14
H H
H
C
H C
C H
H

H C
C H
C
H
H
H H

H H H H H H
H C C C C C C H
H H H H H H

Physical Properties:
Variation of boiling and melting point of alkanes with chain length
650

For the straight chain alkanes:

Low molecular weight alkanes (C1 to
C4 are gases at room temperature

600
550

A little heavier molecular weight

alkanes (C5 C17) are liquids at room
temperature

Temperature (K)

500
450
400
350
300
250

Room temperature

Higher molecular weight alkanes (C18

and above) are solids at room
temperature.

200
150
100
50
0

10 11 12 13 14 15 16 17 18 19 20 21

Chain length (C-atoms)

Trend in melting and boiling points:

As the number of carbons increases, the melting and boiling points get higher.
We say that the volatility of the alkanes decreases with increasing number of carbons in the alkane
molecule. [volatility: the ease with which a substance turns into a vapour].
Explanation:
The lack of polarity of alkane molecules means that only weak induced dipole-dipole forces (London
forces) are present between molecules. There are no permanent dipole-dipole interactions or hydrogen
bonds. As the number of electrons in the molecule increases (with increasing number of atoms) the
strength of the London forces also increases. More energy is needed to separate the molecules, so
melting and boiling points rise.

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Effect of branching:
For isoelectronic alkanes, the melting and boiling points decrease as the chain gets more branched.
Explanation:
As the molecule gets more ball shaped and less long and thin the molecules cant get so close
together. There are fewer points of contact and so the intermolecular forces are weaker. The vapour is
formed more easily, and so the boiling point gets lower.
Shapes of molecules:
The atoms in alkanes are held together by -molecular orbitals which lie along
the axis of each bond, as shown here for an ethene molecule. The molecular
orbitals can be considered as the overlap of two atomic orbitals. The two
electrons in each -orbital attract both nuclei binding them together in a bond.

We need to be able to draw 3D displayed formulae for alkanes, so we

used dashed bonds to represent bonds going into the plane of the paper
and wedged bonds to show those coming out of the plane of the paper:
Each C atom in an alkane has a tetrahedral arrangement of 4 -bonds
around it, so it has:
109.5o bond angles
free rotation about bonds
which makes alkane chains are very flexible
Check your understanding:
i) List all the physical properties of pentane you can, based on the information so far in this section.

Chemical Properties:
General: alkanes are remarkably inert, showing no reaction with acids or alkalis for example. There are
two reasons for this:
very low polarity of C-H and C-C bonds as C and H have similar electronegativities, C-C and C-H
bonds are non polar. Consequently the bonds in alkanes are not susceptible to attack by most
common chemical reagents
high bond enthalpies of C-H and C-C bonds. These bonds require a significant amount of energy
to break, so reactions have a high activation energy.
For some uses, the chemical inertness of the alkanes is their greatest asset. Compounds that are noncorrosive to metals (lubricating oils), harmless to our skin (vaseline), and safe in contact with foods
(poly(ethene)), are enormously useful to us.

Reactions:
1: Combustion:
When an excess of oxygen is available, alkanes combust completely giving carbon dioxide and water as
the only products. Alkanes make excellent fuels for domestic, industrial and transport use because they
react with oxygen exothermically (a fuel is defined as a source of useful chemical energy). They have low
toxicity, and short chain alkanes are easily ignited.
e.g.

CH4 + 2O2 CO2 + 2H2O

Hc = -890 kJmol-1

When only limited oxygen is available, combustion is incomplete and carbon monoxide, or even carbon
particles (soot) may be formed. The presence of carbon particles can be detected when hydrocarbons
burn because the flame becomes yellow and smoky rather than pale blue.
e.g.

2CH4 + 3O2 2CO + 4H2O

or 2CH4 + 2 O2 CO + C + 4H2O

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Dangers of incomplete combustion arise because CO binds permanently to haemoglobin, preventing O2

and CO2 transport. CO is therefore toxic, and is particularly dangerous because it is a colourless and
odourless gas so hard for people to detect.
Check your understanding:
ii) Write a balanced symbol equation (including state symbols) for the complete combustion of hexane.
iii) Write another equation to show combustion with a limited supply of oxygen, where equal volumes of
carbon monoxide and carbon dioxide are produced.
2: Substitution reaction of alkanes with halogens:
Hydrogen atoms in an alkane can be substituted by halogen atoms. The mechanism involves the
formation of free radicals, so it is referred to as a (free) radical substitution mechanism.
Conditions for the reaction: ultraviolet light is required (the amount present in sunlight is sufficient), so
this is an example of a photochemical reaction.
Application
When chlorine is mixed with methane and exposed to sunlight, chloromethane is formed and hydrogen
chloride gas is evolved:
CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)
Mechanism of Radical Substitution:
The example here is for the reaction of methane with chlorine, but other halogens and other alkanes react
in the same way and can be substituted for each other in this mechanism.
INITIATION STEP
The energy of UV light is enough to break the Cl-Cl bond in the Cl2 molecule. Absorption of light energy to
break a bond is called photodissociation. The type of bond fission (breaking) is homolytic, resulting in
two Cl radicals being formed:
uv
Cl-Cl(g)

Cl(g) + Cl(g)
Radicals are very reactive, and react rapidly with other molecules or chemical species
PROPAGATION STEPS
A chlorine radical reacts with methane to produce hydrogen chloride and a methyl radical
Cl

H-CH3

Cl-H

CH3

The methyl radical is able to react with a chlorine molecule to produce chloromethane and regenerate a
chlorine radical:
Cl-Cl

CH3

CH3Cl +

Cl

Forming a new chlorine radical means the reaction can happen again and again - a chain reaction which
needs no more UV to keep going. Measurements show these steps can occur some 10,000 times for one
UV photon initiation.
TERMINATION STEPS
The reaction only stops when two radicals combine to form a new molecule. This removes radicals from
the reaction mixture, stopping the chain reaction.
There are several possibilities:
Cl
+
Cl

Cl
+
CH3
CH3 +
CH3

Cl2
CH3Cl
C2H6 so a small amount of ethane is also formed

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Formation of a mixture of products

The mechanism of radical substitution does not produce a single pure product. A mixture of products is
formed, so there are limitations on the use of this reaction for synthesising a specific desired product.
There are three ways in which more than one product might be formed:
e.g. if we want to use this reaction to make 1-bromopropane from propane:
CH3CH2CH3 + Br2 CH3CH2CH2Br + HBr

The bromine radical can attack any position in the alkane chain, so 2-bromopropane can also be
formed by this pair of propagation steps:
CH3CH2CH3 + Br CH3CHCH3 + HBr
CH3CHCH3 + Br2 CH3CHBrCH3 + Br

One possible termination step is the reaction of two alkyl radicals, forming an alkane of twice the
length of the original alkanes, so two propyl radicals can react to form hexane:
CH3CH2CH2 + CH3CH2CH2 CH3(CH2)4CH3
But because there are two types of propyl radical that can be formed, depending on which
position in the chain was attacked, 2-methylpentane and 2,3-dimethylbutane are also possible
products that can be formed in termination steps.

There is no reason why any of the products formed in any of the reactions cannot themselves
react with bromine radicals in further radical substitution reactions, e.g. 1-bromopropane formed
in the original reaction could react again to form 1,2-dibromopropane in these propagation steps:
CH3CH2CH2Br + Br CH3CHCH2Br + HBr
CH3CHCH2Br + Br2 CH3CHBrCH2Br + Br

Check your understanding:

iv) Chlorine reacts with cyclohexane in the presence of uv light. Show the mechanism steps in this
reaction.
Bromine reacts with ethane to produce bromoethane when illuminated with uv light.
v)
Show the initiation step in the mechanism for this reaction
vi)
Show the propagation steps in the mechanism for this reaction
vii)
Show a termination step in which bromoethane is produced and suggest two reasons why
bromoethane is not the only organic product in this reaction

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Answers to Check Your Understanding questions:

i) List all the physical properties of pentane you can, based on the information given:
- liquid at room temperature (but very close to its boiling point)
- higher boiling point than similar isoelectronic alkanes
- fairly volatile
- insoluble in water
- flexible chain, can flex into different conformations
- 109.5 bond angles throughout

ii) Write a balanced symbol equation (including state symbols) for the complete combustion of hexane:
C6H14(l) + 9 O2(g) 6 CO2(g) + 7 H2O(l) - or quantities all x 2
iii) Write another equation to show combustion with a limited supply of oxygen, where equal volumes of
carbon monoxide and carbon dioxide are produced:
Equal volumes of CO and CO2 mean equal numbers of moles of each gas produced
therefore three C atoms in each hexane make CO and the other three C atoms make CO2
C6H14(l) + 8O2(g) 3 CO(g) + 3 CO2(g) + 7 H2O(l)
iv)

v)

Cl2

Propagation

C6H12 + Cl2 C6H11 + HCl

Cl2 + C6H11 C6H11Cl + Cl

Termination

e.g. Cl + Cl

vii)

Cl

Cl

Cl2

Show the initiation step in the mechanism for this reaction

Br2
vi)

uv

Initiation

uv

Br

Br

Show the propagation steps in the mechanism for this reaction

Br

H3C-CH3

Br-Br

CH2CH3

CH2CH3

Br

CH3CH2Br

HBr

Show a termination step in which bromoethane is produced and suggest two reasons why
bromoethane is not the only organic product in this reaction
CH3CH2

Br

CH3CH2Br

Ethyl radicals can combine to produce butane

CH3CH2 + CH2CH3 CH3CH2CH2CH3
Bromoethane can itself react by the same mechanism to make e.g. 1,1-dibromoethane
uv
CH3CH2Br + Br2 CH3CHBr2 + HBr
(N.B formation of 1,2-dibromoethane would be an equally acceptable answer)

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