The Radical Substitution

Initiation
Propagation
Termination
Overall reaction
equation
CH4 + Br2 CH3Br + HBr
 • In the presents of UV, alkanes react with halogens. The UV
The overall reaction provides the initial energy for the reaction to take place
of methane and • This is a substitution reaction, as a hydrogen atom has
been substituted by a halogen atom.
bromine •
Initiation Equation

Br2  Br • + Br •
Initiation
• A Br2 molecule is exposed to UV
light.
• The UV light provides the energy
for the covalent bond to break.
• Each one of the Bromines take
one of the electron from the
covalent bond (homolytic
fission.)
• Homolytic fission means each
atom now has a single pair of
electrons.
• This forms two Bromines which
are free radicals. These are a
very reactive species as they
have an unpaired electron.
Propagation step 1 Equation

CH4 + Br •  •CH3 + HBr

 • Bromine collides with the hydrogen atom on the CH4 this
breaks the C—H bond in methane.
• Then the hydrogen forms a covalent bond with a bromine
Propagation to make hydrogen bromide.

Step 1 • This leaves a •CH3 (methyl) radical which is highly reactive.

• In propagation, there are always radicals on both sides of
the reaction.
Prpagation Step 2 Equation

•CH3 + Br2 CH3Br + Br•

Propagation Step 2 • In the second step, a methyl
radical (•CH3) collides with a
bromine molecule.
• The Br—Br covalent bond is
broken in the bromine
molecule and then a C-–Br
covalent bond is made to
form CH3Br
(Bromomethane).
• A bromine radical is formed.
This will then repeat the
propagation process to form
a chain reaction.
Termination Equations

Br• + Br•  Br2

•CH3 + •CH3  C2H6

•CH3 + Br•  CH3Br

Step 3 Termination
• Br• radicals collide together to form a covalently bonded
Br2.
• A •CH3 and a •CH3 radical collide to form C2H6 (ethane)
• A •CH3 collides and a Br• collide to from CH3Br.
• In termination, two radicals react to from a non-radical
compound, and this stops the reaction.