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How are halogenoalkanes made?

There are several ways by which halogenoalkanes can
be made, including:

 free radical substitution of an alkane:

CH4 + Cl2  CH3Cl + HCl

 electrophilic addition of HX or X2 to an alkene:

C2H4 + HBr  C2H5Br

C2H4 + Br2  C2H4Br2

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Free radical substitution: Cl2 + CH4

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Other products of chain reactions
If an alkane is more than two carbons in length then any of
the hydrogen atoms may be substituted, leading to a mixture
of different isomers. For example:

1-chloropropane 2-chloropropane

The mixture of products is difficult to separate, and this is

one reason why chain reactions are not a good method of
preparing halogenoalkanes.

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Further substitution in chain reactions
Some chloromethane molecules formed during free radical
substitution between methane and chlorine will undergo
further substitution to form dichloromethane. Further
substitution can occur until all hydrogens are substituted.

  

The further substituted chloroalkanes are impurities that

must be removed. The amount of these molecules can be
decreased by reducing the proportion of chlorine in the
reaction mixture.

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Chain reactions and ozone

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Free radical reactions: true or false?

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Bonding in alkenes

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Structure of alkenes summary

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Double bonds and electrophiles
The double bond of an alkene is an area of high electron
density, and therefore an area of high negative charge.

The negative charge of the double bond may be attacked

by electron-deficient species, which will accept a lone pair
of electrons.

These species have either a full positive charge or slight

positive charge on one or more of their atoms. They are
called electrophiles, meaning ‘electron loving’.

Alkenes undergo addition reactions when attacked by

electrophiles. This is called electrophilic addition.

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Electrophilic addition mechanism: 1
In the first stage of electrophilic addition,
the positive charge on the electrophile is
attracted to the electron density in the
double bond.
δ+ δ-
As the electrophile approaches the
double bond, electrons in the A–B


bond are repelled towards B.

The pi bond breaks, and A bonds to the

carbon, forming a carbocation – an ion
with a positively-charge carbon atom.
The two electrons in the A–B bond
move to B forming a B- ion.

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Electrophilic addition mechanism: 2
In the second stage of electrophilic
addition, the B- ion acts as a nucleophile
and attacks the carbocation.


The lone pair of electrons on the B- ion
are attracted towards the positively-
charged carbon in the carbocation,
causing B to bond to it.

Because both electrons in the bond that joins B- to the

carbocation ion come from B-, the bond is a co-ordinate bond.

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More on the bromine water test
A simple equation for the bromine water test with ethene is:

CH2=CH2 + Br2 + H2O  CH2BrCH2Br + H2O

However, because water is present in such a large

amount, a water molecule (which has a lone pair) adds to
one of the carbon atoms, followed by the loss of a H+ ion.

CH2=CH2 + Br2 + H2O  CH2BrCH2OH + HBr

The major product of the test is not 1,2-dibromoethane

(CH2BrCH2Br) but 2-bromoethan-1-ol (CH2BrCH2OH).

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Electrophilic addition reactions

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Addition to unsymmetrical alkenes
When an electrophile
(e.g. HBr) attacks an
alkene with three or
more carbon atoms
(e.g. propene), a mix HBr
of products is
formed. This is
because these
alkenes are
unsymmetrical.
minor product: major product:
1-bromopropane 2-bromopropane

Unequal amounts of each product are formed due to the

relative stabilities of the carbocation intermediates.

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Structure of carbocations
A chain of carbon atoms can be represented by R when
drawing organic structures. This is an alkyl group (general
formula CnH2n+1).
 Primary (1°) carbocations have
one alkyl group attached to the
positively-charged carbon.

 Secondary (2°) carbocations

have two alkyl groups attached
to the positively-charged carbon.

 Tertiary (3°) carbocations have

three alkyl groups attached to
the positively-charged carbon.

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Stability of carbocations
The stability of carbocations increases as the number of alkyl
groups on the positively-charged carbon atom increases.

primary secondary tertiary

increasing stability

The stability increases because alkyl groups contain a

greater electron density than hydrogen atoms. This
density is attracted towards, and reduces, the positive
charge on the carbon atom, which has a stabilizing effect.

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Structure of carbocations

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Electrophiles: true or false?

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Glossary

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