Chemsheets AS 1138 (Free Radical Substitution 2)

FREE RADICAL SUBSTITUTION 2
WHAT HAPPENS H atoms on alkanes or halogenoalkanes are replaced by halogen atoms (F / Cl / Br / I)
OVERALL EQUATION For every H atom replaced by F / Cl / Br / I, one molecule of F2 / Cl2 / Br2 / I2 is used
and one molecule of HF / HCl / HBr / HI is released.
In order to replace many H atoms with F / Cl / Br / I atoms, an excess of F2 / Cl2 / Br2 /
I2 is used. In order to only replace one H atom, an excess of the alkane /
halogenoalkane is used.
e.g. CH4  CH3Cl CH4 + Cl2 CH3Cl + HCl
e.g. CH4  CF4 CH4 + 4F2 CF4 + 4HF
e.g. CH3-CBr3  CBr3-CBr3 CH3-CBr3 + 3Br2 CBr3-CBr3 + 3HBr
e.g. CH2Cl2  CCl4 ………………………………………………………………………………………..………….
e.g. CH3-CH3  CF3-CF3 …………………………………………………………………………………………..……….
e.g. CHF2-CH3  CBrF2-CBr3 ……………………………………………………………………………………..…………….
e.g. CF3-CH3  CF3-CCl3 ……………………………………………………………………………………..…………….
INITIATION When exposed to ultraviolet light, a molecule of a halogen F2 / Cl2 / Br2 / I2 breaks apart
into two halogen atom free radicals F / Cl / Br / I. The ultraviolet light provides
the energy to break the covalent bond between the two halogen atoms.
(Free radicals are species with an odd number of electrons – they are very reactive –
the atom with the odd number of electrons is shown with a )
fluorine: F2  2F bromine: Br2  2Br
chlorine: Cl2  2Cl  iodine: I2  2I
PROPAGATION (molecule + radical  molecule + radical)
For every H that is replaced, there is one pair of propagation reactions.

Step 1 the alkane / halogenoalkane reacts with the F / Cl / Br / I – this removes
an H atom from the alkane / halogenoalkane – this produces HF / HCl / HBr /
HI and a C based free radical.
Step 2 the C based radical from step 1 reacts with F2 / Cl2 / Br2 / I2 to put an atom of F
/ Cl / Br / I onto the C based radical – this also produces another halogen free
radical (F / Cl / Br / I) to continue the chain reaction in another step 1.
© www.CHEMSHEETS.co.uk 4-February-2016 Chemsheets AS 1138

e.g. CH4  CH3Cl (1) CH4 + Cl  CH3 + HCl
(2) CH3 + Cl2  CH3Cl + Cl
e.g. CH3-CHBr2  CH3-CBr3 (1) CH3-CHBr2 + Br  CH3 + HCl

(2) CH3 + Cl2  CH3Cl + Cl
e.g. CH3Cl  CH2Cl2 (1) ………………….…………………………………………………………………….
(2) ………………….…………………………………………………………………….
e.g. CHCl3  CCl4 (1) ………………….…………………………………………………………………….
(2) ………………….…………………………………………………………………….
e.g. CHF2-CH3  CF3-CH3 (1) ………………….…………………………………………………………………….
(2) ………………….…………………………………………………………………….
e.g. CHF2-CH3  CHF2-CH2F (1) ………………….…………………………………………………………………….
(2) ………………….…………………………………………………………………….
e.g. CH3-CH2-CF3  CH3-CHBr-CF3 (1) ………………….…………………………………………………………………….
(2) ………………….…………………………………………………………………….
TERMINATION (2 radicals  molecule)

If two free radicals collide, they will form a molecule and stop the chain reaction. Any
two free radicals involved in the mechanism could collide in this way.
Write an equation to show how each of the molecules shown could be formed by a termination step in the
reactions shown.
e.g. CH3-CH3 in CH4  CH3Cl 2 CH3  CH3-CH3
e.g. CCl3-CCl 3 in CH4  CCl4 2 CCl3  CCl3-CCl3
e.g. CH2Cl-CCl 3 in CH4  CCl4 CH2Cl + CCl3  CH2Cl-CCl 3
e.g. CF3-CH2F in CH4  CF4 ………………………………………………..……………………..…………….
e.g. butane in CH3-CH3  CH3-CH2F ………………………………………………..……………………..…………….
e.g. CBr3-CBr3 in CH4  CBr4 ………………………………………………..……………………..…………….
e.g. 1,3-dibromobutane in
CH3-CH3  CBr3-CBr3 ………………………………………………..……………………..…………….
© www.CHEMSHEETS.co.uk 4-February-2016 Chemsheets AS 1138

Chemsheets AS 1138 (Free Radical Substitution 2)

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FREE RADICAL SUBSTITUTION 2

WHAT HAPPENS H atoms on alkanes or halogenoalkanes are replaced by halogen atoms (F / Cl / Br / I)

e.g. CH4  CH3Cl CH4 + Cl2 CH3Cl + HCl

e.g. CH4  CF4 CH4 + 4F2 CF4 + 4HF

e.g. CH3-CBr3  CBr3-CBr3 CH3-CBr3 + 3Br2 CBr3-CBr3 + 3HBr

e.g. CH2Cl2  CCl4 ………………………………………………………………………………………..………….

e.g. CH3-CH3  CF3-CF3 …………………………………………………………………………………………..……….

e.g. CHF2-CH3  CBrF2-CBr3 ……………………………………………………………………………………..…………….

e.g. CF3-CH3  CF3-CCl3 ……………………………………………………………………………………..…………….

PROPAGATION (molecule + radical  molecule + radical)

For every H that is replaced, there is one pair of propagation reactions.

© www.CHEMSHEETS.co.uk 4-February-2016 Chemsheets AS 1138

e.g. CH3-CHBr2  CH3-CBr3 (1) CH3-CHBr2 + Br  CH3 + HCl

e.g. CH3Cl  CH2Cl2 (1) ………………….…………………………………………………………………….

e.g. CHCl3  CCl4 (1) ………………….…………………………………………………………………….

e.g. CHF2-CH3  CF3-CH3 (1) ………………….…………………………………………………………………….

e.g. CHF2-CH3  CHF2-CH2F (1) ………………….…………………………………………………………………….

e.g. CH3-CH2-CF3  CH3-CHBr-CF3 (1) ………………….…………………………………………………………………….

TERMINATION (2 radicals  molecule)

e.g. CH3-CH3 in CH4  CH3Cl 2 CH3  CH3-CH3

e.g. CCl3-CCl 3 in CH4  CCl4 2 CCl3  CCl3-CCl3

e.g. CH2Cl-CCl 3 in CH4  CCl4 CH2Cl + CCl3  CH2Cl-CCl 3

e.g. CF3-CH2F in CH4  CF4 ………………………………………………..……………………..…………….

e.g. butane in CH3-CH3  CH3-CH2F ………………………………………………..……………………..…………….

e.g. CBr3-CBr3 in CH4  CBr4 ………………………………………………..……………………..…………….

© www.CHEMSHEETS.co.uk 4-February-2016 Chemsheets AS 1138

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