THE HYDROCARBONS (Alkanes, Alkenes)

These are compounds which consist of carbon and hydrogen only, e.g. alkanes and alkenes.

Hydrocarbons are named according to the number of carbon atoms which they contain in their
main chain/branch (if it is a branched compound), using the following prefixes:

meth- 1 carbon hex- 6 carbons

eth- 2 carbons hept- 7 carbons
prop- 3 carbons oct- 8 carbons
but- 4 carbons non- 9 carbons
pent- 5 carbons dec- 10 carbons

ALKANES

Alkanes are saturated hydrocarbons (they contain single bonds only). This means that each
carbon atom is bonded to the maximum number of hydrogen bonds.

General formula: CnH2n+2 (where n is the number of carbon atoms)

Sources of alkanes include natural gases and petroleum.

Name of Alkane Molecular Formula

Methane CH4
Ethane C2H6
Propane C3H8
Butane C4H10
Pentane C5H12
Hexane C6H14

Structural Formula

This shows the arrangement of atoms with respect to each other. This can be shown by grouping
the atoms, i.e. the abbreviated form, or by the graphical formula, i.e. the spatial arrangement of
the atoms.

E.g. Ethane

CH3CH3, or CH3-CH3 or
Propane
CH3CH2CH3 or CH3-CH2-CH3 or

Structural Isomerism

This is the existence of two or more compounds with the same molecular formulae but different
structural formulae. Structural isomers can belong to the same homologous series or to a
different homologous series.

Structural isomers found within a homologous series (i.e. the same functional group) have
different physical properties, but similar chemical properties. We call these structural chain
isomers.

Structural isomers can also belong to different homologous series. This means they have
different functional groups, and therefore, different physical and chemical properties. These
types of isomers are called functional group isomers.

There are three types of structural isomers:

1. Chain isomers
2. Functional group isomers
3. Positional isomers

Chain Isomers

Chain isomers are structural isomers in which the carbon skeletons are arranged differently. They
have the same functional group and belong to the same homologous series.

E.g. C4H10

Butane 2-methylpropane
C5H12

Pentane

2-MethylButane

Chain isomers have different physical properties because the different shapes change the strength
of the dispersion forces. (Dispersion forces are weak temporary attractive forces that form
between non-polar molecules when the two electrons in two adjacent electrons occupy positions
such that the atoms form temporary dipoles.)

Functional Group Isomers

Functional group isomers are structural isomers that have different functional groups and thus,
belong to different homologous series. They have different physical properties as well as
different chemical properties.

E.g. C2H6O

Ethanol Methoxymethane/dimethyl ether

C3H6O

Propanal Propanone
C4H8O2

Butanoic acid methylpropanoate

Ethylpropanoate

Positional Isomers

Positional isomers are structural isomers that have a functional group or substituent group in
different positions on the same carbon skeleton (parent chain). In positional isomers, the parent
chains are the same. Positional isomers are chemically similar because they possess the same
functional group.

E.g. Propan-1-ol and Propan-2-ol

Pent-1-ene and Pent-2-ene

Benzene derivatives

Properties and Reactions of Alkanes

There is a gradual change in physical state as the number of carbon atoms in the chain increases.
This is because of the increase in van der Waals forces between molecules of unbranched chains.
The larger alkanes have greater van der Waals forces of attraction because their surface area is
larger. Thus, the larger the alkanes, the higher the boiling point.

Branched alkanes that are more compact have a smaller surface area on which van der Waals
forces act; thus, they have a lower boiling temperature than their straight chain isomers with the
same number of carbon atoms. Solid alkanes that are normally soft have low melting points.
These alkanes are soft because there are strong repulsive forces between the electrons on
neighbouring atoms. These repulsive forces counterbalance the weak van der Waals forces.

In summary:

 Alkanes are colourless, non-polar compounds with distinctive odours.

 Alkanes are less dense than water.
 The first four alkanes are gases, the next twelve are liquids, and the rest are solids at
room temperature and pressure.
 The boiling point increases with increasing mass

Because alkanes are saturated compounds, they are quite unreactive. There are two main
reactions:

1. Combustion
Alkanes burn completely in a plentiful supply of air to produce CO 2 and H2O vapour. A non-
smoky flame is produced.
E.g. 𝐶𝐻4 (𝑔) + 2𝑂2 → 𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑔)
𝐶3 𝐻8 (𝑔) + 5𝑂2 → 3𝐶𝑂2 (𝑔) + 4𝐻2 𝑂(𝑔)
2𝐶4 𝐻10 (𝑔) + 13𝑂2 → 8𝐶𝑂2 (𝑔) + 10𝐻2 𝑂(𝑔)

A lot of heat energy is given off when alkanes burn and therefore the smaller ones are used as
fuels, e.g. cooking gas contains C1 – C4 (Methane – Butane).
If the oxygen is insufficient in the air, then the combustion is incomplete and carbon
monoxide (CO) and water vapour (H2O) are produced. In petrol and gasoline engines, the
exhaust fumes contain CO2, CO and carbon.

2. Substitution reaction with halogens

This reaction takes place because alkanes are saturated. In the reaction, an atom of the
halogen molecule displaces a hydrogen atom from the alkane. This displaced hydrogen atom
reacts with the other halogen atom to form a hydrogen halide. Substitution reactions occur in
steps, where the H atoms are successively displaced by the halogen. The reaction occurs best
in sunlight.

E.g. reaction of methane with chlorine

i. 𝐶𝐻 4(𝑔) + 𝐶𝑙2 (𝑔) → 𝐶𝐻3 𝐶𝑙(𝑔) + 𝐻𝐶𝑙(𝑔)
ii. 𝐶𝐻3 𝐶𝑙(𝑔) + 𝐶𝑙2 (𝑔) → 𝐶𝐻2 𝐶𝑙2 (𝑔) + 𝐻𝐶𝑙(𝑔)
iii. 𝐶𝐻 2 𝐶𝑙2 (𝑔) + 𝐶𝑙2 (𝑔) → 𝐶𝐻𝐶𝑙3 (𝑔) + 𝐻𝐶𝑙(𝑔)
iv. 𝐶𝐻𝐶𝑙3(𝑔) + 𝐶𝑙2 (𝑔) → 𝐶𝐶𝑙4 (𝑔) + 𝐻𝐶𝑙(𝑔)
 Uses of Alkanes

1. They are used as fuels, e.g. cooking gas from C1 – C4 (methane – butane), gasoline (C5 –
C12), kerosene (C12 – C18)

2. Some are used as solvents, e.g. paint thinners, kerosene

3. Alkanes are used to manufacture other chemicals, e.g. Vaseline (Petroleum jelly), plastics,
synthetic rubber, detergents, pesticides

4. Larger alkanes can be cracked to form hydrocarbons.

Cracking occurs when a larger hydrocarbon molecule splits up or cracks to form smaller
hydrocarbon molecules. Cracking occurs when the alkanes are exposed to high temperatures
and, as a result, they decompose. Methane and ethane are stable to heat.

E.g.
i. 𝐶3 𝐻8 → 𝐶𝐻4 + 𝐶2 𝐻4 (chain breaking)
ii. 𝐶3 𝐻8 → 𝐶3 𝐻6 + 𝐻2 (de-hydrogenation)
iii. 𝐶10 𝐻22 → 𝐶7 𝐻11 + 𝐶3 𝐻6 (chain breaking)

Alkane Derivatives

Halogenoalkanes

Some halogenoalkanes are:

 Solvents, e.g. tetrachloromethane and trichloromethane

 Anaesthetics, e.g. Halothane is widely used in hospitals. It contains the atoms bromine and
fluorine as well as chlorine. Chloromethane is used for local anaesthesia on the skin.
 Pesticides