Module 1.

Functional Groups Analysis, Reactions and

Mechanism

ALKANES
Learning Outcomes
2.1. Identify homologous series of alkanes;
2.2. Describe chemical reactions of alkanes;
2.3.Explain the steps involved in the
mechanism of free radical substitution.
ALKANES are saturated
hydrocarbons which have the general
formula CnH2n+2.

They contain only strong C-C and C-H

bonds, which make them relative inert.
 Alkane Homologous Series
▣ Alkanes have the general formula CnH2n+2
▣ Their names end with “ane”.
▣ The carbon atoms are joined by single covalent bonds.
▣ Each member in the homologous series differs from the
next one by -CH2.
No. of Chemical name Molecular Relative Boiling
carbon formula molecular point / °
atoms mass C
1 Methane CH4 16 –162
2 Ethane C 2H 6 30 –89
3 Propane C 3H 8 44 –42
4 Butane C4H10 58 –0.5
5 Pentane C5H12 72 36
 Boiling point Melting point [° Density [g·cm3]
ALKANE Formula
[°C] C] (at 20°C)
Methane CH4 -162 -183 gas
Ethane C 2 H6 -89 -182 gas
Propane C3H8 -42 -188 gas
Butane C4H10 0 -138 gas
Pentane C5H12 36 -130 0.626(liquid)
Hexane C6H14 69 -95 0.659(liquid)
Heptane C7H16 98 -91 0.684(liquid)
Octane C8H18 126 -57 0.703(liquid)
Nonane C9H20 151 -54 0.718(liquid)
Decane C10H22 174 -30 0.730(liquid)
Methane, ethane, propane and butane are gases and used
directly as fuels.

Alkanes from pentane up to around C17H36 are liquids.

Gasoline is a mixture of alkanes from pentane up to about

decane.

Above n=17 they are solids at room temperature.

Alkanes with higher values of n are found in diesel fuel, fuel

oil, petroleum jelly, paraffin wax, motor oils, and for the
highest values of n, asphalt.
STRUCTURE OF METHANE
STRUCTURE OF ETHANE
What is hybridization?
•Are alkanes molecules polar or non-polar?

•What type of intermolecular forces are found in

alkanes?

•Why alkanes are insoluble in water?

Alkanes are relatively inert, and do not react with
acids, bases, oxidizing and reducing agents,
nucleophiles, electrophiles or polar reagent in
general.
Alkanes have only three significant reactions:
• Combustion

• Halogenation

• Cracking
 REACTION
OF
ALKANES

CRACKING
COMBUSTION MOLECULES ARE
IS AN IMPORTANT CRACKED INTO
HALOGENATION
SOURCE OF SMALLER
(FREE RADICAL
ENERGY MOLECULES
SUBSTITUTION)
( ALKANE AND
ALKENE)
 FREE RADICALS

DEFINITION: A free radical is a reactive species which possess an

unpaired electron.

When a bond breaks by homolytic fission it forms free radicals. Free

radicals DO NOT HAVE a charge and are represented by a E.g.
 Chemical Properties of Alkanes
The alkanes are generally unreactive due to their saturated
carbon-carbon bonds. However, they can undergo some types
of chemical reactions.

COMBUSTION
Alkanes undergo combustion in air or oxygen to form carbon
dioxide and water vapour. The following two equations illustrate
this

CH4(g) + 2O2(g) 🡪 CO2(g) + 2H2O(g)

2C2H6(g) + 7O2(g) 🡪 4CO2(g) + 6H2O(g)
 Chemical Properties of Alkanes
HALOGENATION: Substitution Reactions with Halogens
Alkanes react with halogens, such as fluorine, chlorine and
bromine under UV light or heat to form a mixture of
halogenoalkanes.
E.g. methane reacts with chlorine as follows:
CH4 + Cl2 🡪 CH3Cl + HCl
CH3Cl + Cl2 🡪 CH2Cl2 + HCl

CH2Cl2 + Cl2 🡪 CHCl3 + HCl

CHCl3 + Cl2 🡪 CCl4 + HCl

 Chemical Properties of Alkanes

Substitution Reactions with Halogens

The type of reaction in which the hydrogen

atom of the hydrocarbon is replaced by the
halogen atom is called a
SUBSTITUTION REACTION.
 Chemical Properties of Alkanes
Free Radical Substitution Mechanism
FREE RADICALS are atoms or groups
of atoms which have a single unpaired
electron.

HOMOLYTIC FISSION
the symmetrical splitting of a bond in
which each atom takes an equal share of
the bonding electrons forming free
radicals.
Cl2 → Cl. + Cl.
 Free Radical Substitution Mechanism
uv
CH4(g) + Cl2(g) CH3Cl(g) + HCl(g

THE MECHANISM INVOLVES A CHAIN REACTION.

⚫ During a chain reaction, for every reactive species you start
off with, a new one is generated at the end
⚫ this keeps the process going.

⚫ The over-all process is known as free radical substitution,

or as a free radical chain reaction
 INITIATION

The chain is initiated (started) by UV light breaking a chlorine

molecule into free radicals. It is broken in preference to the
others (e.g. CH4(g) ) because it is the weakest.

Show bond breaking using curve fishhook ( ↼ )

uv
Cl : Cl 2Cl.
 Free Radical Substitution Mechanism

PROPAGATION reactions this involves two steps.

CH4 + Cl. → .CH3 + HCl

.CH3 + Cl2 → CH3Cl + Cl.

TERMINATION reactions (involves recombination
of two free radicals).

Cl. + Cl. → Cl2

.CH3 + Cl. → CH3Cl

.CH3 + .CH3 → C2H6

 INITIATION
Homolytic
fission of X2

MECHENISM
PROPAGATION
OF FREE
Chain reactions
RADICAL

TERMINATION
Recombination
of free radicals
 Cracking of hydrocarbons
▣ CRACKING is the process of breaking large petroleum molecules into
smaller molecules with the use of heat and catalyst.
▣ So, high Mr alkanes smaller Mr alkanes+ alkenes + (hydrogen)

▣ Gaseous alkanes are passed over SiO2, Al2O3, at 450oC

Types of cracking include:
▣ thermal cracking,
▣ catalytic cracking and
▣ hydrocracking
which are geared towards producing specific products needed by the
industry.

ALKANE → ALKANE + ALKENE + HYDROGEN

with smaller
molecules
• Straight chain alkanes are relatively poor motor fuels.
• They cause knocking in the engine by detonating rapidly
rather than burning steadily.

• Branched chains are much better in this respect.

• REFORMING is the process where straight chain alkanes are

heated under pressure with a platinum catalyst.
• The chains break up and reform as branched chain
molecules.
Economic reasons for cracking

• The petroleum fractions with shorter C chains (e.g. petrol and

naphtha)are in more demand than larger fractions.

• To make use of excess larger hydrocarbons and to supply

demand for shorterones, longer hydrocarbons are cracked.

• The products of cracking are more valuable than the starting

materials (e.g. ethene used to make poly(ethene), branched
alkanes for motorfuels, etc.)
There are two main types of cracking: thermal and catalytic. They need
different conditions and are used to produce different products
 C6H14
Burns as
a fuel Pass over SiO2,
Cl2 diffuse Al2O3 at 450oC
sunlight

C6H13Cl + HCl
CO2 +H2O + + further E.g. C2 H4
Energy substitution + C4H10
products
RECALL
Alkanes three significant reactions:
combustion, cracking and radical substitution.

⚫ Complete combustion produces carbon dioxide and water

⚫ Incomplete combustion produces carbon dioxide, carbon monoxide,

carbon and water.

⚫ Cracking produces shorter-chain alkanes and alkenes.

RECALL

• Radical substitution reactions are initiated by ultraviolet light.

• Free Radical Substitution reactions have three stages:
• initiation where radicals are formed
• propagation where products are formed and radicals are regenerated
• termination where radicals are removed.

• To reduced the chain lengths and produce alkanes, longer chain fractions
are cracked.

• To produced branched chains which are more suitable for petrol,

straight-chain alkanes may be reformed.
Write equations for the following
reactions:

(i) Combustion of octane

(i) Cracking of decane

(i) Chlorination of ethane

Butane reacts with chlorine, in a free radical chain reaction, to form
1-chlorobutane as one of the products. The reaction takes place in a
number of steps:

Step 1. Cl-Cl → 2Cl. INITIATION

Step 2. Cl. + CH3CH2CH2CH3 → CH3CH2CH2CH2. + HCl
Step 3. CH3CH2CH2CH2. + Cl2 → CH3CH2CH2CH2Cl + Cl.
Step 4. CH3CH2CH2CH2. + Cl. → CH3CH2CH2CH2Cl TERMINATION

a. What conditions is needed to promote Step 1?

b. What type of bond breaking occurs in Step 1?
c. Classify the type of reaction occurring in steps 2 and 3?
d. Suggest an equation for another possible chain termination step.
e. Give one other example of a reaction with a free radical chain
mechanism.
When irradiated with ultraviolet light, methane reacts with chlorine to
form a mixture containing several organic products.

a. Name the type of mechanism involved.

b. Explain why UV light is needed.
c. Write an equation to show the formation of chloromethane from
chlorine and methane.
d. Another product has a RMM of 85. Identify this product and write the
part of the mechanism which shows its formation from
chloromethane.
e. Explain how a small amount of ethane is formed in the process and
name the mechanism step with leads to its formation.
f. Give the major product formed when methane reacts with a large
excess of chlorine.