Module 1

2.7 Describe selected chemical reactions of halogenoalkanes

2,8 Explain the steps involved in the mechanism of selected reactions of halogenoalkanes

Halogenoalkanes
Halogenoalkanes are compounds that have an alkane hydrocarbon chain with one or more of
its hydrogen(s) replaced by halogen atoms. They can be produced from the halogenation of
alkanes and alkenes. Halogenoalkanes like alcohols can be classified as primary, secondary or
tertiary.

Primary halogenoalkanes are those with the carbon possessing the halogen atom(X) being
attached to only 1 or 0 other carbon atoms

The halogen atom is at the

end of the chain

The carbon with the halogen atom attached, has 2

hydrogen attached in a primary halogenoalkane

Secondary halogenoalkanes are those with the carbon atom attached to the halogen atom
being joined to two other carbon atoms.

The halogen atom is in

the body of the chain

The carbon with the halogen atom

attached, has 1 hydrogen attached
in a secondary halogenoalkane
Teritiary halogenoalkanes has the halogen attached to a carbon which is surrounded by 3 other
carbons
The carbon with the halogen atom
attached, has no hydrogen attached in
a teritiary halogenoalkane

The halogen atom is attached, to

a carbon with a branch in the
chain

Reactions of Halogenoalkanes

Halogenoalkanes react with nucleophiles and this reaction is called nucleophilic substitution.

The halogen atoms are more electronegative than carbon i.e. electronegativity describes the
tendency of an atom in a covalent bond to attract the bonding pair of electrons.

Hence if the halogen atoms are more electronegative than carbon, in the bond the electrons will
be closer to the halogen atoms. For example

Since the electrons are not fully transferred (closer to the halogen), the halogen atom carries a
partial negative charge and since the electrons are farther away from the carbon it carries a
partial positive charge. This end of the molecule is said to be polar.

A polar bond is a covalent bond in which there is a separation of charge between one end and
the other i.e. two different charged ends.
Halogen Electronegativity
F 4.0
Cl 3.0
Br 2.8
X = halogen atom
I 2.5
C 2.5

The nucleophilic reactions will be the focus of the lesson.

Nucleophilic Substitution of Halogenoalkanes

Substances that acts as nucleophiles are NaOH(OH-), water(H2O:), ammonia (:NH3)

The general reaction is:

The nucleophilic reaction can happen in two ways(two types of mechanism). The two ways or
two mechanism are called:

 Sn1( step by step, two stage mechanism)

 Sn2 (a single step mechanism)

The mechanism that occurs depends on class of halogenoalkane reacting.

Sn2

This is a single step mechanism where the nucleophile attaches itself to the Cd+ atom at the same
time the halogen atom leaves. At some middle stage in the reaction the nucleophile and the
halogen atom are both partially bonded to the carbon atom

This is the transition state and the intermediate formed is called an activated complex.

As shown below

Sn1

This is a two step mechanism. The first step is relatively slow which involves the breaking of
the C-X bond, by the halogen atom pulling the two electrons in the bond towards itself because
it is more electronegative than the carbon atom. The halogen atom leaves as a halide ion and is
often called the leaving group.

A positive ion is left behind called a carbocation and is the intermediate in the reaction
First step

In second step, the carbocation which is very unstable and reactive readily reacts with the
nucleophile present. This step in the reaction is fast.

Second step:

For an Sn1 mechanism it is important that the carbocation formed has to be relatively stable.

Look at the structures below:

Remember the alkyl groups release electrons (inductive effect) giving increase stability.

The teritiary halogenoalkanes which have three alkyl groups would give the most stable ion
after loss of the halogen atom. This is due to the inductive effect of the three alkyl groups
stabilizing the positive charge. This allows time for the ion to be attacked by the nucleophile
Therefore

 Teritiary halogenoalkanes react via Sn1

 Secondary halogenoalkanes react by both Sn1 and Sn2

 Primary alcohols can react only by Sn2

Hydrolysis of Halogenoalkanes

The hydrolysis of halogenoalkanes is carried by heating it under reflux with aqueous sodium
hydroxide.

For example:

Hence hydroysis of a halogenoalkane produces an alcohol. The reaction is nucleophilic

substitution and the mechanism for the reaction depends on the class or type of alcohol used.

For an Sn1 mechanism it is important that the carbocation formed has to be relatively stable.

Examples: Hydrolysis of halogenoalkanes

Hydrolysis of 1o
halogenoalkanes

Hydrolysis of 2o
halogenoalkanes
Uses

 Halogenoalkanes dissolves oil and grease because of this they are used in the dry
cleaning industry

 Chloroflourocarbons are used as aerosol propellants, refrigerants. But their use in these
areas are on the decrease because of their effects on the environment.
Chloroflourocarbons are unreactive but they are responsible for some depletion of the
ozone layer. When they reach the upper atmosphere and undergo a photochemical
reaction with ozone, converting it to oxygen

 The halogenoalkane fluothane( 1 bromo-1 chloro-2,2,2,-trifluoroethane) is used as an

anaesthetic gas in over 500 million operations.

 Fully halogenated alkanes are non-flammable, volatile and dense and hence are used in
fire extinguishers. CCl4 are now replaced by safer gases CBr2ClF called ‘BCF’.

 PVC s is a polymer and its monomer unit is a halogenoalkane. PVC is one of the most
widely used plastics and one of the most versatile.