4.2.

2 Haloalkanes
H
Naming Haloalkanes H H H
H C H
H H H
Based on original alkane, with a prefix indicating halogen atom: H C C C H
H C C C C H
Fluoro for F; Chloro for Cl; Bromo for Br; Iodo for I.
Br H H H Cl H H
Substituents are listed alphabetically
1-bromopropane 2-chloro-2-methylbutane

Classifying haloalkanes
Haloalkanes can be classified as primary, secondary or tertiary depending on
the number of carbon atoms attached to the C-X functional group.
H

H H H H H H H C H
H H H

H C C C H H C C C H H C C C C H

Br H H H Br H H Cl H H

Primary haloalkane Secondary haloalkane Tertiary haloalkane

One carbon attached to the Two carbons attached to the Three carbons attached to the
carbon atom adjoining the carbon atom adjoining the carbon atom adjoining the halogen
halogen halogen

Nucleophilic substitution reactions

Substitution: swapping a halogen atom for another atom or groups of atoms

Nucleophile: electron pair donator e.g. :OH-, :NH3, CN-

:Nu represents any nucleophile – they
The mechanism: We draw (or outline) mechanisms to always have a lone pair and act as
show in detail how a reaction proceeds electron pair donators

Nu:-
The nucleophiles
H H The carbon has a small
attack the positive H H positive charge because
carbon atom
of the electronegativity
H C C δ+ X δ- H C C Nu + X- difference between the
carbon and the halogen
H H
H H

We use curly arrows in mechanisms (with

A curly arrow will always start
two line heads) to show the movement of
from a lone pair of electrons or
two electrons
the centre of a bond

The rate of these substitution reactions depends on the strength Bond enthalpy /
of the C-X bond kJmol-1
The weaker the bond, the easier it is to break and the faster the reaction.
C-I 238
C-Br 276
The iodoalkanes are the fastest to substitute and the
fluoroalkanes are the slowest. The strength of the C-F bond is C-Cl 338
such that fluoroalkanes are very unreactive
C-F 484

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Nucleophilic substitution with aqueous hydroxide ions
Change in functional group: H H H
H H H
haloalkane  alcohol H C C C
+ KOH  H
Br
C C C OH + KBr
Reagent: potassium (or sodium) hydroxide
Conditions: In aqueous solution; Heat under reflux H H H H H H

Mechanism: Nucleophilic substitution 1-bromopropane propan-1-ol

Type of reagent: Nucleophile, OH-

The aqueous conditions

H H
needed is an important point.
δ+ δ- - If the solvent is changed to
H3C C Br H3C C OH + :Br
-
HO:
ethanol an elimination
H H reaction occurs

Comparing the rate of hydrolysis reactions

Water is a poor nucleophile but it can
Hydrolysis is defined as the splitting of a molecule ( in this react slowly with haloalkanes in a
case a haloalkane) by a reaction with water substitution reaction. Use reflux OR heat
for more than 20 minutes
CH3CH2X + H2O  CH3CH2OH + X- + H+

Aqueous silver nitrate is added to a haloalkane and the CH3CH2I + H2O  CH3CH2OH + I- + H+
halide leaving group combines with a silver ion to form a
Ag+ (aq) + I-(aq)  AgI (s) - yellow precipitate
silver halide precipitate.
The precipitate only forms when the halide ion has left the The iodoalkane forms a precipitate with
haloalkane and so the rate of formation of the precipitate can the silver nitrate first as the C-I bond is
be used to compare the reactivity of the different haloalkanes. weakest and so it hydrolyses the quickest

The quicker the precipitate is formed, the faster the AgI (s) - yellow precipitate
substitution reaction and the more reactive the haloalkane AgBr(s) – cream precipitate forms faster
The rate of these substitution reactions depends on the strength AgCl(s) – white precipitate
of the C-X bond . The weaker the bond, the easier it is to break
and the faster the reaction.

Chlorofluorocarbons (CFC’s)
Many of these uses have now been stopped
CFC’s were developed for use as aerosols, due to the toxicity of haloalkanes and also their
refrigerants, and in air-conditioning due their low detrimental effect on the ozone layer in the
reactivity, volatility and non-toxicity. atmosphere.

Legislation to ban the use of CFCs was supported by chemists and chemists
have now developed alternative chlorine-free compounds.

HFCs (Hydro fluoro carbons) e.g..

CH2FCF3 are now used for refrigerators CO2 is now used as a blowing agent for producing
and air-conditioners. These are safer expanded polymers instead of CFC’s.
as they do not contain the C-Cl bond.

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The Ozone Layer

The naturally occurring ozone (O3) layer in the upper Ozone in the lower atmosphere
atmosphere is beneficial as it filters out much of the sun’s is a pollutant and contributes
harmful UV radiation. towards the formation of smog.

Ozone is continuously being formed and broken down

in the stratosphere by the action of ultraviolet radiation. O + O2 O3
Ozone formation Ozone depletion
UV light causes an O2 molecule to split into free radicals This is the reverse of the formation reaction..
O2 + UV-light  O + O The energy is supplied by ultraviolet light
When the free radical hits another O2 molecule ozone O3 + ultraviolet light  O2 + O
forms
O + O2  O3 There is a continuous cycle of formation
and depletion of ozone
The frequency of ultra-violet light absorbed equals the rate of ozone formation = rate of ozone removal
frequency of biologically damaging ultra-violet
radiation. These reactions therefore filter out harmful So there is a constant amount of ozone in
UV and allow life to survive on earth. the atmosphere
UV light can increase risk of skin cancer and increase
crop mutation.
Destruction of Ozone Layer Chlorine radicals are formed in the upper
atmosphere when energy from ultra-violet
Radicals from CFCs, and NOx from thunderstorms or radiation causes C–Cl bonds in
aircraft, may catalyse the breakdown of ozone chlorofluorocarbons (CFCs) to break
CF2Cl2  CF2Cl  + Cl

The chlorine free radical atoms catalyse the .

Cl + O3  ClO + O2
.
decomposition of ozone due to these reactions
because they are regenerated. (They provide an
. .
ClO + O  O2 + Cl
.
alternative route with a lower activation energy) Overall equation
.
O3 + O  2 O2
They contributed to the formation of a hole in the
ozone layer.
The regenerated Cl radical means
that one Cl radical could destroy
NO + O3  NO2 + O2 many thousands of ozone molecules
.
NO2 + O  O2 + NO
Overall equation
.
O3 + O  2 O 2
HFCs (Hydro fluoro carbons) e.g..
Legislation to ban the use of CFCs was supported by CH2FCF3 are now used for refrigerators
chemists and that they have now developed and air-conditioners. These are safer as
alternative chlorine-free compounds they do not contain the C-Cl bond

CFC’s still concern us because CFCs are still entering the atmosphere from disused items and are still used
for some purposes and by some countries.

CFCs have a long lifetime in the atmosphere and it takes a long time for CFCs to reach upper atmosphere.

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